JP2000292970A - Electrostatic charge image developing nonmagnetic toner, and electrophotographic developer containing this toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner capable of not reducing image density and not causing a fog and stably obtaining images even in environments of a high temperature and humidity and a low temperature and low humidity. SOLUTION: This nonmagnetic toner contains a mother toner containing a binder resin and a colorant, and fine inorganic particles treated with a silicone compound represented by the formula together with a silane coupling agent and having a BET specific surface area of 10-100 m2 measured by the nitrogen adsorption method. In the formula, each of R1-R6 is a 1-3C alkoxy group and (n) is an integer of 2-6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to an electrostatic toner used for visualizing an electrostatic image such as electrophotography.

[0002]

2. Description of the Related Art An electrophotographic process is a process in which an electrostatic latent image is formed on a photoreceptor using a photoconductive phenomenon, and toner is attached to the electrostatic latent image by electrostatic force to form a visible image. And a method of directly forming a toner image on a photosensitive paper (CPC) and a method of transferring a toner image formed on a photoconductor to recording paper (PPC). Electrophotographic developing methods include a dry developing method and a wet developing method. The main dry developing methods are a cascade developing method (U.S. Pat. No. 2,221,776) and a two-component magnetic brush developing method (U.S. Pat. No. 2,874).
063 specification), a one-component insulating toner developing method (Japanese Patent Publication No. Sho 4)
1-9475), a one-component conductive toner developing method (US Pat. No. 3,909,258), and the like. The cascade developing method is a method in which a developer is dropped on a photoreceptor by using gravity to attach toner, but it is hardly used at present. Currently, two-component magnetic brush development and one-component insulated toner development are the mainstream development methods.

[0003] The electrophotographic developing method by the developing method includes a positive developing method in which a toner having a charge having a polarity opposite to that of a latent image is adhered, and a method in which a charge on the photosensitive member is removed from the photosensitive member. There are two types of reversal development, in which a toner charged to the same polarity as the toner is attached. The normal development method is mainly used in plain paper copying machines, but the reversal development method is used in printers and digital copying machines. For example, in a laser beam printer, a semiconductor laser (emission wavelength 76
The laser beam emitted from the light source is scanned on the surface of the photoreceptor by a polygon mirror to remove the electric charges in the image area and form an electrostatic latent image. In this method, since the light source is very small, a high resolution can be obtained, and the demand has been growing along with office automation.

[0004] The two-component magnetic brush developing method uses a mixture of toner particles and carrier particles in a developer, and conveys and develops the developer by a developing roller on a magnet roller. It has the advantage that conversion is possible. However, since a mechanism for keeping the ratio of the toner and the carrier constant or a mechanism for stirring the developer is required, the apparatus becomes large and complicated, and the charging ability of the carrier is reduced due to the adhesion of the toner to the carrier surface. For,
If used for a long time, the carrier particles will be deteriorated and the developer needs to be replaced. Further, in a low-temperature and low-humidity environment, a so-called charge-up phenomenon occurs in which the toner has an unnecessary charge.

On the other hand, in the one-component insulating toner developing method, since no carrier particles are used, a mechanism for controlling and stirring the toner concentration is not required, and the apparatus can be downsized. In addition, there is an advantage that no waste such as an unnecessary carrier is generated. A typical one-component insulated toner developing method includes a BMT method using frictional charging between toners,
A jumping development method and the like are known in which a sleeve or a blade is frictionally charged, or a blade of polyurethane rubber or the like is pressed against the sleeve, and the blade and the toner are frictionally charged when the sleeve is rotated to fly magnetic toner. Further, the one-component jumping developing method includes a magnetic one-component jumping developing method in which the toner has a magnetic force and a non-magnetic one-component developing method in which the toner has no magnetic force.

Among these, the magnetic one-component jumping development method is a non-contact development as a development method, and applies a bias voltage between a gap provided between a toner layer and a photoconductor to apply static toner to the photoconductor. This is a development method in which toner flies onto the photoreceptor with a balance between the electro-attraction force and the centrifugal force due to the rotation of the sleeve and the magnetic attraction force due to the magnet in the sleeve to perform development. It is characterized in that the stains on the part are small and development can be performed at high speed. However, in this method, it is necessary to include a so-called magnetic powder in order to give the toner a magnetic force.
Many of these magnetic powders are colored and are not suitable for color development.

On the other hand, the non-magnetic one-component jumping developing method is a non-contact developing method similar to the magnetic one-component jumping developing method, and does not require magnetic powder. is there. However, since it does not have a magnetic attraction to the sleeve, dirt and ground dirt due to scattering inside the machine are likely to occur. Further, there is a problem that the concentration is reduced if the scattering in the machine is prevented too much.

In the case of a one-component developing method, since a carrier having the ability to control the charge of the toner is not used, control of the charge ability of the toner itself is very important. In particular,
The jumping development method in a high-temperature and high-humidity environment has disadvantages in that the image density is reduced and scattering in the machine easily occurs as compared with other environments.

The toner to be applied to each of the one-component and two-component development methods is prepared by dispersing a dye, a pigment and the like in a binder resin, melt-kneading with a twin-screw extruder or the like, and then pulverizing and classifying to 1 to 30 μm. That is used. Dry colloidal silica or the like is used as an external additive of the toner, and greatly contributes to improvement of fluidity. By improving the fluidity, the replenishment of the toner is improved, and the developer is smoothly supplied onto the developer carrier, so that the image quality such as image uniformity is improved. In addition, an external additive having an effect of preventing filming of the toner and refreshing the drum surface is used. Examples of these substances include metal oxides, carbides, nitrides, and the like, and organic resin fine particles.

In order to obtain good images in all environments, it is necessary to provide a stable charge to the toner. As one of the methods, a metal oxide such as aluminum oxide or zinc oxide serving as a charge assistant is added to the toner,
A method of compensating for the charged charge is generally adopted. But,
With conventional metal oxides, it has been difficult to obtain good images in any environment.

In general, the toner contains a so-called charge control agent. As positively charged charge control agents, nigrosine dyes, triphenylmethane compounds, metal salts of higher fatty acids or quaternary ammonium salt compounds are well known. As a negatively charged charge control agent,
Metal complexes of monoazo dyes, metal complexes of alkylsalicylic acid, metal salts and quaternary ammonium salt compounds are well known. These charge control agents impart charge to the toner, but it has been difficult to secure sufficient charge stability using only these charge control agents.

[0012]

The objects of the present invention are: 1. The image density does not decrease and does not cause fogging. An object of the present invention is to provide an electrostatic image developing toner capable of obtaining a stable image even in a high-temperature and high-humidity environment and a low-temperature and low-humidity environment.

[0013]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, by adding specific inorganic fine powder and silica fine powder to the base toner, the above-mentioned problems have been solved. We found that we could solve it. That is, the first
The invention relates to a BE by a nitrogen adsorption method, which is treated with a base toner containing a binder resin and a colorant, and a silicone compound represented by the following general formula 1 and a silane coupling agent.
A non-magnetic toner for developing electrostatic images, characterized by containing treated inorganic fine particles having a T specific surface area of 20 to 100 m ² / g.

[0014]

Embedded image

According to a second aspect of the present invention, the treated inorganic fine particles contain 100 parts by weight of alumina and 5 to 40 parts by weight of a silicone compound and
Treated with 10-40 parts by weight of silane coupling agent,
The non-magnetic toner for developing an electrostatic image according to the first invention, wherein the degree of hydrophobicity of the treated toner by a methanol titration method is 40 to 80%.

A third aspect of the present invention is the non-magnetic toner for developing an electrostatic image according to the first or second aspect, wherein the non-magnetic toner is negatively chargeable.

According to a fourth aspect, there is provided an electrophotographic developer comprising the nonmagnetic toner for developing an electrostatic image according to any one of the first to third aspects, and a carrier.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples of the binder resin used in the present invention include polystyrene, poly-p-chlorostyrene, polyvinyltoluene, styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer and the like. Homopolymers of styrene and its substituted products and copolymers thereof; styrene and acrylate such as styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-n-butyl acrylate copolymer A styrene-methyl methacrylate copolymer,
Copolymers of styrene and methacrylic ester such as styrene-ethyl methacrylate copolymer and styrene-n-butyl methacrylate copolymer; multi-component copolymers of styrene with acrylate and methacrylate; other styrene-acrylonitrile Styrene such as copolymer, styrene-vinyl methyl ether copolymer, styrene-butadiene copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile indene copolymer, styrene-maleic acid ester copolymer, etc. Styrene-based copolymers of styrene and other vinyl monomers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate,
Polyester, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid, polyvinyl acetate, polyethylene, polypropylene, rosin, modified rosin, tempel resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, paraffin Wax, carnauba wax and the like can be used alone or in combination.

The colorants contained in the present invention include, for example, the following dyes or pigments. Examples of the dye include C.I. I. Direct red 1;
I. Direct red 4; I. Acid Red 1;
C. I. Basic Red 1; I. Modant Red 30; I. Direct blue 1; I. Direct blue 2; I. Acid Blue 9; I. Acid blue 15; I. Basic blue 3;
I. Basic blue 5; I. Modant Blue 7
Etc. As the pigment, naphthol yellow S; permanent yellow NCG; permanent orange GT
R; pyrazolone orange; benzidine orange G; permanent red 4R; watching red calcium salt; brilliant carmine 3B; fast violet B; methyl violet lake; phthalocyanine blue;
C and the like. Preferably, C.I. I. Pigment Yellow 17; I. Pigment Yellow 15; I. Pigment Yellow 13; I. Pigment Yellow 1
2; I. Pigment Yellow 180; C.I. I. Pigment Yellow 93; I. Pigment Red 5;
C. I. Pigment Red 3; I. Pigment Red 2; I. Pigment Red 6; I. Pigment Red 7; I. Pigment Blue 15; I.
Pigment Blue 16 or dyes and pigments having a phthalocyanine skeleton. In the case of a black toner, it is preferable to use carbon black.

In the present invention, a conventionally known charge control agent can be used. Examples of the positive charge control agent include a nigrosine dye; a triphenylmethane dye and a laked pigment thereof; and a quaternary ammonium salt. Further, the toner of the present invention is preferably negatively chargeable. As the negatively chargeable charge control agent, metal-containing monoazo dyes; metal complexes or metal salts of alkylsalicylic acid; alkylsalicylic acid-containing compounds; calix-n- Allene compound; a polymer in which a part or all of the counter anion of diallylalkylammonium chloride is substituted.

The base toner in the present invention can be obtained according to a conventional method. For example, the binder resin, the colorant, and, if necessary, the charge control agent are mixed at a desired ratio, melted and kneaded by a kneader, an extruder, or the like, cooled, and then pulverized by means such as a jet mill. Then, the obtained pulverized product can be obtained by classifying it with an air classifier.

Next, the treated inorganic fine particles which are external additives used in the present invention will be described. The treated inorganic fine particles used in the present invention are obtained by treating the surface of the inorganic fine particles with a silicone compound represented by the following general formula 1 and a silane coupling agent.

[0023]

Embedded image

Although it has been known to treat the surface of inorganic fine powder with silicone oil or silicone varnish in order to make the surface of the inorganic fine particle hydrophobic, it is almost impossible to control the chargeability of the toner by such treatment. Did not.
In the present invention, the function of controlling the chargeability of the toner, particularly the negative function, is achieved by using a specific silicone compound in which O is always interposed between Si and C as shown in the general formula 1 as the treatment agent. The charging function has been dramatically improved.
The effect is particularly remarkable when all of R _{1 to} R ₆ are methoxy groups having 1 carbon atom.

Generally, silica fine particles have a considerably large negative (about
(Approximately -200 to 500 μC / g). On the other hand, the chargeability of most of the inorganic fine particles other than the silica fine particles is close to neutral (about ± 10 μC / g). For this reason, when inorganic fine particles other than silica fine particles are used for the negatively chargeable toner, the charge amount is reduced, and problems such as generation of background stain and scattering occur. Conversely, when the silica fine particles are used for the negatively chargeable toner, background contamination and scattering are suppressed, but a problem of charge-up occurs. On the other hand, the silicone compound represented by the general formula 1 has a large amount of Si—O bonds in its skeleton as described above, and its surface has a pseudo-silica fine particle-like structure.
It is considered that when added to the base toner, the whole toner is likely to be negatively charged.

In the present invention, examples of the inorganic particles serving as the base material of the treated inorganic particles include alumina, titanium oxide, and zinc oxide, and alumina having a low specific gravity is particularly preferable. Also,
In the present invention, 100 parts by weight of inorganic particles serving as a base material is
It is preferable to treat with up to 40 parts by weight of the silicone compound represented by the aforementioned general formula 1. If the amount is less than 5 parts by weight, the charge control function tends to decrease. If the amount is more than 40 parts by weight, the effect of increasing the amount of addition is small, and conversely the cost increases, which is not preferable.

Although these silicone compounds represented by the general formula 1 have an effect as a charge control aid, they have no effect as a surface hydrophobizing agent as is apparent from their structures. For this reason, for example, in an environment such as high temperature and high humidity, the performance is rapidly reduced. In order to solve this problem, the external additive used in the present invention is not limited to the silicone compound represented by the general formula 1, but it is necessary to further hydrophobize the surface with a silane coupling agent. The silane coupling agent used for the treatment in the present invention is represented by, for example, the following general formula 2. (General Formula 2) R _m SiY _n (wherein R represents an alkoxy group or a chlorine atom, Y represents a hydrocarbon group including an alkyl group, a vinyl group, a glycidoxy group, and a methacryl group, and m and n are 1 to 3) Indicates an integer.
However, m + n = 4. Examples of the compound represented by the general formula 2 include dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, decyltrimethoxysilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethylchlorosilane, and vinyltriethoxy. Examples thereof include silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, and dimethylvinylchlorosilane.

It is preferable to treat 100 parts by weight of the substrate with 10 to 40 parts by weight of the silane coupling agent. Ten
If the amount is less than the weight part, the hydrophobicity tends to be insufficient, and
If the amount is more than the weight part, aggregation is likely to occur.

The inorganic fine particles after the treatment preferably have a degree of hydrophobicity by methanol titration of from 40 to 80%, more preferably from 45 to 75%. If the degree of hydrophobicity exceeds 80%, the surface of the inorganic fine particles is covered with the hydrophobizing agent, so that the effect as the charge control aid, which is the object of the present invention, is unpreferably reduced. On the other hand, if it is less than 40%, the effect of the hydrophobizing treatment is small, which is not preferable.

The treated inorganic fine particles used in the present invention are BE
The above-mentioned treatment is applied to a substrate having a T specific surface area of about 50 to 200 m ² / g, and it is important that the BET specific surface area after the surface treatment is 20 to 100 m ² / g. is there. If the specific surface area is less than 20 m ² / g, the agglomeration increases sharply. On the other hand, if it exceeds 100 m ² / g, the surface treatment is not performed uniformly.

The toner of the present invention contains the above-mentioned base toner and treated inorganic fine particles, and it is preferable to add 0.05 to 2.0 parts by weight of the treated inorganic fine particles to 100 parts by weight of the toner. If the amount is less than 0.05 part by weight, the effect cannot be sufficiently obtained. If the amount is more than 2.0 parts by weight, the effect of the added amount is small, and the cost is undesirably high.

Further, in the present invention, other additives can be used in combination as long as the effects of the present invention are not impaired.
Examples of usable additives include fine particles having a fluidity improving effect such as silica fine powder and titanium oxide fine powder, higher fatty acid salts such as zinc stearate and magnesium stearate, fine particles of polymethyl methacrylate resin, and fine particles of polyvinylidene fluoride resin. Organic resin fine particles such as WC, SiC, T
It is preferable to use a non-oxide type powder such as iC or SiN or an oxide type powder such as titanium oxide, strontium titanate, calcium titanate, silicon oxide, aluminosilicate, magnetite, ferrite, etc., alone or as a mixture. .

The toner of the present invention can be used as a one-component developer or as a two-component developer used in combination with various carriers. As a carrier used in the case of a two-component developer, any conventionally known carriers can be used.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

EXAMPLES Preparation Examples of Treated Inorganic Fine Particles 1 to 6 Treated inorganic fine particles were produced by the following methods. About 500 g of alumina having a BET specific surface area of about 100 m ² / g are introduced into a dispersion in which water and methanol have a ratio of 1: 1. After stirring with a disperser for about 10 minutes, a predetermined amount of methyl silicate solution (20% by weight solution) to secure the treatment amount shown in Table 1.
And surface treatment is performed. Thereafter, a predetermined amount of a decylmethoxysilane solution (20% by weight solution) is introduced to secure the treatment amount shown in Table 1, and surface treatment is performed. Next, drying under reduced pressure is performed to remove water and alcohol. The obtained powder was pulverized with a pulverizer to obtain surface-treated inorganic fine particles.
Table 1 shows a list of the obtained surface-treated inorganic fine powder.

[0035]

[Table 1]

[0036]

Example 1 A toner was manufactured as follows. 97 parts by weight of polyester resin Phthalocyanine pigment Pigment Blue 15-3 (manufactured by Toyo Ink Mfg. Co., Ltd.) 3 parts by weight The above materials are mixed by a mixer having high-speed rotating blades (Henschel mixer manufactured by Mitsui Mining Co., Ltd.) and then barreled About temperature
The mixture was kneaded with a twin-screw kneading extruder set at 120 ° C. The obtained kneaded material is cooled and coarsely pulverized with a hammer mill to a particle size of about 3 mm or less, and then finely crushed using a supersonic jet crusher (IDS-2 type manufactured by Nippon Pneumatic) having a coarse powder classification function. The powder was pulverized, and the fine powder portion of the obtained fine powder was removed with an airflow classifier (DS-2, manufactured by Nippon Pneumatic) to obtain a base toner having a weight average particle size of about 8 μm. To 100 parts by weight of the obtained base toner, 0.5 parts by weight of the inorganic fine particles of Production Example 1 were added, and dry-mixed by a mixer having a high-speed rotating blade (Henschel mixer manufactured by Mitsui Mining Co., Ltd.), and then a mesh of 150 mesh was set. Aggregates were removed with a vibrating sieve to obtain a toner.

Next, a ferrite carrier 100 having an average particle size of 60 μm coated with a styrene-acrylic copolymer resin was used.
6 parts by weight of the toner was added to the parts by weight, and the mixture was mixed by a ball mill for 45 minutes to obtain a developer.

The obtained developer was set in a commercially available copying machine (CLC-500 manufactured by Canon Inc.), and the temperature and the humidity were low (10 ° C./25%).
R. H. When an image was formed under the environment of (3), a copy without background contamination was obtained at an image density of 1.53. When a 10,000-sheet printing test was performed, the image density of the 10,000th copy was 1.51 which was about the same as the initial copy, and high quality images were continuously obtained without the occurrence of background contamination. Was done.

Furthermore, high temperature and high humidity (30 ° C./80% R.F.)
H. In the same manner, in (2), image formation was performed. As a result, the image density of the copy was sufficiently obtained as 1.52, and no soiling occurred. Further, a printing durability test of 10,000 sheets was performed under the same environment, and the image density of the 10,000th copy was 1.54, which was almost the same as that of the initial copy, and there was no background stain. Further, when the inside of the apparatus was confirmed, no high-quality images were obtained continuously without any dirt due to scattering.

[0040]

Example 2 A toner was manufactured as follows. Styrene-acrylic copolymer 87 parts by weight Carbon black MA-100 (manufactured by Mitsubishi Chemical Corporation) 5 parts by weight Spiron Black TRH (manufactured by Hodogaya Chemical Company) 5 parts by weight Viscol 660-P (manufactured by Sanyo Chemical) 3 parts by weight After mixing the materials with a mixer having a high-speed rotor (Henschel mixer manufactured by Mitsui Mining Co., Ltd.), the barrel temperature was reduced to about
The mixture was kneaded with a twin-screw kneading extruder set at 140 ° C. The obtained kneaded material is cooled and coarsely pulverized with a hammer mill to a particle size of about 3 mm or less, and then finely crushed using a supersonic jet crusher (IDS-2 type manufactured by Nippon Pneumatic) having a coarse powder classification function. The powder was pulverized, and the fine powder portion of the obtained fine powder was removed with an airflow classifier (DS-2, manufactured by Nippon Pneumatic) to obtain a base toner having a weight average particle diameter of about 10 μm. To 100 parts by weight of the obtained base toner, 0.5 parts by weight of the inorganic fine particles of Production Example 2, 0.3 parts by weight of polyvinylidene fluoride resin particles and 0.5 part by weight of polymethyl methacrylate resin fine particles were added, and a mixing machine having a high-speed rotating blade (Mitsui Mining Co., Ltd.) After dry-mixing with a Henschel mixer (manufactured by Henschel Co., Ltd.), aggregates were removed with a vibrating sieve equipped with a mesh having openings of 150 mesh to obtain a toner.

Next, 100 parts by weight of a ferrite carrier coated with an acrylic melamine resin having an average particle diameter of about 130 μm and 10 parts by weight of a test toner were mixed for 30 minutes by a ball mill to prepare a developer.

The obtained developer was set in a commercially available copying machine (FP-2230 manufactured by Matsushita Electric Industrial Co., Ltd.), and was set to a low temperature and a low humidity (10 ° C./25%).
R. H. When an image was taken out under the environment of (2), the image density of the copy was 1.35, and no soiling occurred.
When a 10,000-sheet printing test was performed, the image density of the 10,000th copy was 1.29, which was almost the same as the initial value. Was done.

Further, at a high temperature and a high humidity (30 ° C./80% R.C.).
H. In the same manner, in (2), image output was performed. As a result, the image density was 1.37, and there was no background stain. Also,
A 10,000-sheet press life test was carried out under the same environment, and the image density of the 10,000-th copy was 1.37, the same as the initial copy, and there was no background stain. Further, when the inside of the apparatus was confirmed, no high-quality images were obtained continuously without any dirt due to scattering.

[0044]

Example 3 Polyester resin: Same as Example 1 except that 97 parts by weight was 93 parts by weight and carbon black MA-100 (manufactured by Mitsubishi Chemical Corporation) was 7 parts by weight instead of 3 parts by weight of phthalocyanine pigment. Thus, a base toner, a toner and a developer were obtained.

The obtained developer was set in a commercially available copying machine (CLN-730, manufactured by Canon Inc.), and the temperature and the humidity were low (10 ° C./25%).
R. H. When an image was taken out in the environment of (1), the image density of the copy was 1.45, and there was no background stain.
When a 10,000-sheet printing test was performed, the image density of the 10,000th copy was 1.44, which was almost the same as the initial value. Was done.

Further, at a high temperature and a high humidity (30 ° C./80% R.C.).
H. In the same manner as in (1), when an image was formed, the image density of the copy was 1.42, and there was no background stain. When a 10,000-sheet press life test was conducted under the same environment, the image density of the 10,000th copy was about the same as the initial one.
45, and there was no occurrence of soiling. Further, when the inside of the apparatus was confirmed, no high-quality images were obtained continuously without any dirt due to scattering.

Example 4 A mother toner, a toner and a developer were obtained in the same manner as in Example 3 except that the inorganic fine particles of Production Example 6 were used instead of the inorganic fine particles of Production Example 3.

The obtained developer was set in a commercially available copying machine (CLC-730 manufactured by Canon Inc.), and the temperature and the humidity were low (10 ° C./25%).
R. H. When an image was taken out under the environment of (2), the image density of the copy was 1.43, and there was no background stain.
When a 10,000-sheet printing test was performed, the image density of the 10,000th copy was 1.42, which was almost the same as the initial value. Was done.

Furthermore, high temperature and high humidity (30 ° C./80% R.F.)
H. In the same manner, in (2), image output was performed. The image density of the copy was 1.45, and no background staining occurred. When a 10,000-sheet press life test was conducted under the same environment, the image density of the 10,000th copy was about the same as the initial one.
43, and no soiling occurred. Further, when the inside of the apparatus was confirmed, no high-quality images were obtained continuously without any dirt due to scattering.

[0050]

Comparative Example 1 Production Example 4 in place of the inorganic fine particles of Production Example 1
A toner and a developer were obtained in the same manner as in Example 1, except that the treated inorganic fine particles were used. The obtained developer was set in a commercially available copying machine (CLN-500 manufactured by Canon Inc.),
0 ° C / 25% R. H. When an image was taken out under the environment of (2), the image density of the copy was 1.21 and there was no background stain. However, when the printing durability test was performed on 10,000 sheets, only a copy having an image density of 1.18 was obtained on the 10,000th sheet.

Further, at a high temperature and a high humidity (30 ° C./85% R.C.).
H. In the same manner, in the environment described in (1), when an image was displayed, the image density was 1.35, and no soiling occurred. In addition, a printing durability test of 10,000 sheets was performed under the same environment, and the image density of the 10,000th sheet was 1.42.
Ground dirt has occurred. In addition, when the inside of the aircraft was checked, it was found that the inside of the aircraft was scattered by scattering.

[0052]

Comparative Example 2 A toner and a developer were obtained in the same manner as in Example 2, except that the inorganic fine particles of Production Example 5 were used instead of the inorganic fine particles of Production Example 2. The obtained developer was set in a commercially available copying machine (FP-2230 manufactured by Matsushita Electric Industrial Co., Ltd.), and an image was formed in a low-temperature and low-humidity environment (10 ° C./25% RH). The image density was inadequate at 1.21, but no background staining occurred. When a 10,000-sheet printing test was carried out, the image density at the 10,000th sheet was 1.24, which is the same as the initial one, which was insufficient, but no background smearing occurred.

Furthermore, high temperature and high humidity (30 ° C./80% R.F.)
H. In the same manner as in (1), when an image was formed, a copy having an image density of 1.30 was obtained, but the background was stained.
In the same environment, a 10,000-sheet printing test was performed.
However, soiling occurred. When the inside of the machine was checked, there was no dirt due to scattering.

[0054]

Example 5 Polyester resin: 97 parts by weight was 94 parts by weight, and quinacridone pigment Ket Red 309 (Dainippon Ink Chemical Industry Co., Ltd.) was used instead of 3 parts by weight of a phthalocyanine pigment.
) Was obtained in the same manner as in Example 1 except that 6 parts by weight were used.

The obtained toner was set in a commercially available laser beam printer (LBP-2030 manufactured by Canon Inc.) and subjected to an image test in a low-temperature and low-humidity environment (10 ° C./25% RH). In the solid part of the test pattern, the image density was sufficiently obtained as 1.40, and there was no occurrence of background contamination. When an image test was conducted in a high-temperature and high-humidity environment (30 ° C./80% RH), the image density was sufficiently obtained as 1.38 in the solid portion of the built-in test pattern. There was no outbreak. Furthermore, room temperature and normal humidity (23 ° C / 50
% R. H. A printing durability test was performed on 2,000 sheets under the environment of (2). As a result, even at the 2,000th sheet mark, an image density of 1.41 was obtained in the solid portion of the built-in test pattern, and no background stain was generated. In addition, when the inside of the apparatus was checked, there was no dirt due to scattering, and high quality images were continuously obtained.

[0056]

Example 6 A commercially available laser beam printer (LP-9200 manufactured by Seiko Epson Corporation) was used for the toner obtained in Example 2.
And the image test was conducted in a low-temperature and low-humidity environment (10 ° C./25% RH). Did not. In addition, high temperature and high humidity (30 ° C./80% R.F.
H. The same image test was performed under the environment of (3), and the image density was 1.33 in the solid part of the built-in test pattern.
Was sufficiently obtained, and there was no occurrence of soiling. Further, under the environment of normal temperature and normal humidity (23 ° C./50% RH),
As a result of the 2,000-sheet printing test,
An image density of 1.34 was obtained at the solid portion of the built-in test pattern, and no background contamination occurred. In addition, when the inside of the apparatus was checked, there was no dirt due to scattering, and high quality images were continuously obtained.

[0057]

Example 7 A toner was manufactured as follows. 86 parts by weight of polyester resin Phthalocyanine pigment Pigment Blue 15-3 (manufactured by Toyo Ink Mfg. Co., Ltd.) 7 parts by weight Bontron E-82 (manufactured by Orient Chemical) 5 parts by weight Viscol TP-32 (manufactured by Sanyo Chemical) 2 parts by weight Using the above materials, a weight average particle size of about
An 8 μm parent toner was obtained. 0.5 parts by weight of the inorganic fine particles of Production Example 3 were added to 100 parts by weight of the obtained base toner, and a toner was obtained in the same manner as in Example 1 below.

The obtained toner was set in a commercially available laser beam printer (LBP-2030 manufactured by Canon Inc.), and an image test was performed in a low temperature and low humidity (10 ° C./25% RH) environment. A sufficient image density of 1.38 was obtained in the solid portion of the built-in test pattern, and there was no background stain.
When an image test was performed in the same manner at a high temperature and a high humidity (30 ° C./80% RH), a sufficient image density of 1.35 was obtained in the solid portion of the built-in test pattern, and no background contamination occurred. Was. Furthermore, room temperature and normal humidity (23 ° C / 50%
R. H. A printing durability test was performed on 2,000 sheets under the environment of (2). As a result, even on the 2,000-th sheet, an image density of 1.41 was obtained in the solid portion of the built-in test pattern, and there was no background stain. In addition, when the inside of the apparatus was checked, there was no dirt due to scattering, and high quality images were continuously obtained.

[0059]

Example 8 Production Example 6 was used instead of the inorganic fine particles of Production Example 3.
A toner was obtained in the same manner as in Example 7, except that the inorganic fine particles were used. The obtained toner was set in a commercially available laser beam printer (LBP-2030 manufactured by Canon Inc.), and an image test was performed in a low-temperature and low-humidity (10 ° C./25% RH) environment. The image density is
It was sufficiently obtained as 1.25, and there was no occurrence of soiling. Also,
When an image test was conducted in the same manner at high temperature and high humidity (30 ° C./80% RH), a sufficient image density of 1.18 was obtained at the solid portion of the built-in test pattern, and no background dirt was generated. Further, a printing durability test was performed on 2,000 sheets under an environment of normal temperature and normal humidity (23 ° C./50% RH). As a result, on the 2,000th sheet, the image density was 1.12 in the solid portion of the built-in test pattern.
Although it was a little low and insufficient, there was no occurrence of soiling. When the inside of the aircraft was checked, some dirt due to scattering was observed.

[0060]

Comparative Example 3 Production Example 4 in place of the inorganic fine particles of Production Example 1
A toner was obtained in the same manner as in Example 5, except that the inorganic fine particles were used. The obtained toner was set in a commercially available laser beam printer (LBP-2030 manufactured by Canon Inc.), and an image test was performed in a low-temperature and low-humidity (10 ° C./25% RH) environment. The image density is
0.91 was not sufficiently obtained, but no background dirt was generated. An image test was also performed at high temperature and high humidity (30 ° C./80% RH). As a result, the image density was 0.85 at the solid portion of the built-in test pattern, and no background stain was generated. Further, room temperature and normal humidity (23 ° C / 50% RH)
2,000-sheet printing test was conducted under the following environment.
On the 1000th sheet, the image density is
0.88 was not obtained enough, and soiling occurred. When the inside of the machine was checked, it was found that the inside of the machine was stained by scattering.

[0061]

Comparative Example 4 Production Example 5 in place of the inorganic fine particles of Production Example 2
A toner was obtained in the same manner as in Example 6, except that the inorganic fine particles were used. The obtained toner is set in a commercially available laser beam printer (LP-9200 manufactured by Seiko Epson Corporation),
When an image test was conducted in a low-temperature and low-humidity environment (10 ° C./25% RH), the image density was insufficient at 1.19 at the solid portion of the built-in test pattern, but no background dirt was generated. When an image test was similarly performed at high temperature and high humidity (30 ° C./80% RH), a sufficient image density of 1.28 was obtained in the solid portion of the built-in test pattern.
Ground dirt has occurred. Furthermore, room temperature and normal humidity (23 ° C / 50%
R. H) A 2,000-sheet printing test was performed in an environment. On the 2,000-th sheet, an image density of 1.30 was obtained in the solid portion of the built-in test pattern, but background staining occurred. Also, when the inside of the aircraft was checked, there was no dirt due to scattering.

[0062]

According to the present invention, by adding, as an external additive, treated inorganic fine particles obtained by treating a base toner with a specific silicone compound and a silane coupling agent, high image quality can be obtained even when copying or printing is repeated. The density can be maintained, fogging does not occur, and a copy having stable image quality can be obtained even in an environment of high temperature and high humidity and an environment of low temperature and low humidity.

Claims (4)

[Claims] 1. A nitrogen adsorption method which is treated with a base toner containing a binder resin and a colorant, and a silicone compound represented by the following general formula 1 and a silane coupling agent.
A non-magnetic toner for developing an electrostatic image, comprising treated inorganic fine particles having a BET specific surface area of 20 to 100 m ² / g. Embedded image 2. The treated inorganic fine particles are obtained by treating 100 parts by weight of alumina with 5 to 40 parts by weight of a silicone compound and 10 to 40 parts by weight of a silane coupling agent. 2. The non-magnetic toner according to claim 1, wherein said toner has a degree of 40 to 80%. 3. The non-magnetic toner according to claim 1, wherein the non-magnetic toner is negatively chargeable. 4. A developer for electrophotography, comprising the non-magnetic toner for developing an electrostatic image according to claim 1, and a carrier.