JP2001013718A - Toner and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner excellent in image quality and the stability of image density even after long-term use and not causing fusion to an electrifying member, a photoreceptor, etc. SOLUTION: This toner has toner particles containing at least a bonding resin and a colorant and fine powders added to the toner particles. The toner has an average circularity of 0.950-0.995 measured with a flow type particle image measuring device, and in the particle size distribution of equivalent circular diameter, the toner has a maximum value X at 3-9 μm equivalent circular diameter and a maximum value Y at 0.6-2 μm equivalent circular diameter. The toner includes 8-30 number % particles having 0.60 to <2.00 μm equivalent circular diameter based on the total number and contains a spherical fine resin powder (A) having 0.05-2.0 μm number average particle diameter, a shape factor SF-1 of 100-150, a shape factor SF-2 of 100-200 and a nitrogen atom-containing high molecular compound and an inorganic fine powder (B) having 1-30 nm number average particle diameter of primary particles on the surfaces of the toner particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image used in an electrostatic copying machine, a laser printer, and the like, and to an image forming method using the toner. .

[0002]

2. Description of the Related Art Electrophotography is disclosed in U.S. Pat. No. 2,297,6.
Numerous methods are known, as described in U.S. Pat. No. 91, in which an electrical latent image is generally formed on a photoreceptor by various means using a photoconductive material, Is developed using a toner, a toner image is transferred to a recording material such as paper as necessary, and then fixed by heating, pressure, solvent vapor, or the like to obtain a copy. Conventionally, various methods have been proposed as a method of developing using a toner or a method of fixing a toner image, and a method suitable for each image forming method is adopted. In recent years, with the spread of copiers and printers, further speed-up, downsizing, long life, and high image quality have been demanded.

[0003] Further, as the number of users expands, the cost of copying machines and printers and the ease of maintenance are also required, and as a result, the number of parts and the simplification of the machine configuration of the machine body are also required.

[0004] As a result, the technical requirements for consuming members such as toner and drum are increasing year by year.

In the non-magnetic one-component developing method, not only is the toner body excellent in low-temperature fixability than a magnetic toner,
Since it has the feature that the constitution of the consumed developer and the developing device is simple, it is particularly excellent in downsizing and free maintenance.

On the other hand, it is known that by defining the average particle diameter and the sphericity of the toner particles, a long life of the developer, a high definition of the image quality, a high reproducibility, etc. can be achieved.
A method that combines these technologies has been used,
In the prior art, there has been a problem particularly when the device is used for a long period of time under low-temperature and low-humidity conditions.

That is, in the non-magnetic one-component developing device, the toner is charged by using a toner carrier and a toner applying means such as an elastic blade for applying the toner to the toner carrier. In particular, the ability of the toner coating means to regulate the thickness of the developer layer becomes non-uniform immediately after the start of the developing device, resulting in a variation in the amount of triboelectric charge of the toner, which is a factor of image quality deterioration. Had become.

Specifically, "fog" in which a part of the toner adheres to the non-image area; shading on the streaks on the fixed recording paper despite the formation of a uniform latent image on the photosensitive drum "Image streaks" appearing in the image; "deterioration of image density stability", which causes a difference in image density between immediately after the start of the developing device and when the developing device is used continuously for a long time;

The reason why the ability of regulating the thickness of the developer layer becomes non-uniform when used under low temperature or low humidity conditions is not clear for the detailed reason. However, thermal expansion of the toner applying means and the toner carrier is not clear. As a result, a change occurs in the regulation pressure or the like, resulting in an uneven developer layer thickness, or a substance contained in the toner is continuously accumulated in the vicinity of the toner application means such as an elastic blade. It is presumed to be due to several reasons.

[0010]

The present invention is excellent in image density stability and image quality even when used for a long time without being affected by a temperature change accompanying use, and does not cause fusion to a charging member, a photoreceptor and the like. It is intended to provide a toner.

Further, the present invention provides a toner carrier, and
A toner image is formed on the electrostatic image carrier by developing with a charged toner using a toner application unit for applying the toner to the toner carrier, and the toner image is transferred onto a transfer material. It is an object of the present invention to provide an image forming method for heating and fixing a toner image, wherein the toner having the above characteristics is used.

[0012]

As a result of voluntary studies, the present inventors have found that an external additive fine powder having a specific circularity and a specific particle size distribution with a circular equivalent diameter has a specific shape and material. By using at least two types of fine powders having the following characteristics, even when used for a long time under the same conditions of low temperature and low humidity, an image having excellent image density stability can be obtained without causing fusion to a charging member, a photoreceptor, and the like. I found something. The present invention has been completed based on this finding.

The present invention provides a toner having toner particles containing at least a binder resin and a colorant, and a fine powder externally added to the toner particles, wherein the toner is measured by a flow type particle image measuring apparatus. , Average circularity is 0.9
In the particle size distribution of the circle equivalent diameter, the maximum value X is 3 to 9 μm in the circle equivalent diameter, and the circle equivalent diameter is 0.6 to 2 μm.
m has a local maximum value Y, and particles having a circle equivalent diameter of 0.60 or more and less than 2.00 μm are 8 to 30% by number of the whole;
A polymer having at least (A) a number average particle diameter of 0.05 to 2.0 μm, a shape factor SF-1 of 100 to 150, a shape factor SF-2 of 100 to 200, and a nitrogen atom-containing polymer A spherical resin fine powder A having a compound and
(B) A toner (hereinafter, also referred to as toner of the present invention) containing two types of fine particles of inorganic fine powder B having a number average particle diameter of primary particles of 1 to 30 nm on the surface of toner particles. .

In the toner of the present invention, preferred embodiments are the following and combinations thereof. -The number average particle diameter of the resin fine powder A is 0.1 to 1.0 m. -Resin fine powder A is 0.01 to 0.
It is contained at 5% by weight. -Resin fine powder A is composed of melanin formaldehyde resin or benzoguanamine-formaldehyde resin. -Resin fine powder A and / or inorganic fine powder B contains silicone oil. -The inorganic fine powder B is silica. -The inorganic fine powder B is 0.1 to 4.0 with respect to the toner particles.
% By weight. Further, an inorganic fine powder C which is alumina and / or titanium oxide is contained on the surface of the toner particles. Preferably,
The number average particle diameter of the primary particles of the inorganic fine powder C is less than 0.6 μm. Preferably, the inorganic fine powder C is contained in an amount of 0.1 to 3% by weight based on the toner particles. The toner particles are produced by a polymerization method in which a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is polymerized in a liquid medium in the presence of a polymerization initiator. The liquid medium is preferably an aqueous medium. -The toner is a non-magnetic toner, or the toner is used as a one-component developer, or the toner is a non-magnetic toner, and the non-magnetic toner is used as a non-magnetic one-component developer. The toner contains a release agent on the surface and / or inside of the toner particles, and the release agent has a DS in a region of 40 ° C. to 120 ° C.
Includes wax with maximum endothermic peak as measured by C.
The release agent preferably has a D content in the range of 40 ° C to 90 ° C.
Includes wax with maximum endothermic peak from SC measurements. The toner particles contain at least a binder resin, a colorant and a release agent, and the toner particles contain 3 to 40 parts by weight of the release agent based on 100 parts by weight of the binder resin. -It includes a release agent, and the release agent includes an ester wax having at least one long-chain ester moiety having 10 or more carbon atoms.

According to the present invention, there is also provided a toner carrier for carrying a toner, and an electrostatic image carrier by developing with a charged toner using a toner applying means for applying the toner to the toner carrier. An image forming method for forming a toner image thereon, transferring the toner image onto a transfer material, and heating and fixing the toner image on the transfer material, wherein the toner is the toner of the present invention. About.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The toner of the present invention has an average circularity measured by a flow type particle image measuring apparatus of 0.950 to 0.950.
0.995 (preferably 0.960 to 0.995), and an equivalent circle diameter of 3 to 9 μm in the particle size distribution of the equivalent circle diameter.
(Preferably 3 to 8 μm) with a maximum value X and an equivalent circle diameter of 0.6.
To a maximum value Y of about 2 μm (preferably 0.6 to 1.5 μm).
Particles having a circle equivalent diameter of 0.60 or more and less than 2.00 μm account for 8 to 30% by number of the total (preferably 12 to 2%).
7% by number).

Here, the flow type particle image measuring device is a device for statistically analyzing the image of particle imaging, and the average circularity is calculated by the arithmetic mean of the circularity obtained by the following equation using the device. You.

[0018]

(Equation 1)

In the above equation, the perimeter of the particle projection image is
The length of the outline obtained by connecting the edge points of the binarized particle image, and the perimeter of the equivalent circle is the length of the outer circumference of a circle having the same area as the binarized particle image. is there.

The particle size distribution measured by the apparatus is a particle size distribution based on the diameter (equivalent circle diameter) of a circle having the same area as the binarized particle image. On the basis of the particle size distribution based on the circle equivalent diameter, the maximum% X, the maximum value Y, and the number% of the whole particles having a circle equivalent diameter of 0.60 or more and less than 2.00 μm are calculated. When there are a plurality of maximum values in the above specific range in the particle size distribution, the maximum values are defined as maximum values X and Y, respectively.

When the average circularity of the toner is less than 0.950, the friction between the toner particles or between the toner particles and a member such as a toner carrier, which imparts charge to the toner, becomes large. Damage to toner particles,
Fine particles are formed, the charge of the toner particles becomes non-uniform, and the image is likely to be fogged. When the average circularity of the toner exceeds 0.995, the toner is less likely to be charged by friction, and an image having poor uniformity tends to be obtained.

In the present invention, known means can be used as means for obtaining the toner having the above average circularity.
More specifically, a method for forming a toner into a spherical shape as disclosed in JP-A-59-212848, and a toner composition containing a polymerizable monomer in an aqueous medium as disclosed in JP-A-59-53856 Any method of directly adding particles to obtain particles can be suitably used. Known means can also be used as means for adjusting the particle size distribution to obtain the toner having the above particle size distribution.
In particular, while making the content of particles having a circle equivalent diameter of 0.60 μm or more and less than 2.00 μm, which is a feature of the present invention, an appropriate value,
Since it is easy to simultaneously satisfy the average circularity of the toner, the toner particles can be obtained by mixing a polymerizable monomer composition containing at least a polymerizable monomer and a colorant in a liquid medium (preferably, in the presence of a polymerization initiator). (Aqueous medium), and is preferably produced by a polymerization method for directly obtaining toner particles.

The toner of the present invention has a particle size distribution based on a circle equivalent diameter measured by a flow type particle image measuring apparatus,
It has a local maximum X at a circle equivalent diameter of 3 to 9 μm and a circle equivalent diameter of 0.6.
Having a maximum value Y of about 2.0 μm and a circle equivalent diameter of 0.60 μm
8 to 30% by number of particles having a particle size of 2.00 μm or less. In the present invention, the particles constituting the maximum value Y are considered to have a role of reducing the fluidity to an appropriate value. In the present invention, the particles constituting the maximum value X are particles substantially having a function as a developer.
Particles having an equivalent circle diameter of 3 μm or more and less than 9 μm are preferably present in 40 to 92% by number.

In the particle size distribution of particles measured by a flow type particle image measuring device according to the circle equivalent diameter, a spherical toner having only a single peak becomes a toner having an excessively good fluidity. Is not sufficiently performed, and unevenness occurs in the initial image. 0.60μ equivalent circle diameter
Even when the content of the particles having a particle size of m or more and less than 2.00 μm is less than 8% by number, the toner has an excessively good fluidity, and thus the initial image tends to be uneven. When the content of the particles having an equivalent circle diameter of 0.60 μm or more and less than 2.00 μm exceeds 30% by number, the effect of lowering the fluidity works excessively and the toner becomes poor in fluidity. And the image density is not stable.

The toner of the present invention contains at least two kinds of fine powder on the surface of toner particles. The first fine powder is a spherical resin fine powder A having a polymer compound containing a nitrogen atom, and the number average particle diameter of the resin fine powder A is 0.05 to
2.0 μm.

Examples of the polymer compound containing a nitrogen atom, ie, a resin containing a nitrogen atom, include amino resins, more specifically, melamine resins, and more specifically, melanin formaldehyde resins and benzoguanamine-formaldehyde resins. And a resin obtained by condensation of melanin or a derivative thereof with formaldehyde.

In the present invention, the number average particle diameter is determined by randomly sampling a fine particle image on a toner using an electron microscope, obtaining an arithmetic average of the major axis diameter and the minor axis diameter, and calculating the arithmetic mean value. The average value obtained by performing the same operation over 100 particles and performing arithmetic averaging.

In the present invention, it is considered that the resin fine powder A plays a role in preventing image streaks. That is, particles having an equivalent circle diameter of 0.60 μm or more and less than 2.00 μm in the particle size distribution measured by a flow type particle image measurement device act as a fluidity modifier as described above. A phenomenon occurs in which particles are not subjected to development and accumulate in the vicinity of a charging member such as a blade. As a result, the toner supply near the blade becomes non-uniform, resulting in poor image density stability. This phenomenon is particularly remarkable under low temperature and low humidity conditions. In addition, some of the particles fuse to the charging member and cause image defects such as image streaks.

When the resin fine particles A are added here, the resin fine particles A have a spherical shape, and thus easily pass through the nip portion of the charging member than other particles. When the resin fine particles A pass through the nip portion of the charging member, both side surfaces of the resin fine particles A are slightly lifted, so that the equivalent circle diameter is 0.60 μm or more.
Some of the toner particles having a size of less than 00 μm can pass through the nip. Thereby, the phenomenon that the particles are not subjected to the development and are accumulated in the vicinity of the charging member such as the blade can be suppressed.

The number average particle diameter of the resin fine particles A is 0.05 μm.
If it is less than 0.1 m, the resin fine particles A enter the nip portion but are difficult to pass through, so that the equivalent circle diameter is 0.1 mm.
The toner particles having a size of 60 μm or more and less than 2.00 μm cannot be effectively removed. When the number average particle diameter of the resin fine particles A is 2.0 μm or more, it is difficult to enter the nip portion, so that the toner particles having an equivalent circle diameter of 0.60 μm or more and less than 2.00 μm can be effectively removed. It cannot be removed.

The shape factor SF-1 of the resin fine particles A is 100 to 150, and SF-2 is 100 to 200. SF-1 and SF-2 indicating the shape factor used in the present invention are FE-SEM (S-80) manufactured by Hitachi, Ltd.
Using (0), 100 fine particle images on the toner particle surface were randomly sampled, and the image information was introduced into an image analysis device (Luzex3) manufactured by Nicole via an interface, analyzed, and calculated by the following equation. Value to shape factor SF
-1 and SF-2.

[0032]

(Equation 2)

The shape factor SF-1 indicates the degree of sphericity, and is 10
As the size increases from 0, the shape gradually changes from a spherical shape to an irregular shape. SF-2 indicates the degree of roughness, and as the value increases from 100, the roughness of the particle surface becomes more conspicuous.

The shape factor SF-1 of the fine resin particles A is 150
When it exceeds, the frictional resistance on the surface of the resin fine particles A is large, and the ability to slip through the nip portion of the charging member is inferior.
The toner particles having an equivalent circle diameter of 0.60 μm or more and less than 2.00 μm cannot be effectively removed. Further, even when the shape factor SF-2 of the resin fine particles A exceeds 200, the frictional resistance of the surface of the resin fine particles A is large, so that the equivalent circle diameter is 0.1 mm.
The toner particles having a size of 60 μm or more and less than 2.00 μm cannot be effectively removed.

The above specific shape factors SF-1 and SF
-2 resin fine powder A is a soap-free emulsion polymerization,
Seed polymerization, dispersion polymerization, suspension polymerization, two-stage swelling method, etc.
Polymerization granulation method using polymerizable monomers to form particles during the polymerization process; spray drying method, liquid curing method (coagulation method),
It is obtained by appropriately adjusting the production conditions by a method such as a phase separation method (coacervation method), a solvent evaporation method, a reprecipitation method, or a dispersion granulation method in which particles are formed from a polymer solution formed into fine droplets. Can be

The second fine powder of the toner of the present invention on the surface of the toner particles is an inorganic fine powder B, and the primary particles of the inorganic fine powder B have a number average particle diameter of 1 to 30 nm (number average particle diameter). Is as described above).

In the present invention, the inorganic fine powder B uniformly adheres to the surfaces of the toner particles and the resin fine particles A, thereby increasing the surface hardness of these particles and preventing the particles from flattening. If the inorganic fine powder B is not contained in the toner, the toner particles and / or the resin fine particles A become flat with the use over a long period of time, so that a desirable particle shape cannot be maintained. When the number average particle diameter of the primary particles of the inorganic fine powder B is less than 1 nm, the inorganic fine particles B are easily buried in the toner particles and / or the resin fine particles A. Can not.
When the number average particle diameter of the primary particles of the inorganic fine powder B is 30 nm or more, it is difficult to uniformly exist on the surface of the toner particles and / or the resin fine particles A, and the effect of addition is not sufficiently exhibited.

In the present invention, the number average particle size of the resin fine powder A is preferably 0.1 to 1.0 μm. When the number average particle diameter of the resin fine powder A is less than 0.1 μm, the frictional resistance value per unit volume of the resin fine powder A increases, so that it may be difficult to slip through the nip portion. The number average particle diameter of the resin fine powder A is 1.0 μm.
If it exceeds m, it may be difficult for the resin fine powder A to enter the nip portion.

In the present invention, the resin fine powder A is preferably contained in an amount of 0.01 to 0.5% by weight based on the toner particles. Resin fine powder A content is 0.01% by weight
If it is less than the above, the effect of adding the resin fine powder A may not be sufficiently obtained. When the content of the resin fine powder A is 0.5% by weight or more, the effect of slipping through the nip portion becomes excessive, and toner scattering may occur.

In the present invention, it is preferable that the inorganic fine powder B is contained in an amount of 0.1 to 4.0% by weight based on the toner particles. When the content of the inorganic fine powder B is less than 0.1% by weight, the effect of adding the inorganic fine powder B may not be sufficiently obtained. Content of inorganic fine powder B is 4.0
If the content is not less than% by weight, the inorganic fine particles B released from the surface of the toner particles and / or the resin fine particles A may contaminate the charging member, which is not preferable.

In the present invention, resin fine powder A and / or
Alternatively, it is preferable that the inorganic fine powder B contains silicone oil. When a minute amount of the silicone oil contained in one or both of the silicone oils exudes through long-term use, the resin fine powder A can easily pass through the nip portion.

The effect of the present invention can be achieved by using any kind of nitrogen atom-containing resin fine particles and inorganic fine particles for the resin fine particles A and the inorganic fine powders B, respectively. This is most preferably achieved when it is composed of a formaldehyde resin or a benzoguanamine-formaldehyde resin, and when the inorganic fine powder B is silica. Although the detailed reason is unknown, it is considered that the surface properties of the fine particles, the charging characteristics, and the uniformity of the oil treatment are related.

The toner of the present invention has an inorganic fine powder C on the surface of the toner particles in addition to the resin fine powder A and the inorganic fine powder B, and the inorganic fine powder C may be alumina and / or titanium oxide. preferable. In the present invention, the inorganic fine powder C functions as an auxiliary agent for the resin fine particles A.
Although the detailed mechanism is unknown, the inorganic fine powder C has a circular equivalent diameter of 0.60 μm or more and 2.00 near the charging member nip.
It is considered that the toner particles having a particle diameter of less than μm are prevented from being aggregated and unevenly distributed, and the effect of adding the resin fine particles A is enhanced. The number average particle diameter of the inorganic fine particles C is preferably less than 0.6 μm (more preferably, less than 0.4 μm) (the method of measuring the number average particle diameter is as described above). When the number average particle diameter of the inorganic fine particles C is 0.6 μm or more, the effect of the inorganic fine particles C as an auxiliary of the resin fine particles A may be reduced. Further, the inorganic fine powder C is
The content is preferably 0.1 to 3% by weight based on the toner particles. When the content of the inorganic fine powder C is less than 0.1% by weight, the effect of the resin fine particles A as an auxiliary may be reduced. If the content of the inorganic fine powder C exceeds 3% by weight, an excessive amount of the inorganic fine particles C may damage the charging member or the like, which is not preferable.

The toner of the present invention contains a release agent on the surface and / or inside of the toner particles.
It is preferable that a wax having a maximum endothermic peak measured by DSC is contained in a region of 20 ° C., more preferably in a region of 40 ° C. to 90 ° C. In order to achieve a reduction in size and power consumption of an image forming apparatus, a method of incorporating a low melting point wax into a toner is widely known. Therefore, a phenomenon that a fused material is seen on a charging member, a photoreceptor, or the like with long-term use, which is a problem to be solved by the present invention, is likely to occur. In such a case, the phenomenon can be suppressed by using the toner having the configuration shown in the present invention.

The other components in the present invention will be described. The toner of the present invention usually comprises a binder resin and a colorant.

Examples of the binder resin of the toner of the present invention include homopolymers of styrene such as polystyrene and polyvinyltoluene and substituted products thereof, styrene-propylene copolymers,
Styrene-vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, sterene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer , Styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer,
Styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-
Styrene copolymers such as maleic acid ester copolymers, polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, fat Group or alicyclic hydrocarbon resin, aromatic petroleum resin, paraffin wax, carnauba wax and the like.
These can be used alone or as a mixture.

As the colorant used in the toner of the present invention, known dyes and pigments can be used. In particular,
As the black colorant, carbon black, a magnetic material, or the like, and those toned to each color using the following yellow / magenta / cyan colorants are used.

Specific examples of the yellow colorant include compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds and the like. In particular,
C. I. Pigment Yellow 12, 13, 14, 15,
17, 62, 74, 83, 93, 94, 95, 109,
110, 111, 128, 129, 147, 168, 1
80 and the like are preferably used.

Specific examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Can be Specifically, C.I. I. Pigmentlets 2, 3, 5, 6, 7, 2
3, 48; 2, 48; 3, 48; 4, 57; 1, 81;
1, 122, 144, 146, 166, 169, 17
7, 184, 185, 202, 206, 220, 22
1, 254 are particularly preferred.

Specific examples of the cyan coloring agent include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15;
1, 15; 2, 15; 3, 15; 4, 60, 62, 66
Etc. can be used particularly preferably.

These colorants can be used alone or as a mixture or in the form of a solid solution.

When the colorant of the present invention is a color toner,
It is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, dispersibility in toner, and the like. The amount of the colorant is usually 1 to 20 parts by weight based on 100 parts by weight of the resin. When a magnetic material is used as a black colorant, unlike other colorants, usually 40 to 150 parts per 100 parts by weight of resin.
Used in parts by weight.

In the toner of the present invention, a charge control agent can be used if necessary. As the charge control agent used in the present invention, a known charge control agent can be used. In the case of a color toner, in particular, a charge control agent that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable. preferable.

Specific examples of the negative compound include salicylic acid, naphthoic acid, dicarboxylic acid, metal compounds of their derivatives, sulfonic acid, high molecular compounds having carboxylic acid in the side chain, boron compounds, urea compounds, and silicon compounds as negative compounds. , Calixarene, etc., and quaternary ammonium salts, high molecular weight compounds having the quaternary ammonium salt in the side chain, guanidine compounds, imidazole compounds and the like are preferably used.

The charge control agent is preferably used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the resin. However, in the present invention, the addition of a charge control agent is not indispensable, and the toner need not necessarily contain a charge control agent by actively utilizing frictional charging with the blade member or the sleeve member.

In the toner of the present invention, a substance having a low softening point, so-called wax, can be used if necessary. Wax usually functions as a release agent.

Examples of the low softening substance used in the toner for developing an electrostatic image of the present invention include polymethylene wax such as paraffin wax, polyolefin wax, microcrystalline wax and Fischer-Tropsch wax, amide wax, higher fatty acid, and higher fatty acid. Chain alcohols, ester waxes and their graft compounds,
Derivatives such as block compounds are mentioned, and those having a sharp maximum endothermic peak in a DSC endothermic curve from which low molecular weight components have been removed are preferred.

Preferred waxes include linear alkyl alcohols having 15 to 100 carbon atoms, linear fatty acids, linear acid amides, linear esters, and montan derivatives. It is also preferable that these waxes have impurities such as liquid fatty acids removed in advance.

Further, as the wax preferably used, a low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or polymerized under low pressure using a Ziegler catalyst or another catalyst; The resulting alkylene polymer;
Low-molecular-weight alkylene polymer by-produced when polymerizing alkylene is separated and purified;-Hydrogenation of hydrocarbon polymer distillation residue obtained from the synthesis gas consisting of carbon oxide and hydrogen by the Age method, or hydrogenation of distillation residue Polymethylene wax obtained by extracting and fractionating a specific component from the synthetic hydrocarbon obtained by the above method. An antioxidant may be added to these waxes.

The low softening point substance used in the present invention is DS
In the C endothermic curve, 40 to 120 degrees Celsius (more preferably 40 to 90 degrees Celsius, and particularly preferably 45 to 8 degrees Celsius).
(5 °) preferably has a maximum endothermic main peak. Further, the half width of the endothermic main peak is 10 degrees Celsius.
A material having a low softening point having a sharp melt property within the temperature (more preferably within the temperature of 5 degrees Celsius) is preferable. In particular, the low softening point substance is preferably an ester wax having at least one long-chain ester moiety having 10 or more carbon atoms, and a long-chain alkyl alcohol having 15 to 45 carbon atoms and a long-chain alkyl alcohol having 15 to 45 carbon atoms. An ester wax containing an ester compound with a carboxylic acid as a main component is more preferable.

For the measurement of the temperature of the maximum peak value of the present invention, for example, DSC-7 manufactured by PerkinElmer is used. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. An aluminum pan was used as a sample, an empty pan was set as a control, and the temperature was raised at a rate of 10 ° C./min. Perform the measurement with.

The low softening point substance is usually contained on the surface and / or inside of the toner, preferably 3 to 40 parts by weight, more preferably 3 to 40 parts by weight, based on 100 parts by weight of the binder resin in the toner particles. It is preferable to contain 5 to 35 parts by weight.

When the content of the low softening point substance is less than 5 parts by weight, it is difficult to obtain a sufficient high-temperature offset resistance, and further, at the time of fixing the image on both sides of the recording material, at the time of the second (back side) fixing. The first (front) image offset may occur.

When the content of the low softening point substance exceeds 40 parts by weight, when toner particles are produced by a pulverization method during the production of the toner, the toner components are liable to be fused in the toner production apparatus, When producing toner particles by a polymerization method,
At the time of granulation, the granulation property is reduced, and coalescence of toner particles is likely to occur.

The toner of the present invention is a non-magnetic toner,
Alternatively, it is preferable that the toner is used as a one-component developer, or that it is a non-magnetic toner and used as a one-component developer. In a non-magnetic one-component developing device, generally, a toner carrier, and a toner as a developer is charged by toner applying means such as an elastic blade for applying the toner to the toner carrier, so that the toner applying means Along with the thermal expansion of the toner carrier, a change occurs in the developer layer thickness regulating ability and the like, resulting in a non-uniform developer layer thickness. Although a phenomenon such as accumulation tends to occur, the toner of the present invention is suitable for charging by a charging member such as a blade as described above, so that such a phenomenon can be suppressed.

The method for producing the toner particles of the present invention includes known methods such as a pulverization method / suspension polymerization method / a method of aggregating particles obtained by emulsion polymerization to obtain a toner / interfacial polymerization method / dispersion polymerization. Can be used, but any method may be used as long as the toner to be produced is within the scope of the present invention. Hereinafter, some examples of the manufacturing method will be described.

When the pulverization method is used as the production method of the present invention, the resin, the release agent, the colorant, the charge control agent and the like are uniformly dispersed using a pressure kneader, an extruder or a media disperser, and then further dispersed. Through a classification step, the particle size distribution is sharpened to form a toner.

When a polymerization method by suspension polymerization is used, a releasing agent, a coloring agent, a charge control agent, a polymerization initiator and other additives are added to the polymerizable monomer, and a homogenizer / ultrasonic dispersion is used. The monomer composition uniformly dissolved or dispersed by an apparatus or the like is dispersed in an aqueous phase containing a dispersion stabilizer by a homomixer or the like. Granulation is stopped when the droplets of the monomer composition have reached the desired toner particle size. Thereafter, by the action of the dispersion stabilizer, the particles may be stirred to such an extent that the particle state is maintained and the particles are prevented from settling. The polymerization temperature is 40 ° C. or higher, generally 5
The polymerization is carried out at a temperature of 0 to 90 ° C. In order to adjust the molecular weight distribution, the temperature may be raised in the latter half of the polymerization reaction, and the temperature may be further increased in the latter half of the reaction or after completion of the reaction to remove unreacted polymerizable monomers and by-products. The partial aqueous medium may be distilled off.

After the completion of the reaction, the generated toner particles are washed and
Collect by filtration and dry. In the suspension polymerization method,
Usually 300 to 3 parts of water per 100 parts by weight of the monomer composition.
It is preferable to use 000 parts by weight as a dispersion medium.

In the present invention, when toner particles are obtained by a polymerization method, the polymerizable monomer may be styrene,
styrene-based monomers such as o- (m-, p-) methylstyrene and m- (p-) ethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, ( Butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
(Meth) acrylate monomers such as dimethylaminoethyl acrylate and diethylaminoethyl (meth) acrylate; butadiene, isoprene, cyclohexene,
Ene monomers such as (meth) acrylonitrile and acrylamide are preferably used. These may be used alone or generally in the published Polymer Handbook, 2nd edition III-P
139-192 (issued by John Wiley & Sons) has a theoretical glass transition temperature (Tg) of 40-8.
The monomers are appropriately mixed and used so as to show 0 ° C. If the theoretical glass transition temperature is lower than 40 ° C., problems arise in terms of the storage stability of the toner and the durability stability of the developer. In such a case, the color mixture of the toners of each color is insufficient, resulting in poor color reproducibility, and furthermore, the transparency of the OHP image is significantly reduced, which is not preferable from the viewpoint of high image quality.

In the method of obtaining toner particles by using the polymerization method, it is particularly preferable to add a polar resin at the same time from the viewpoint that the polymerization reaction of the polymerizable monomer can be performed without inhibition. As the polar resin used in the present invention, a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, a polyester resin, an epoxy resin and the like are preferably used. It is particularly preferable that the polar resin does not contain an unsaturated group capable of reacting with a monomer in the molecule.

Examples of the polymerization initiator used in the polymerization method include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile,
1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-
Azo-based polymerization initiators such as dimethylvaleronitrile and azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-
Peroxide-based polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide are exemplified.

The particle size distribution and the particle size of the toner can be controlled by changing the type and amount of the hardly water-soluble inorganic salt or the dispersing agent that acts as a protective colloid, or by mechanical device conditions such as the peripheral speed of the rotor and the path. The toner of the present invention can be obtained by controlling the stirring conditions such as the number of times and the shape of the stirring blade, the shape of the container, and the solid content concentration in the aqueous solution.

In the toner of the present invention, in addition to the fine powder used in the present invention, organic or inorganic fine particles generally widely known as an external additive can be added. Specifically, examples of the inorganic fine particles include metal oxides (such as aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, and zinc oxide), nitrides (such as silicon nitride), and carbides (such as silicon nitride). Silicon carbide and the like, metal salts (calcium sulfate, barium sulfate, calcium carbonate, and the like), fatty acid metal salts (zinc stearate, calcium stearate, and the like), carbon black, silica, and the like can be used. Examples of the organic fine particles include homopolymers or copolymers of monomer components such as styrene, acrylic acid, methyl methacrylate, butyl acrylate, and 2-ethylhexyl acrylate, which are used in a binder resin for a toner, obtained by an emulsion polymerization method or a spray drying method. Polymers can be used. Further, it is also possible to use a plurality of these fine particles in combination as needed.

The image forming method of the present invention comprises the steps of:
And developing the toner image on the electrostatic image carrier by developing with a charged toner using a toner application unit for applying the toner to the toner carrier, transferring the toner image onto a transfer material, and transferring An image forming method for heating and fixing a toner image on a material, wherein the toner is the toner of the present invention.

An example of the toner applying means is an elastic blade which is in surface contact with the outer peripheral surface of a toner carrier such as a developing sleeve. As an elastic blade,
Rubber elastics such as silicone rubber, urethane rubber and NBR; elastomers such as polyethylene terephthalate and polyamide; metal elastics such as stainless steel, steel and phosphor bronze can be used, and even composites thereof can be used. For example, a material obtained by injection-molding a rubber material such as urethane or silicone or various elastomers such as polyamide elastomer on a metal sheet of SUS or phosphor bronze having spring elasticity is preferably used.

The contact pressure between the elastic blade and the developing sleeve is usually 0.3 linear pressure in the generatrix direction of the developing sleeve.
-5.0 kgf / m, preferably 0.5-4.0 kgf
/ M is effective. The linear pressure is a load applied per blade length. For example, when a blade having a contact length of 1 m is contacted with a sleeve by applying a load of 1.2 kg weight to the sleeve, the linear pressure is It becomes 1.2 kgf / m. If the linear pressure is less than 0.3 kgf / m, it becomes difficult to apply the non-magnetic one-component developer uniformly, and the charge amount distribution of the non-magnetic one-component developer becomes broad, which may cause fogging and scattering. When the contact pressure exceeds 5.0 kgf / m, a large pressure is applied to the non-magnetic one-component developer, and the non-magnetic one-component developer is deteriorated, so that aggregation of the non-magnetic one-component developer may occur. Is not preferred. Further, a large torque is required to drive the developing sleeve, which is not preferable.

In the image forming method of the present invention, the above-described toner image forming step, transfer step and heat fixing step may be the same as those in the conventional image forming method using a dry developer. Since the toner of the present invention is suitable for charging using the toner carrier and the toner applying unit, according to the image forming method of the present invention, the heat generated in the toner applying unit and the toner carrier, etc., generated in such a charging step. Along with the expansion, a change occurs in the ability of regulating the thickness of the developer layer and the like, resulting in a non-uniform thickness of the developer layer, and a phenomenon that a substance contained in the toner is continuously accumulated near the toner applying means. Can be suppressed.

[0079]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which do not limit the present invention in any way. First, the measurement method used will be described.

As a flow type particle image measuring device for measuring the average circularity and the particle size distribution, a flow type particle image measuring device (FPIA-1000) manufactured by Toa Medical Electronics Co., Ltd. was used. About 0.02 g of the toner for measuring the average circularity is weighed, and ion-exchanged water (about 10 ml,
(20 ° C.). As means for dispersing, an ultrasonic dispersing machine UH-5 manufactured by SMT Co., Ltd.
0 (the vibrator is a 5φ titanium alloy chip) was used. Dispersion time is 5 minutes or more, and at this time, the temperature of the dispersion medium is 40 ° C.
It cooled appropriately so that it might not become above. Using the above-mentioned flow type particle image measuring device, 1000 or more toner particles are measured, the arithmetic mean of circularity calculated using the following equation is calculated, and the same area as the binarized particle image is obtained. The particle size distribution of the circle diameter (equivalent circle diameter) was determined.

[0081]

(Equation 3)

In the above equation, the perimeter of the particle projection image is
This is the length of the contour obtained by connecting the edge points of the binarized particle image. The perimeter of the equivalent circle is the length of the outer circumference of a circle having the same area as the binarized particle image. is there.

The outline of the measurement is described in the catalog of FPIA-1000 (June 1995 edition) issued by Toa Medical Electronics Co., Ltd.
No. 6439, which is as follows.

The sample dispersion is passed through a flow path (spread along the flow direction) of a flat and flat transparent flow cell (about 200 μm thick). The strobe and the CCD camera are mounted on the flow cell so as to be positioned on opposite sides of the flow cell so as to form an optical path that intersects with the thickness of the flow cell. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a range parallel to the flow cell 2
Photographed as a two-dimensional image. The diameter of a circle having the same area is calculated as the equivalent circle diameter from the area of the two-dimensional image of each particle.

In about 1 minute, the equivalent circle diameter of 900 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of the particles having the specified equivalent circle diameter can be measured. .

As shown in Table 1, the results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave). In actual measurement, particles are measured in a range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm.

[0087]

[Table 1]

The following method was used to calculate the number average particle size of the resin fine particles (fine powder) A of the present invention.

Using FE-SEM manufactured by Hitachi, Ltd.
The fine particle image on the toner magnified 000 times is sampled at random, and the arithmetic mean value of the major axis diameter and the minor axis diameter is obtained.
The average particle diameter of the fine particles was used. The same operation was performed for 100 fine particles, and arithmetic average was performed to obtain the number average particle size of the fine particles.

The following method was used to calculate the number average particle size of the inorganic fine powder B of the present invention.

Using FE-SEM manufactured by Hitachi, Ltd., 10
The fine particle image on the toner magnified 0000 times was sampled at random, and the arithmetic mean value of the major axis diameter and the minor axis diameter was determined to be the average particle diameter of the fine particles. Perform the same operation for 100
The number average particle diameter of the fine particles was obtained by arithmetically averaging over the fine particles.

Shape factor of fine particles (SF-1, SF-2)
Is defined using the following method.

FE-SEM (S-800) manufactured by Hitachi, Ltd.
Is used to sample 100 fine particle images on the toner particle surface at random, and the image information is introduced into an image analyzer (Luzex3) manufactured by Nicole via an interface, analyzed, and the value obtained by the following equation is calculated. Shape factor SF-1
And SF-2.

[0094]

(Equation 4)

Next, a method for measuring the molecular weight will be described. The molecular weight of the resin was measured by GPC (gel permeation chromatography). As a specific GPC measurement method, a developer (toner) is extracted in advance with a toluene solvent using a Soxhlet extractor for 20 hours, and then toluene is distilled off with a rotary evaporator. After thoroughly washing or extracting with an organic solvent in which the point substance is soluble but the resin is insoluble, for example, chloroform, etc., the solution dissolved in THF (tetrahydrofuran) is passed through a solvent-resistant membrane filter having a pore diameter of 0.3 μm. For the filtered sample, use Waters 1
The molecular weight was measured using 50C. The column configuration is A-801, 802, 803, 804, 805, 8 manufactured by Showa Denko
06 and 807 were connected, and a calibration curve of a standard polystyrene resin was used.

[0096]

Embodiment 1 0.1 M-
After adding 450 parts by weight of an aqueous solution of Na ₃ PO ₄ and heating to 50 ° C., the mixture was stirred at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). 1.0M-Ca
70 parts by weight of a Cl ₂ aqueous solution was gradually added to obtain an aqueous medium containing a calcium phosphate salt.

On the other hand, a material having the following formulation was heated to 60 ° C.
Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.),
It was uniformly dissolved and dispersed at 00 rpm. Into this, 2 parts by weight of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

(Monomer) Styrene 170 parts by weight n-butyl acrylate 30 parts by weight (colorant) I. Pigment Blue 15: 3 15 parts by weight (charge control agent) Metallic salicylate compound 2 parts by weight (polar resin) Saturated polyester 20 parts by weight (acid value 10, peak molecular weight: 15,000) (release agent) Behenyl stearate 30 parts by weight ( Crosslinking agent) 1.0 parts by weight of divinylbenzene

The above salicylic acid metal compound had the following structural formula.

[0100]

Embedded image

[0102] 3 parts by weight of potassium persulfate was added as a water-soluble initiator in the aqueous medium, was charged with the polymerizable monomer composition, 50 ° C., under N ₂ atmosphere, 8000 at TK homomixer The mixture was stirred at rpm to granulate the polymerizable monomer composition. Then, after stirring for 4 hours while stirring with a paddle stirring blade, the temperature was raised at a rate of 40 ° C./Hr. Raise the temperature to 70 ° C with 5
Allowed to react for hours. After the completion of the polymerization reaction, the remaining monomer was distilled off under reduced pressure. After cooling, hydrochloric acid was added to dissolve the calcium phosphate salt, followed by filtration, washing with water, and drying.
8 μm cyan toner particles (1) were obtained. The average circularity and particle size distribution of the obtained cyan toner particles (1) were measured using a flow-type particle image measuring device manufactured by Toa Medical Electronics Co., Ltd., and the average circularity was 0.972, and the equivalent circle diameter was obtained. The maximum value X was at 5.8 μm, and the maximum value Y was at 0.7 μm. 0.60μm equivalent circle diameter
The content of particles having a size of less than 2.00 μm was 21% by number.

For 100 parts by weight of the cyan toner particles (1), 0.2 part by weight of a melanin formaldehyde resin (A-1) having a number average particle diameter of 0.2 μm, and a number average particle diameter of 7 nm treated with silicone oil. Silica fine particles (B
-1) and 1.0 part by weight of titanium oxide fine particles (C-1) having a number average particle size of 0.27 μm were added.
Using a Henschel mixer manufactured by Mitsui Mining Co., Ltd., the mixture was uniformly stirred to obtain toner (1).

The average circularity and particle size distribution of the obtained toner (1) were measured using a flow type particle image measuring device manufactured by Toa Medical Electronics Co., Ltd., and the average circularity was 0.973. The equivalent diameter had a maximum value X at 5.8 μm, and the circle equivalent diameter had a maximum value Y at 0.7 μm. The content of particles having an equivalent circle diameter of 0.60 μm or more and less than 2.00 μm is 2
It was 2% by number.

For the obtained toner (1), 100 fine particle images on the surface of toner particles were randomly sampled using FE-SEM (S-800) manufactured by Hitachi, Ltd., and fine resin powder A, fine inorganic powder B, And the number average particle diameter of the inorganic fine powder C was calculated. Regarding the resin fine particles A, image information was introduced into an image analyzer (Luzex3) manufactured by Nicole, and SF-1 and SF-2 were calculated.

The obtained developer was subjected to image evaluation using an image forming apparatus as shown in FIGS. 1 and 2. The outline of the image forming apparatus will be described below.

In FIG. 1, reference numeral 1 denotes a photosensitive drum as a latent image carrier. The photosensitive drum 1 rotates in the direction of arrow A in FIG. 3 forms an electrostatic latent image on its surface.

The electrostatic latent image is developed by the developing device 4 and is visualized as a toner image. The developing device 4 is disposed close to the photosensitive drum 1 and is detachably attached to the image forming apparatus main body as a process cartridge. It is configured. In this apparatus, so-called reversal development for forming a toner image on an exposed portion is performed.

The visualized toner image on the photosensitive drum 1 is transferred to the recording medium paper 13 by the transfer roller 9, and the transfer residual toner remaining on the photosensitive drum 1 without being transferred is scraped off by the cleaning blade 10. The photosensitive drum 1 stored and cleaned in the waste toner container 11 repeats the above-described operation to form an image.

On the other hand, the paper 13 to which the toner image has been transferred is subjected to a fixing process by the fixing device 12, and is discharged out of the device to complete the printing operation.

Next, the developing device 4 will be described with reference to FIG. In FIG. 2, reference numeral 14 denotes a developing container for storing a non-magnetic toner 8 as a one-component developer, and an opening extending in the longitudinal direction in the developing container 14 includes a photosensitive drum 1.
Sleeve 5 as a developer carrying member disposed opposite to
The electrostatic latent image on the photoconductor 1 is developed by the non-magnetic toner 8 carried on the developing sleeve 5 and is visualized.

The developing sleeve 5 extends laterally with the right half peripheral surface shown in the drawing protruding into the developing container 14 at the opening of the developing container 14 and the left half peripheral surface exposed outside the developing container 14. . The surface of the developing sleeve 5 exposed to the outside of the developing container 14 faces the photosensitive drum 1 located on the left side of the developing device 4 with a small gap. The developing sleeve 5 is driven to rotate in the direction indicated by the arrow B in FIG. 2, and has a surface with moderate unevenness. The unevenness increases the probability of sliding of the developing sleeve 5 with the non-magnetic toner 8. At the same time, the conveyance of the non-magnetic toner 8 is favorably performed.

An elastic regulating blade 7 is provided above the developing sleeve 5 so as to be supported by a holding metal plate 15. The vicinity of the free end of the elastic regulating blade 7 is near the outer peripheral surface of the developing sleeve 5. Are in contact with each other.
Note that the contact direction of the elastic regulating blade 7 with the developing sleeve 5 is a so-called counter (reverse) direction in which the tip side with respect to the contact portion is located on the upstream side in the rotation direction of the developing sleeve 5. The elastic blade 7 is in contact with the developing sleeve 5 via a rubber elastic layer at a contact portion with the developing sleeve 5, and the contact pressure between the elastic blade and the developing sleeve is 1.2 kgf / m as a linear pressure in the developing sleeve generatrix direction. is there.

Further, in FIG. 2, reference numeral 6 denotes an elastic roller as a developer replenishing member. The elastic roller 6 is located upstream of a contact portion of the elastic regulating blade 7 with the surface of the developing sleeve 5 in the rotation direction of the developing sleeve. And is rotatably supported. A bias voltage is applied to the elastic roller 6 and the developing sleeve 5 by a bias power supply 21.

In the developing device 4 having the above configuration,
During the developing operation, the non-magnetic toner 8 in the developing container 14 is sent toward the elastic roller 6 with the rotation of the stirring member 19 in the direction of arrow C.

The non-magnetic toner 8 is applied to the elastic roller 6
Is rotated in the direction of arrow D in the figure, and is conveyed to the vicinity of the developing sleeve 5, and the non-magnetic toner 8 carried on the elastic roller 6 at the contact portion between the developing sleeve 5 and the elastic roller 6 is in contact with the developing sleeve 5. The rubbing causes the toner to receive triboelectric charge and adhere to the developing sleeve 5.

Thereafter, the non-magnetic toner 8 is applied to the developing sleeve 5
Is sent under the pressure of the elastic regulating blade 7 along with the rotation in the direction of arrow B, and receives a proper tribo (amount of frictional charge) to form a thin layer on the developing sleeve 5.
Is conveyed to a developing unit which is a part facing the developing unit and subjected to development.

Using the image forming apparatus having the above configuration, 7000 sheets were durable in an environment of a temperature of 15 ° C. and a humidity of 10% RH, and evaluated.

Fog amount on paper at initial and at each durable number,
The evaluation was performed as follows for the image streak, the drum fusion, and the image density stability.

Amount of fog on paper An image having a solid white image portion was printed using a commercially available CLC paper A4 (available from Canon Inc., basis weight: 81.4 g / cm ² ) as a recording material, and a reflection densitometer ( TOKYO
Using DENSHOKU CO., LTD, REFLECTOMETER ODEL TC-6DS), the reflection density of the solid white portion after printing and the reflection density of the paper before printing were measured.

The worst value of the reflection density of the white background after printing (D
s), the difference (Ds-Dr) between the reflection density average values (Dr) of the paper before printing was defined as the fog amount on paper.

The evaluation described above was carried out when the initial image and the number of printed sheets were 500, 1,000, 3,000, and 5,000.
This was performed on images at the time of printing and 7000 sheets.

Image streaks 7000 halftone images were printed continuously over the entire printing area. With respect to the obtained 7,000 sheets of images, the number of image streaks, that is, the number of image streaks that appear for the first time on the recording paper after fixing in the direction parallel to the arrow A in FIG. .

The closer the evaluation value is to 7000 sheets, the less the image streaks appear.
This is a toner in which image streaks tend to appear.

Drum Fusing After printing 50 halftone images continuously over the entire printing area, the image forming apparatus was stopped.

The photosensitive drum 1 was removed from the image forming apparatus, and it was visually observed whether or not a fused material was generated on the photosensitive drum.

In the case where a fused material was generated, the evaluation was stopped at this point. If no fusing occurs,
After attaching the photosensitive drum 1 to the image forming apparatus as before, and printing 50 halftone images continuously again,
The apparatus was stopped, the photosensitive drum was removed again, and the presence or absence of fusion was observed.

This operation was repeated until a fused material was recognized or the total number of prints reached 7000.

The cumulative number of printed sheets at the time when the evaluation was completed was used as an evaluation value for drum fusion.

As the evaluation value approaches 7000 sheets, the toner is less likely to fuse with the drum, and as the evaluation value is smaller, the toner is more likely to fuse with the drum.

Image Density Stability After printing 50 halftone images over the entire printable area, the image forming apparatus was stopped. After 24 hours, the apparatus was operated again, 50 similar halftone images were printed, and the apparatus was stopped again. Such a procedure was repeated.

In this evaluation procedure, the first sheet, the 51st sheet,
101st, 151st, 201st, and 1501
The image density of the sheet was measured using a Macbeth densitometer (manufactured by Macbeth). The smaller the image density of the first sheet, the 51st sheet, the 101st sheet, the 151st sheet, the 201st sheet, and the 1501th sheet, the better the image density stability.

Various physical properties of the toner are shown in Table 2, and the evaluation results are shown in Table 3. In Table 2, “content of 0.6 to 2 μm”
Is the number% based on the whole of the particles having a circle equivalent diameter of 0.60 μm or more and less than 2.00 μm. Department.

[0133]

Example 2 A toner (2) was obtained in the same manner as in Example 1 except that the amount of the melamine formaldehyde resin (A-1) used in Example 1 was changed to 0.6 part by weight. .

Evaluation was performed in the same manner as in Example 1 using this toner (2). Table 2 shows various physical properties of the toner.
Table 3 shows the evaluation results.

[0135]

Example 3 Instead of the silicone oil-treated silica fine particles (B-1) used in Example 1, silica fine particles having a number average particle diameter of 7 nm (B
Example 1 except that 1.0 part by weight of -2) was used.
In the same manner as in the above, a toner (3) was obtained.

Evaluation was performed in the same manner as in Example 1 using this toner (3). Table 2 shows various physical properties of the toner.
Table 3 shows the evaluation results.

[0137]

Example 4 Instead of the silica oil-treated silica fine particles (B-1) used in Example 1, alumina oil-treated alumina fine particles having a number average particle diameter of 13 nm (B-
A toner (4) was obtained in the same manner as in Example 1 except that 0.3 part by weight of 3) was used.

Evaluation was performed in the same manner as in Example 1 using this toner (4). Table 2 shows various physical properties of the toner.
Table 3 shows the evaluation results.

[0139]

Example 5 Toner (5) was prepared in the same manner as in Example 1 except that the addition amount of the silicone oil-treated silica fine particles (B-1) used in Example 1 was changed to 0.07 parts by weight. I got

Evaluation was performed in the same manner as in Example 1 using this toner (5). Table 2 shows various physical properties of the toner.
Table 3 shows the evaluation results.

[0141]

Example 6 Except that 0.1 part by weight of a melamine formaldehyde resin (A-2) having a number average particle diameter of 1.2 μm was used instead of the melamine formaldehyde resin (A-1) used in Example 1. In the same manner as in Example 1, a toner (6) was obtained.

Evaluation was performed in the same manner as in Example 1 using this toner (6). Table 2 shows various physical properties of the toner.
Table 3 shows the evaluation results.

[0143]

Example 7 The titanium oxide fine particles (C-
A toner (7) was obtained in the same manner as in Example 1, except that 0.7 parts by weight of alumina fine particles (C-2) having a number average particle diameter of 0.01 μm were used instead of 1).

Evaluation was performed in the same manner as in Example 1 using this toner (7). Table 2 shows various physical properties of the toner.
Table 3 shows the evaluation results.

[0145]

Example 8 Cyan toner particles (1) used in Example 1
A benzoguanamine-formaldehyde resin (A-3) having a number average particle size of 1.0 μm was added to 0.5 parts by weight per 100 parts by weight.
Parts by weight, number average particle diameter 7nm treated with silicone oil
After adding 4.2 parts by weight of the silica fine particles (B-1), the mixture was uniformly stirred using a Henschel mixer manufactured by Mitsui Mining Co., Ltd. to obtain a toner (8).

Evaluation was performed in the same manner as in Example 1 using this toner (8). Table 2 shows various physical properties of the toner.
Table 3 shows the evaluation results.

[0147]

Embodiment 9 The titanium oxide fine particles (C-
A toner (9) was obtained in the same manner as in Example 1, except that the addition amount of 1) was 3.4 parts by weight.

Evaluation was performed in the same manner as in Example 1 using this toner (9). Table 2 shows various physical properties of the toner.
Table 3 shows the evaluation results.

[0149]

Example 10 Cyan toner particles (2) were obtained in the same manner as in Example 1 except that the formulation of the cyan toner particles (1) in Example 1 was as follows.

(Monomer) Styrene monomer 165 parts by weight n-butyl acrylate 35 parts by weight (colorant) Copper phthalocyanine pigment 14 parts by weight (CI Pigment Blue 17) (charge control agent) salicylic acid metal compound 2 parts by weight (in Example 1) (Same as used) (Polar resin) Saturated polyester 20 parts by weight (Acid value 10, peak molecular weight; 15,000) (Release agent) Paraffin wax (mp 60 ° C) 30 parts by weight (Cross-linking agent) Divinylbenzene 1.0 part by weight

[0151] For 100 parts by weight of the cyan toner particles (2), 0.1 part by weight of a melanin formaldehyde resin (A-1) having a number average particle diameter of 0.2 µm, and a number average particle diameter of 7 nm treated with silicone oil. Silica fine particles (B
-1) and 1.0 part by weight of titanium oxide fine particles (C-1) having a number average particle size of 0.27 μm were added.
Using a Henschel mixer manufactured by Mitsui Mining Co., Ltd., the mixture was uniformly stirred to obtain toner (10).

Evaluation was performed in the same manner as in Example 1 using this toner (10). Table 2 shows various physical properties of the toner, and Table 3 shows the evaluation results.

[0153]

Example 11 The procedure of Example 1 was repeated, except that the amount of the release agent behenyl stearate was changed to 48 parts by weight in the formulation of the cyan toner particles (1). Thus, toner particles (3) were obtained. The number average particle size of the cyan toner particles (3) is 100 parts by weight.
0.1 part by weight of 2 μm melanin formaldehyde resin (A-1), 1.0 part by weight of silica oil-treated silica fine particles (B-1) having a number average particle diameter of 7 nm, and a number average particle diameter of 0.27 μm Titanium oxide fine particles (C-
After adding 1.0 part by weight of 1), the mixture was uniformly stirred using a Henschel mixer manufactured by Mitsui Mining Co., Ltd., to obtain a toner (11).

Evaluation was performed in the same manner as in Example 1 using this toner (11). Table 2 shows various physical properties of the toner, and Table 3 shows the evaluation results.

[0155]

Example 12 Yellow toner particles (1) were obtained in the same manner as in Example 1 except that the formulation of the cyan toner particles (1) in Example 1 was as follows.

(Monomer) Styrene monomer 170 parts by weight n-butyl acrylate 35 parts by weight (colorant) I. Solvent Yellow 17 13.5 parts by weight (charge control agent) metal salicylate compound 3.4 parts by weight (same as used in Example 1) (polar resin) 20 parts by weight of saturated polyester (acid value 10, peak molecular weight; 15,000) (release) Agent) Behenyl stearate 30 parts by weight (crosslinking agent) divinylbenzene 1.0 part by weight

As in Example 1, the number average particle diameter was 0.2 μm with respect to 100 parts by weight of the yellow toner particles (1).
0.2 parts by weight of a melanin formaldehyde resin (A-1), and a silicone oil-treated number average particle diameter of 7 nm
1.0 parts by weight of silica fine particles (B-1) and titanium oxide fine particles (C-1) having a number average particle size of 0.27 μm.
After adding 0 parts by weight, the mixture was uniformly stirred using a Henschel mixer manufactured by Mitsui Mining Co., Ltd. to obtain toner (12).

Evaluation was performed in the same manner as in Example 1 using this toner (12). Table 2 shows various physical properties of the toner, and Table 3 shows the evaluation results.

[0159]

COMPARATIVE EXAMPLE 1 Nitrogen-substituted water 180 was placed in a four-necked flask.
Part by weight and 0.2 wt% aqueous solution of polyvinyl alcohol 2
After 0 parts by weight, 75 parts by weight of styrene, 25 parts by weight of n-butyl acrylate, 3.0 parts by weight of benzoyl peroxide, and 0.2 parts by weight of divinylbenzene were added, and stirred to form a suspension. . Next, after the inside of the flask was replaced with nitrogen, the temperature was raised to 80 ° C. and maintained at the same temperature for 10 hours to carry out a polymerization reaction.

After the obtained polymer was washed with water, the temperature was lowered to 6.
The resin was dried in a reduced pressure environment while maintaining the temperature at 5 ° C. to obtain a resin. 88 parts by weight of the resin, 4 parts by weight of a metal salicylate compound (same as used in Example 1), 4 parts by weight of copper phthalocyanine pigment, and 10 parts by weight of paraffin wax were mixed by a fixed-tank type dry mixer, and the vent was opened. Melt kneading was performed with a twin-screw extruder while suction was connected to a suction pump.

This melt-kneaded product was crushed by a hammer mill to obtain a crushed toner composition of 1 mm mesh pass.
Further, the coarsely crushed product is crushed by a mechanical crusher to a volume average diameter of 20 to 30 μm, and then crushed by a jet mill utilizing collision between particles in a swirling flow. The toner composition was modified by mechanical and mechanical shearing force, and classified by a multi-stage classifier to obtain cyan toner particles (4) having a weight average diameter of 7.6 μm.

To 100 parts by weight of the cyan toner particles (4), 0.2 parts by weight of a melanin formaldehyde resin (A-1) having a number average particle diameter of 0.2 μm was treated with silicone oil in the same manner as in Example 1. 1.0 parts by weight of silica fine particles (B-1) having a number average particle diameter of 7 nm, and 1.0 parts by weight of titanium oxide fine particles (C-1) having a number average particle diameter of 0.27 μm.
After the addition by weight, the mixture was uniformly stirred using a Henschel mixer manufactured by Mitsui Mining Co., Ltd. to obtain a toner (13).

Evaluation was performed in the same manner as in Example 1 using this toner (13). Table 2 shows various physical properties of the toner, and Table 3 shows the evaluation results.

[0164]

Comparative Example 2 0.1 M-
After adding 450 parts by weight of an aqueous solution of Na ₃ PO ₄ and heating to 50 ° C., the mixture was stirred at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). 1.0M-Ca
70 parts by weight of a Cl ₂ aqueous solution was gradually added to obtain an aqueous medium containing a calcium phosphate salt.

On the other hand, a material having the following formulation was heated to 60 ° C.
Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.),
It was uniformly dissolved and dispersed at 00 rpm.

(Monomer) 170 parts by weight of styrene 30 parts by weight of n-butyl acrylate (colorant) I. Pigment Blue 15: 3 15 parts by weight (charge control agent) Salicylic acid metal compound 2 parts by weight (same as used in Example 1) (polar resin) Saturated polyester 20 parts by weight (acid value 10, peak molecular weight; 15,000) ( Release agent) Behenyl stearate 30 parts by weight (crosslinking agent) Divinylbenzene 0.2 parts by weight

Into this, 2 parts by weight of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

Without adding potassium persulfate to the aqueous medium, the above-mentioned polymerizable monomer composition was charged, and the mixture was heated at 50 ° C.
8,000r with TK homomixer under N ₂ atmosphere
The mixture was stirred at pm to granulate the polymerizable monomer composition.

Thereafter, the mixture was maintained for 4 hours while stirring with a paddle stirring blade, and then the temperature was raised at a rate of 40 ° C./Hr. Raise the temperature to 70 ° C with 5
Allowed to react for hours. After the completion of the polymerization reaction, the remaining monomer was distilled off under reduced pressure. After cooling, hydrochloric acid was added to dissolve the calcium phosphate salt, followed by filtration, washing with water, and drying.
1 μm cyan toner particles (5) were obtained.

The average circularity and particle size distribution of the obtained cyan toner particles (5) were measured using a flow type particle image measuring device manufactured by Toa Medical Electronics Co., Ltd.
The average circularity was 0.970, and the maximum value X was found only at the circle equivalent diameter of 5.8 μm, and the maximum value Y was not found at the circle equivalent diameter range of 0.6 to 2.0 μm. 0.60 equivalent circle diameter
The content of particles having a size of not less than μm and less than 2.00 μm was 4% by number.

A styrene particle (A) having a number average particle diameter of 0.1 μm was added to 100 parts by weight of the cyan toner particle (5).
-4) 0.05 parts by weight of titanium oxide fine particles (C-1) treated with silicone oil and having a number average particle size of 0.27 μm
Was added thereto and uniformly stirred using a Henschel mixer manufactured by Mitsui Mining Co., Ltd. to obtain a toner (14).

Evaluation was performed in the same manner as in Example 1 using this toner (14). Table 2 shows various physical properties of the toner, and Table 3 shows the evaluation results. The toner (14) did not have the maximum value Y in the range of the circle-equivalent diameter of 0.6 to 2.0 μm.

[0173]

Comparative Example 3 Cyan toner particles (1) used in Example 1
To 100 parts by weight, 9.0 parts by weight of a melamine formaldehyde resin (A-2) having a number average particle size of 1.2 μm and 1.0 parts of silica fine particles (B-1) having a number average particle size of 7 nm treated with silicone oil were used. Parts by weight, number average particle size 0.27
After adding 1.0 part by weight of titanium oxide fine particles (C-1) of μm, the mixture was uniformly stirred using a Henschel mixer manufactured by Mitsui Mining Co., Ltd. to obtain a toner (15).

Evaluation was performed in the same manner as in Example 1 using this toner (15). Table 2 shows various physical properties of the toner, and Table 3 shows the evaluation results.

[0175]

Comparative Example 4 A toner (16) was obtained in the same manner as in Example 1 except that the melamine formaldehyde resin (A-1) as the resin fine particles A was not used.

Evaluation was performed in the same manner as in Example 1 using this toner (16). Various physical properties of the toner are shown in Table 2, and the evaluation results are shown in Table 2.

[0177]

Comparative Example 5 In place of the melamine formaldehyde resin (A-1) used in Example 1, 0.4 part by weight of a styrene-acrylic copolymer (A-5) having a number average particle size of 1.8 μm was used. Except for, toner (17) was obtained in the same manner as in Example 1.

Evaluation was performed in the same manner as in Example 1 using this toner (17). Table 2 shows various physical properties of the toner, and Table 3 shows the evaluation results.

[0179]

Comparative Example 6 A toner (18) was obtained in the same manner as in Example 1, except that the silica fine particles (B-1) treated with silicone oil as the inorganic fine powder B were not used.

Evaluation was performed in the same manner as in Example 1 using this toner (18). Table 2 shows various physical properties of the toner, and Table 3 shows the evaluation results.

[0181]

Comparative Example 7 The number average particle diameter was 50 in place of the silicone oil-treated silica fine particles (B-1) used in Example 1.
A toner (19) was obtained in the same manner as in Example 1, except that 1.4 parts by weight of the silica fine powder (B-4) having a thickness of nm was used.

Evaluation was performed in the same manner as in Example 1 using this toner (19). Table 2 shows various physical properties of the toner, and Table 3 shows the evaluation results.

[0183]

[Table 2]

[0184]

[Table 3]

[0185]

According to the present invention, even when used for a long time under the same conditions of low temperature and low humidity, the toner which does not cause fusing to the charging member, the photoreceptor and the like and which can provide an image having excellent image density stability can be obtained. And an image forming method using the toner.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of an image forming apparatus used for evaluating a toner of the present invention.

FIG. 2 is an explanatory diagram of a developing device constituting an image forming apparatus used for evaluating the toner of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 photosensitive drum 2 charging device 3 laser beam 4 developing device 5 developing sleeve 6 elastic roller 7 elastic regulating blade 8 non-magnetic toner 9 transfer roller 10 cleaning blade 11 waste toner container 12 fixing device 13 paper 14 developing container 15 holding sheet metal 19 stirring member 21 Bias power supply

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tatehiko Chiba 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Satoshi Handa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Masanori Ito 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H005 AA06 AA08 AA15 AA21 AB06 CA12 CA14 CA21 CB07 CB13 EA03 EA05 EA07 FA07

Claims (20)

[Claims] 1. A toner having toner particles containing at least a binder resin and a colorant, and a fine powder externally added to the toner particles, wherein the toner has an average particle size measured by a flow-type particle image measuring apparatus. Roundness is 0.950 ~
0.995, a circle having a maximum value X at a circle equivalent diameter of 3 to 9 μm and a maximum value Y at a circle equivalent diameter of 0.6 to 2 μm in a particle size distribution of a circle equivalent diameter, and a circle of 0.60 to less than 2.00 μm. Particles having an equivalent diameter are 8 to 30% by number of the whole, and at least (A) the number average particle diameter is 0.05 to 2.0 μm;
The shape factor SF-1 is 100 to 150, and the shape factor S
F-2 is 100 to 200, and a spherical resin fine powder A having a nitrogen-containing polymer compound and (B) an inorganic fine powder B having a primary particle having a number average particle diameter of 1 to 30 nm are used. A toner characterized in that it contains a kind of fine powder on the surface of toner particles. 2. The resin fine powder A has a number average particle diameter of 0.1 to
The toner according to claim 1, wherein the thickness is 1.0 μm. 3. The toner according to claim 1, wherein the resin fine powder A is contained in an amount of 0.01 to 0.5% by weight based on the toner particles. 4. The toner according to claim 1, wherein the resin fine powder A is composed of a melanin formaldehyde resin or a benzoguanamine-formaldehyde resin. 5. The toner according to claim 1, wherein the fine resin powder A and / or the fine inorganic powder B contains silicone oil. 6. The toner according to claim 1, wherein the inorganic fine powder B is silica. 7. The toner according to claim 1, wherein the inorganic fine powder B is contained in an amount of 0.1 to 4.0% by weight based on the toner particles. 8. The toner according to claim 1, further comprising an inorganic fine powder C which is alumina and / or titanium oxide on the surface of the toner particles. 9. The toner according to claim 8, wherein the number average particle diameter of the primary particles of the inorganic fine powder C is less than 0.6 μm. 10. The toner according to claim 8, wherein the inorganic fine powder C is contained in an amount of 0.1 to 3% by weight based on the toner particles. 11. The toner particles are produced by a polymerization method in which a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is polymerized in a liquid medium in the presence of a polymerization initiator. Claims 1 to
11. The toner according to any one of items 10 to 10. 12. The toner according to claim 11, wherein the liquid medium is an aqueous medium. 13. The toner according to claim 1, wherein the toner is a non-magnetic toner. 14. The toner according to claim 1, wherein the toner is used as a one-component developer. 15. The toner according to claim 1, wherein the toner is a non-magnetic toner, and the non-magnetic toner is used as a non-magnetic one-component developer. 16. The toner comprises a releasing agent on the surface and / or inside of the toner particles, wherein the releasing agent has a temperature of 40 ° C. to 120 ° C.
The toner according to any one of claims 1 to 15, further comprising a wax having a maximum endothermic peak measured by DSC in a region of ° C. 17. The toner according to claim 16, wherein the release agent contains a wax having a maximum endothermic peak measured by DSC in a range of 40 ° C. to 90 ° C. 18. The toner particles contain at least a binder resin, a colorant and a release agent, and the toner particles contain 3 to 40 parts by weight of the release agent based on 100 parts by weight of the binder resin. The toner according to any one of claims 1 to 17, wherein the toner is contained. 19. The toner according to claim 16, wherein the release agent contains an ester wax having at least one long-chain ester moiety having 10 or more carbon atoms. 20. A toner image formed on an electrostatic image carrier by developing with a charged toner using a toner carrier for carrying the toner and toner applying means for applying the toner to the toner carrier. 20. An image forming method comprising: forming a toner image on a transfer material; transferring the toner image onto the transfer material; and heat-fixing the toner image on the transfer material.
An image forming method, wherein the toner is the toner according to any one of the above.