JP2002268263A - Electrostatic latent image developer and method/device for development using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-magnetic single-component electrostatic latent image developer and a method/device for development using it by which a picture of an excellent quality can be obtained by keeping the fluidity, chargeability, developing property, fog resistance on photosensitive material, stain resistance in the device, etc., of toner to be good through a long period. SOLUTION: The electrostatic latent image holding body holding an electrostatic latent image and a developer supporter supporting non-magnetic toner are made to face each other. By using the same toner as primary toner as replenishment toner in the case of toner end, the non-magnetic toner of the developer supporter is given to the electrostatic latent image of the electrostatic latent image holding body to perform development with toner of a grain size smaller than that of the toner on the developer supporter. The single component developer consists of the non-magnetic toner to be used for this developing method. The relation between the number average grain sizes of the toner to be supplied to the developer supporter and a volume average grain size is the volume average grain size/number average grain sizes <=1.2. the relation between the volume average grain size (a) of a primary toner A, the volume average grain sizes (b) in the case of toner end and the volume average grain size (c) after toner replenishment is 1.0<=(bc)/a<2> <1.2. The volume average grain sizes is 5 to 11 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer, a developing method, and a developing device in an electrophotographic system, and more particularly, to a non-magnetic one-component developer capable of stably controlling a print density and a background stain over time. And a method for developing an electrostatic latent image using the same, and a developing device.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic developing method using a one-component developer, a toner layer is formed on a developer carrier,
A contact development method of performing development by contacting the electrostatic latent image holding member,
There are non-contact development methods such as a jumping development method and a projection development method in which the toner layer is not directly contacted with the electrostatic latent image holding member and the toner flies on the electrostatic latent image holding member by the electrostatic latent image. When a toner is used in a developing device that forms a thin toner layer on a developer carrying member, it is necessary to minimize the thickness of the toner layer on the surface of the developer carrying member in order to impart uniform charge to the toner. In addition, the particle diameter of the toner developed on the developer holding member is selected, and the particle diameter of the toner developed on the developer holding member is significantly smaller than that of the toner supplied to the developer hopper. As development is repeated,
Since the toner having a smaller particle diameter is consumed, the particle diameter of the toner developed in the popper and on the developer holding member tends to gradually increase. Therefore, the particle diameter of the toner differs between the initial stage and the aging. Accordingly, the chargeability is different, and after continuous copying, background stains, unevenness, and the like are generated on the image, and the color tone tends to fluctuate particularly in the case of a color toner. Furthermore, when replenishing the toner, the residual toner has a reverse charging property due to a difference between the residual toner charge amount at the time of toner end and the initial toner charge amount, and is generated as a background stain on an image.

Several methods have been proposed to solve such a conventional problem. For example, Tokuho 7-8924
In Japanese Patent Application Publication No. 0-204, the types of additives of the initial toner and the replenishment toner are changed, and the charge amounts of the initial toner and the replenishment toner are set to be different. A method to maintain sex has been proposed. But,
The developer is effective for a two-component developer, but when used as a one-component toner, the particle size increases depending on the development selected, and the charge amount of the remaining toner at the time of toner end decreases. If replenishment toner whose charge is set lower than the initial level is replenished so as to match the charge amount of the remaining toner, the replenishment toner set at a lower charge amount must be replenished at the next toner replenishment. It is necessary to keep changing the kind and amount of the agent. It is difficult to lower the toner charge amount each time replenishment is performed.

[0004] Also, in Japanese Patent No. 2527473,
A method has been proposed in which the additive content of the initial toner and the replenishment toner is changed to reduce the difference between the charge amounts of the initial toner and the replenishment toner after a decrease in standing, thereby maintaining image stability. This is to anticipate a decrease in the charge of the initial toner, set the charge amount of the replenishment toner low, and reduce the difference in charge amount. However, the developer is effective for a two-component developer, but when used as a one-component toner, the particle size of the initial toner increases due to development selection, and the charge amount of the remaining toner at the time of toner end is reduced. descend. If replenishment toner with low charge is replenished to the remaining toner, the charge amount is further reduced at the time of the next toner end, and replenishment toner having a lower charge amount must be replenished at the time of the next toner replenishment. And the amount of the additive must be changed continuously. It is difficult to lower the toner charge amount each time replenishment is performed.

Further, Japanese Patent No. 2528511 discloses a replenishing toner containing an external additive of opposite polarity by changing the additive surface treatment agent of the initial toner and the replenishing toner to reduce the charge lowered at the time of toner end of the initial toner. There has been proposed a method for reducing the difference in charge amount and maintaining image stability.
However, the developer is effective for a two-component developer, but when used as a one-component toner, the particle size of the initial toner increases due to development selection, and the charge amount of the remaining toner at the time of toner end is reduced. descend. By replenishing the remaining toner with a replenishing toner having an additive of the opposite polarity, the remaining toner can be prevented from becoming reversely charged, and the background stain on the image does not occur. However, at the time of the next toner end, the charge amount further decreases, and it is necessary to replenish the replenishment toner containing the external additive having a stronger reverse polarity, and it is difficult to change the toner external additive for each replenishment. .

[0006] These effects are not all satisfactory.
In particular, in a full-color developing system in which four colors are superimposed, it is necessary to more precisely control the background contamination and the amount of toner development, and therefore, there remains a problem in long-term stabilization of the toner charge amount.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances of the prior art, and has excellent toner charging stability over time without distinguishing between an initial toner and a replenishment toner. A non-magnetic one-component toner (developer) for an electrostatic latent image developer, which can stably control the print density and background stain caused by the toner, and does not cause the background stain at the time of toner replenishment and the print density fluctuation. An object of the present invention is to provide a developing method and a developing device using the same.

[0008]

Means for Solving the Problems The present inventors have focused on the particle size variation and the charge variation in the non-magnetic one-component development process,
As a result of intensive studies to achieve the above object, the electrostatic latent image holding member holding the electrostatic latent image and the developer holding member holding the non-magnetic one-component toner are opposed to each other. In the developing method of applying the non-magnetic one-component toner to the electrostatic latent image of the electrostatic latent image holding member and developing with a toner having a smaller particle diameter than the toner on the developer carrying member, Using the same toner as the initial toner, the volume average particle diameter a of the initial toner A supplied to the developer carrier, the volume average particle diameter b at the time of toner end, and the volume average particle diameter c after toner replenishment are used. The relationship is 1.0 ≦
(Bc) / a ² <1.2, and the relationship between the number average particle size and the volume average particle size of the toner is volume average particle size / number average particle size ≦ 1.2, and the volume average particle size is From 5 to 11μ
By finding m, it was found that the particle size variation and charging variation were significantly improved, and the present invention was completed.

That is, according to the present invention, the electrostatic latent image holding member for holding the electrostatic latent image and the developer holding member for holding the non-magnetic toner are opposed to each other, and the initial toner And applying the non-magnetic toner of the developer carrying member to the electrostatic latent image of the electrostatic latent image holding member using the same toner as described above, and developing with a toner having a smaller particle diameter than the toner on the developer carrying member. A one-component developer comprising a non-magnetic toner used in the developing method, wherein the relationship between the number average particle diameter and the volume average particle diameter of the toner supplied to the developer carrier is volume average particle diameter / number average particle diameter ≦ 1.2, and the relationship among the volume average particle diameter a of the initial toner A, the volume average particle diameter b at the time of toner end, and the volume average particle diameter c after toner replenishment is 1.0 ≦ (bc) / a ^2. <1.2 and the volume average particle size is 5 to 1 Non-magnetic one-component electrostatic latent image developer, which is a μm is provided. According to the present invention, there is provided the above-mentioned non-magnetic one-component electrostatic latent image developer, wherein the toner contains an external additive.
According to the present invention, there is provided the above-mentioned non-magnetic one-component electrostatic latent image developer, wherein the external additive comprises two or more external additives having different particle diameters. Further, according to the present invention, the external additive has a BET specific surface area of 20 to
The non-magnetic one-component electrostatic latent image developer according to any one of the above, which comprises at least one external additive in the range of 250 m ² / g. According to the invention, the external additive comprises silica, a titanium compound, alumina, cerium oxide, calcium carbonate, magnesium carbonate, calcium phosphate, fluorine-containing resin fine particles, silica-containing resin fine particles, and nitrogen-containing resin fine particles. The non-magnetic one-component electrostatic latent image developer according to any one of the above, wherein the developer is selected from the group. Further, according to the present invention, the electrostatic latent image holding member holding the electrostatic latent image is opposed to the developer holding member holding the non-magnetic toner, and the same toner as the initial toner is used as the replenishment toner at the time of toner end. A developing method of applying the non-magnetic toner of the developer carrier to the electrostatic latent image of the electrostatic latent image holding member and developing the toner having a smaller particle diameter than the toner on the developer carrier. In addition, there is provided a developing method using any one of the non-magnetic one-component electrostatic latent image developers described above as a developer. Furthermore, according to the present invention, an electrostatic latent image holding member for holding at least an electrostatic latent image, a developer holding member for holding a non-magnetic toner provided between the electrostatic latent image holding member, and a developer supply hopper are provided. In a developing device provided with the developing device, a non-magnetic one-component electrostatic latent image developer described in any of the above is used as a developer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The toner constituting the non-magnetic one-component electrostatic latent image developer of the present invention usually comprises at least toner particles and one or more external additives, and the toner particles further comprise a binder resin and a colorant as main components. Contains. (Toner Particles) The relationship between the number average particle diameter and the volume average particle diameter of the toner particles used in the present invention is such that volume average particle diameter / number average particle diameter ≦ 1.2. The relationship between the particle diameter a, the volume average particle diameter b at the time of toner end, and the volume average particle diameter c after toner replenishment is 1.0 ≦ (b
c) / a ² <1.2. The particle size of the toner was measured using a Coulter Counter Multisizer (manufactured by Coulter) with a 100 μm aperture.
This was done by measuring the average of the particle size of the 000 particles. If the relationship between the number average particle diameter and the volume average particle diameter is such that volume average particle diameter / number average particle diameter> 1.2, the particle diameter fluctuation at the time of toner end is large, and filming to the thin layer regulating member is difficult. As a result, the toner development amount cannot be controlled, and the toner charge amount is not stable.

The relationship between the volume average particle diameter a of the initial toner A, the volume average particle diameter b at the time of toner end, and the volume average particle diameter c after toner replenishment is 1.0 ≦ (bc) / a ² <1. .
If the number 2 is not satisfied, it becomes difficult to control the amount of toner charge and the amount of toner development, and therefore, background staining and toner density fluctuation at the time of toner replenishment will be caused.
For example, the relationship between the volume average particle diameters is (bc) / a ² <1.0
In the case of toner replenishment, the replenishment toner has a reverse charging property when the toner is replenished, so that it becomes difficult to control the toner charge amount and the toner development amount, and the background stain and the print density fluctuation at the time of toner replenishment occur. Would. Also, (bc) /
Even when a ² > 1.2, when toner is replenished, the remaining toner has reverse charging properties, making it difficult to control the amount of toner charge and the amount of toner development. Print density fluctuation occurs.

As a method for producing toner particles in which the relationship between the number average particle diameter and the volume average particle diameter is such that volume average particle diameter / number average particle diameter ≦ 1.2, a toner that satisfies the relational expression range can be produced. The method is not particularly limited, and a known method can be used.In general, if necessary, a kneading agent such as a release agent, a charge controlling agent, and an offset preventing agent together with a binder resin and a colorant, Pulverization, kneading and pulverization methods obtained by classification and the like are mentioned, a manufacturing method of changing the shape by applying a mechanical impact force or thermal energy as necessary, and also using the toner particles obtained by the method as a core, Further, a manufacturing method in which agglomerated particles are adhered and fused by heating to have a core-shell structure may be used.

The binder resin used in the present invention includes styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate, methyl acrylate,
Α-methylene aliphatic monocarboxylic esters such as ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and dodecyl methacrylate, vinyl methyl ether,
Vinyl ethyl ethers, vinyl ethers such as vinyl butyl ether, homopolymers and copolymers such as vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone, and particularly, as typical binder resins, Polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyethylene, polypropylene and the like. be able to. Further, polyester resin, polyol resin, polyurethane resin, epoxy resin, silicone resin, polyamide resin, modified rosin, paraffin wax and the like can be mentioned.

Among these, polyester resins and polyol resins are particularly preferred from the viewpoint of color development and image strength. In the case of polyester resins, those having an acid value of 20 KOH mg / g or less are preferred from the viewpoint of chargeability. 5KOH
Those having mg / g or less are more preferred. Polyester resins include those obtained by a reaction between a polyhydric alcohol component and a polyhydric carboxylic acid component. As the polyhydric alcohol component, those using a bisphenol A alkylene oxide adduct as a main component are preferably used. . The polyol resin caps the end of the epoxy resin,
Further, those having a polyoxyalkylene moiety in the main chain are preferred. For example, epoxy resin of both ends glycidyl group,
Those obtained by reacting an alkylene oxide adduct of a dihydric phenol at both terminal brisidyl groups with a polyhydric phenol or the like are preferably used.

The coloring agents used in the present invention include carbon black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate,
Lamp Black, Rose Bengal, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 12
2, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 17, C.I. I. Pigment Blue 15: 1, C.I.
I. Dyes and pigments such as CI Pigment Blue 15: 3 are typical examples.

[0016] In addition to the binder resin and the colorant, a releasing agent for preventing offset can be added to the toner particles of the present invention, if necessary. Examples of the release agent include waxes such as low molecular weight polypropylene and low molecular weight polyethylene. As the charge control agent, known ones can be used, and among them, an azo-based metal complex compound and a charge control agent of a metal complex compound of salicylic acid can be preferably used.

The toner particles of the present invention have a volume average particle size of 5 to 11 μm, and more preferably 4 to 8 μm. If the volume average particle size exceeds 11 μm, the toner particles do not faithfully develop into the latent images of dots and lines, and the reproduction of a photographic image or the reproduction of fine lines may be poor. If the volume average particle size is less than 5 μm, the surface area per toner unit becomes large, and it becomes difficult to control the chargeability and toner fluidity, and a stable image may not be obtained.

(External Additives) As the external additives constituting the toner of the present invention, known external additives such as inorganic fine particles and organic fine particles can be used. Among them, silica, titania, alumina and oxidized fine particles are known. Organic resin fine particles such as inorganic fine particles such as cerium, strontium titanate, calcium carbonate, magnesium carbonate and calcium phosphate, fluorine-containing resin fine particles, silica-containing resin fine particles and nitrogen-containing resin fine particles are preferable. Further, the surface of the external additive may be subjected to a surface treatment according to the purpose. Examples of the surface treatment agent include a silane compound for performing a hydrophobic treatment, a silane coupling agent, and a silicone oil.

Further, it is preferable to contain two or more external additives having different particle diameters, and it is preferable to contain external additives having an average particle diameter having a particle diameter difference of about 2 to 5 times.
The titanium compound used as the external additive preferably has an average primary particle diameter of 100 nm or less, and is preferably 10 nm or less.
Those having a range of 70 nm are more preferable. Further, when this titanium compound is used as the first external additive, aggregation is small and the difference in the amount of adhesion between toner particles is small, which is preferable.

When two or more kinds of external additives having different particle diameters are not contained, the burying of the external additives into the toner matrix with time progresses rapidly, and the deterioration of the toner fluidity progresses rapidly. Image unevenness due to a decrease in the fluidity of the toner is apt to occur, and the adhesion to the toner is hardly increased, and the toner is easily detached from the toner, causing damage to the photosensitive material and image loss. When two or more kinds of external additives having different particle diameters are contained, the external additives having a large particle diameter serve as a spacer, and the external additives having a small particle diameter, which is effective for toner fluidity, are prevented from being embedded in the toner matrix. Thus, toner fluidity can be maintained.

The external additive has a BET specific surface area of 20 to 2
Those having 50 m ² / g are preferred. For example, an external additive having a large particle size has a BET specific surface area of about 20 to 80 m ² /
g means that the BET specific surface area is in this range, various surface-treated ones can be used, and especially those having a surface area of 20 to 50 m ² / g are more preferable.
If it is less than 20 m ² / g, image unevenness due to a decrease in the fluidity of the toner is apt to occur, and the adhesion to the toner is hard to be strong. This may cause the image to drop. These external additives having a large particle size are used in an amount of 0.1 to 100 parts by weight of the toner.
It is preferable to add in a range of 5.0 parts by weight,
More preferably, it is added in the range of 2.0 parts by weight. 0.
When the amount is less than 1 part by weight, transfer failure occurs. When the amount is more than 5.0 parts by weight, detachment from the toner easily occurs, which causes damage to the photosensitive material and image loss.

The external additive having a small particle size means a material having a BET specific surface area in a range of about 100 to 250 m ² / g. Can be used, in particular, from 120 to 200
m ² / g is more preferable, and is effective for reducing the adhesion of toner. It is preferable to add these external additives having a small particle diameter in the range of 0.05 to 10 parts by weight, and more preferably in the range of 0.1 to 5.0 parts by weight, based on 100 parts by weight of the toner. preferable. When the amount is less than 0.05 part by weight, the effect is not sufficiently exhibited, and when the amount is more than 10 parts by weight, the amount of the external additive detached from the toner increases, and the photosensitive member is easily damaged.

The total amount of the external additives to the toner is
In order to uniformly adhere to the toner particles, it is preferable to increase the addition amount of the external additive.However, the charge amount, the powder characteristics, the cost, the aggregation state of the external additive, the defect due to the free external additive, etc. Is appropriately determined in consideration of the balance of

[0024]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following description, all “parts” mean “parts by weight” unless otherwise specified.

(Synthesis Example of Polyester Resin) Synthesis Example 1 Stirrer, thermometer, nitrogen inlet, falling condenser,
In a four-necked separable flask with a cooling tube, 740 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2,
2) 300 g of 2,2-bis (4-hydroxyphenyl) propane, 466 g of dimethyl terephthalate, 80 g of isododecenyl succinic anhydride, and 114 g of tri-n-butyl 1,2,4-benzenetricarboxylate were added together with the esterification catalyst. Under a nitrogen atmosphere, the temperature was raised to normal temperature to 210 ° C. in the first half, and the reaction was performed while stirring at 210 ° C. under reduced pressure in the latter half. Acid value 2.3KOHmg / g, hydroxyl value 28.0KOHmg
/ G, a softening point of 106 ° C and a Tg of 62 ° C were obtained (hereinafter referred to as polyester resin A).

Synthesis Example 2 Polyoxypropylene (2,2) -2,2-bis (4-
(Hydroxyphenyl) propane 725 g, polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 165 g, terephthalic acid 500 g, isododecenyl succinic anhydride 130 g, 1,2,4-benzenetricarboxylic acid triisopropyl 170 g were added to the flask along with the esterification catalyst. These were reacted with the same apparatus and the same recipe as in Synthesis Example 1 to obtain an acid value of 0.5 KO.
A polyester resin having an Hmg / g, a hydroxyl value of 25.0 KOHmg / g, a softening point of 109 ° C, and a Tg of 63 ° C was obtained (hereinafter referred to as polyester resin B).

(Synthesis Example of Polyol Resin) Synthesis Example 1 In a separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a condenser, 378.4 g of a low-molecular bisphenol A type epoxy resin (number average molecular weight: about 360) was added. High molecular weight bisphenol A type epoxy resin (number average molecular weight: about 270
0) 86.0 g, glycidylated bisphenol A-type propylene oxide adduct (total number of moles of propylene oxide added: about 2.1) 191.0 g, bisphenol F 274.5 g, p-cumylphenol 70.1 g, xylene 200 g Was added. 70-100 under nitrogen atmosphere
° C, and 0.1839 g of lithium chloride was added. The temperature was further raised to 160 ° C, and xylene was distilled off under reduced pressure.
Polymerization is carried out at a reaction temperature of 0 ° C. for 6 to 9 hours to obtain an acid value of 0.0K.
A polyol resin having an OH mg / g, a hydroxyl value of 70.0 KOH mg / g, a softening point of 109 ° C. and a Tg of 58 ° C. was obtained (hereinafter referred to as a polyol resin A).

Synthesis Example 2 Using the apparatus of Synthesis Example 1, 205.3 g of a low molecular weight bisphenol A type epoxy resin (number average molecular weight: about 360),
54.0 g of high molecular weight bisphenol A type epoxy resin (number average molecular weight: about 3000), 432.0 g of glycidylated bisphenol A type propylene oxide adduct (total mole number of propylene oxide: about 2.2), bisphenol F282. 7 g, p-cumylphenol 2
6.0 g and 200 g of xylene were added. The temperature was raised to 70 to 100 ° C. in a nitrogen atmosphere, and lithium chloride was added to 0.183.
g was further added, the temperature was raised to 160 ° C., xylene was distilled off under reduced pressure, and polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours to obtain an acid value of 0.0 KOH mg / g and a hydroxyl value of 58.0 KOH mg.
/ G, a softening point of 109 ° C and a Tg of 58 ° C were obtained (hereinafter referred to as polyol resin B).

Example 1 Production Example 1 of Base Toner Binder Resin 100 parts of polyester resin A Colorant 4 parts of quinacridone-based magenta pigment Charge control agent 4 parts of zinc compound of salicylic acid The above raw materials were mixed with a Henschel mixer, The mixture was melted and kneaded by a buscon kneader (manufactured by Buss Corp.) set at 120 ° C., and the obtained kneaded product was cooled and then finely pulverized by a pulverizer using a turbo mill (manufactured by Turbo Kogyo).
Classification was performed using an air classifier to obtain a magenta mother toner a having the following particle diameter. Number average diameter: 5.8 μm Volume average particle diameter: 6.4 μm Volume average particle diameter / number average particle diameter: 1.1 Base toner a10 obtained in Production Example 1 of the base toner
0 parts, HDK2000H (Wack
er company, BET specific surface area: 140 m ² / g)
Wt% and AEROSIL RX50 (Nippon Aerosil Co., Ltd. · BET specific surface area: 50m ² / g) 1.0 wt%, MT150 as titania (manufactured by Tayca Corporation · BET specific surface area: 65m ² / g) 0.5 wt% The mixture was sufficiently mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain a toner for an electrostatic latent image developer.

Example 2 100 parts of the base toner a obtained in Production Example 1 of the base toner were mixed with T as silica.
G-810G (BET specific surface area: 23 manufactured by CABOT)
0 m ² / g) and 0.5% by weight of AEROSILRX
50 (manufactured by Nippon Aerosil Co., Ltd., BET specific surface area: 50 m ²⁾
/ G) and 0.5% by weight of MT150 (manufactured by Teica Co., Ltd., BET specific surface area: 65 m ² / g) as titania, and thoroughly mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.). A toner for an electrostatic latent image developer was obtained.

Example 3 100 parts of the base toner a obtained in Production Example 1 of the base toner were mixed with A as silica.
EROSIL RX200 (BE manufactured by Nippon Aerosil Co., Ltd.)
0.5 wt% of T specific surface area: 200 m ² / g) and AEROSIL RX50 (BE manufactured by Nippon Aerosil Co., Ltd.)
1.0 wt% of T specific surface area: 50 m ² / g) and MT150 (manufactured by Teica Co., Ltd., BET specific surface area: 65) as titania
m ² / g) was added in an amount of 0.5% by weight and sufficiently mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain a toner for an electrostatic latent image developer.

Example 4 100 parts of the base toner a obtained in Production Example 1 of the base toner were mixed with H as silica.
DK2000H (Wacker BET specific surface area:
140 m ² / g) and 0.7% by weight of AEROSIL
RX50 (BET specific surface area: 5 manufactured by Nippon Aerosil Co., Ltd.)
0 m ² / g) in an amount of 1.0% by weight.
0.5 (BET specific surface area: 65 m ² / g, manufactured by Teica), AluminumOx as alumina
ideC (Nippon Aerosil Co., Ltd., BET specific surface area: 10
0m ² / g), and sufficiently mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain a toner for an electrostatic latent image developer.

Example 5 Preparation Example 2 of Base Toner Binder Resin 100 parts of polyester resin B Colorant 4 parts of quinacridone-based magenta pigment Charge control agent 4 parts of chromium compound of salicylic acid The mixture was melted and kneaded by a buscon kneader (manufactured by Buss Corp.) set at 120 ° C., and the obtained kneaded product was cooled and then finely pulverized by a pulverizer using a turbo mill (manufactured by Turbo Kogyo).
Classification was performed using an air classifier to obtain a magenta base toner b having the following particle size. Number average diameter: 5.9 μm Volume average particle diameter: 6.6 μm Volume average particle diameter / number average particle diameter: 1.1 Base toner b10 obtained in Production Example 2 of the base toner
0 parts, HDK2000H (Wack
er company, BET specific surface area: 140 m ² / g)
Wt% and AEROSIL RX50 (Nippon Aerosil Co., Ltd. · BET specific surface area: 50m ² / g) 1.0 wt%, MT150 as titania (manufactured by Tayca Corporation · BET specific surface area: 65m ² / g) 0.5 wt% 0.02% by weight of alumina, AluminumOxideC (manufactured by Nippon Aerosil Co., Ltd., BET specific surface area: 100 m ² / g)
Was added and thoroughly mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain a toner for an electrostatic latent image developer.

Example 6 Production Example 3 of Base Toner Binder Resin Polyol Resin A 100 parts Coloring agent Quinacridone-based magenta pigment 4 parts Charge control agent Salicylic acid zinc compound 4 parts The above raw materials were mixed with a Henschel mixer. I
With a buscon kneader (Bus) manufactured at 120 ° C
After melting and kneading the resulting kneaded product,
Finely pulverized with a pulverizer using (Turbo Industries)
Classify using a wind classifier and obtain a magenta matrix
Nurse c was obtained. Number average diameter: 6.3 μm Volume average particle diameter: 7.0 μm Volume average particle diameter / number average particle diameter: 1.1 Base toner c10 obtained in Production Example 3 of base toner above
AEROSIL RX50 (Nippon Aerospace)
BET specific surface area: 50m^Two/ G) is 1.0 weight
%, Titania as MT150
Surface area: 65m ^Two/ G) was added in an amount of 0.5% by weight.
Mix well with a shell mixer (Mitsui Miike Co., Ltd.)
A toner for a latent image developer was obtained.

Example 7 Production of Base Toner 4 Binder Resin Polyol Resin B 100 parts Colorant Quinacridone-based magenta pigment 4 parts Charge control agent Chromium compound of salicylic acid 2 parts The above raw materials were mixed with a Henschel mixer, The mixture was melted and kneaded by a buscon kneader (manufactured by Buss Corp.) set at 120 ° C., and the obtained kneaded material was cooled and then finely pulverized by a pulverizer using a turbo mill (manufactured by Turbo Kogyo).
Classification was performed using an air classifier to obtain a magenta base toner d having the following particle size. Number average diameter: 6.1 μm Volume average particle diameter: 6.8 μm Volume average particle diameter / number average particle diameter: 1.1 Base toner d10 obtained in Production Example 4 of base toner above
0 parts, AEROSIL R976 as silica
(Nippon Aerosil Co., Ltd., BET specific surface area: 300 m ² /
g) was added thereto and mixed well with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain a toner for an electrostatic latent image developer.

Example 8 Preparation of Base Toner 5 Binder Resin Polyol Resin B 100 Parts Coloring Agent Quinacridone Magenta Pigment 4 Parts Charge Control Agent Salicylic Acid Chromium Compound 2 Parts The above raw materials were mixed with a Henschel mixer. The mixture was melted and kneaded by a buscon kneader (manufactured by Buss Corp.) set at 120 ° C., and the obtained kneaded product was cooled and then finely pulverized by a pulverizer using a turbo mill (manufactured by Turbo Kogyo).
Classification was performed using an air classifier to obtain a magenta base toner e having the following particle diameter. Number average diameter: 7.5 μm Volume average particle diameter: 8.6 μm Volume average particle diameter / number average particle diameter: 1.1 Based on 100 parts of base toner e of Production Example 5 of base toner,
HDK2000H (Wacker B
0.7% by weight of ET specific surface area: 140 m ² / g) and AEROSIL RX50 (BE manufactured by Nippon Aerosil Co., Ltd.)
1.0 wt% of T specific surface area: 50 m ² / g) and MT150 (manufactured by Teica Co., Ltd., BET specific surface area: 65) as titania
m ² / g) was added thereto and mixed thoroughly with a Henschel mixer (manufactured by Mitsui Miike) to obtain a toner for an electrostatic latent image developer.

(Comparative Example 1) Preparation Example 6 of Base Toner Using the same materials as in Preparation Example 1 of base toner, mixing was performed by a Henschel mixer, and then melt-kneaded by two rolls set at 130 ° C. After cooling the kneaded material, it was finely pulverized by a pulverizer using a turbo mill (manufactured by Turbo Kogyo Co., Ltd.) and classified using an air classifier to obtain a magenta base toner f having the following particle diameter. Number average diameter: 5.1 μm Volume average particle diameter: 6.4 μm Volume average particle diameter / number average particle diameter: 1.3 Base toner f10 obtained in Production Example 6 of the base toner
0 parts, HDK2000H (Wack
er company, BET specific surface area: 140 m ² / g)
Wt% and AEROSIL RX50 (Nippon Aerosil Co., Ltd. · BET specific surface area: 50m ² / g) 1.0 wt%, MT150 as titania (manufactured by Tayca Corporation · BET specific surface area: 65m ² / g) 0.5 wt% The mixture was sufficiently mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain a toner for an electrostatic latent image developer.

Comparative Example 2 Preparation of Base Toner 7 A magenta base toner having the following particle size was obtained by using the same materials as in Preparation Example 1 of the base toner and changing the pulverization and classification conditions in Preparation Example 1. g was obtained. Number average particle diameter: 6.1 μm Volume average particle diameter: 6.9 μm Volume average particle diameter / number average particle diameter: 1.1 Base toner g10 obtained in Production Example 7 of base toner above
0 parts, HDK2000H (Wack
er company, BET specific surface area: 140 m ² / g)
1.2% by weight of AEROSIL RX50 (manufactured by Nippon Aerosil Co., Ltd., BET specific surface area: 50 m ² / g), and 0.5% by weight of MT150 (manufactured by Teika Co., Ltd., BET specific surface area: 65 m ² / g) as titania. The mixture was sufficiently mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain a toner for an electrostatic latent image developer.

Comparative Example 3 Production Example 8 of Base Toner Using the same materials as in Production Example 1 of the base toner, they were mixed by a Henschel mixer and then melt-kneaded by a twin screw extruder set at 130 ° C. After cooling the kneaded product, the mixture was finely pulverized by a pulverizer using a jet stream (the pulverizing apparatus of Production Example 1 was changed), and classified using an air classifier to obtain a magenta base toner h having the following particle size. . Number average diameter: 6.2 μm Volume average particle diameter: 7.1 μm Volume average particle diameter / number average particle diameter: 1.1 Base toner h10 obtained in Production Example 8 of base toner above
0 parts, HDK2000H (Wack
er company, BET specific surface area: 140 m ² / g)
Wt% and AEROSIL RX50 (Nippon Aerosil Co., Ltd. · BET specific surface area: 50m ² / g) 1.0 wt%, MT150 as titania (manufactured by Tayca Corporation · BET specific surface area: 65m ² / g) 0.5 wt% The mixture was sufficiently mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain a toner for an electrostatic latent image developer.

[Measurement of Physical Properties] (Particle Size) The particle size of the toner was measured with a particle size analyzer “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. The volume average particle size and the number average particle size were determined by the above particle size analyzer. (Charge amount) Carrier (Powdertech Co., Ltd .: FPC-3)
00) 6 g of the toner was weighed at 5 wt%, charged into a sealable metal cylinder, stirred at 150 rpm for 15 minutes, and the obtained developer was blown to determine the charge amount.

[Evaluation on Actual Apparatus] The electrostatic latent image developer composed of the toner obtained in each of Examples and Comparative Examples was subjected to a copy test using a modified machine of “IPSIO Color 5000” manufactured by Ricoh Co., Ltd., and evaluated. Was. The modified machine is "Co
lor5000 ”process speed up to 6 per minute
An A4 sheet set in a state where a full-color copy can be collected was used. The copy test was performed in a 30,000-sheet full color mode including black. Immediately after start of copy test and 3
After the execution of 10,000 copies, the charge amount of the developer in the developing machine and the obtained image density were measured to evaluate the image quality. (1) The image density is “X-write 938” (X-ri
te). (2) The image quality was visually evaluated to determine whether or not there was any unevenness in image density, non-image portion fogging, missing images, and the like. <Evaluation criteria> ○: good, △: bad, ×: very bad

[0042]

[Table 1]

As shown in Table 1, the electrostatic latent image developers of Examples 1 to 8 of the present invention were manufactured by Ricoh Co., Ltd. as "IPSIO Color".
In a test using a "5000" modified machine, it can be seen that excellent performance was exhibited in density, image quality, and background stain, and there was no problem from the viewpoint of maintainability. On the other hand, the electrostatic latent image developers of Comparative Examples 1 to 3 had no particular problem at the initial stage, but after 30,000 sheets, the particle size of the toner greatly changed due to the selection of the particle size over time, and the chargeability of the toner was changed. Was different from the initial stage, and background color stain, image density fluctuation, blurring, etc. occurred on the image, and the color tone fluctuated. Further, when the toner was replenished, the image density was increased, but the background was stained.

[0044]

According to the present invention, the fluidity, chargeability, developability, fogging on photosensitive material, anti-fouling property, etc. of the toner can be satisfied simultaneously and for a long period of time. To provide a non-magnetic one-component electrostatic latent image developer capable of obtaining a good image over a long period of time, and a developing method and a developing apparatus using the same.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/08 112 G03G 15/08 112 507 507L (72) Inventor Hiroyuki Fushimi 1-chome Nakamagome, Ota-ku, Tokyo No. 3-6 Ricoh Co., Ltd. (72) Kazuyuki Yazaki 1-3-6 Nakamagome 1-chome, Ota-ku, Tokyo Tokyo (72) Inventor Osamu Uchinokura 1-3-3 Nakamagome, Ota-ku, Tokyo No. 6 F-term in Ricoh Co., Ltd. (reference) 2H005 AA08 CA01 CA11 CA12 CB07 CB08 CB13 EA05 EA10 FA07 2H077 AD06 DA16 DB01 EA14

Claims (7)

[Claims] An electrostatic latent image holding member for holding an electrostatic latent image;
The developer carrier that carries the non-magnetic toner is opposed to the toner carrier, and the same toner as the initial toner is used as the replenishment toner at the time of toner end. A one-component developer made of a non-magnetic toner used in a developing method of giving to the electrostatic latent image and developing with a toner having a smaller particle size than the toner on the developer carrier, and supplied to the developer carrier The relationship between the number average particle diameter and the volume average particle diameter of the toner is volume average particle diameter / number average particle diameter ≦ 1.2, and the volume average particle diameter a of the initial toner A and the volume average particle diameter b at the end of the toner 1.0 ≦ (bc) / a with respect to the volume average particle diameter c after toner replenishment.
² <1.2 and a non-magnetic one-component electrostatic latent image developer having a volume average particle size of 5 to 11 μm. 2. The non-magnetic one-component electrostatic latent image developer according to claim 1, wherein the toner contains an external additive. 3. The non-magnetic one-component electrostatic latent image developer according to claim 2, wherein the external additive comprises at least two types of external additives having different particle diameters. 4. The external additive having a BET specific surface area of 2
The non-magnetic one-component electrostatic latent image developer according to claim 2, further comprising at least one external additive in a range of 0 to 250 m ² / g. 5. The external additive is selected from the group consisting of silica, a titanium compound, alumina, cerium oxide, calcium carbonate, magnesium carbonate, calcium phosphate, fluorine-containing resin fine particles, silica-containing resin fine particles, and nitrogen-containing resin fine particles. 5. The method of claim 2, wherein
The non-magnetic one-component electrostatic latent image developer according to any one of the above. 6. An electrostatic latent image holder for holding an electrostatic latent image,
The developer carrier that carries the non-magnetic toner is opposed to the toner carrier, and the same toner as the initial toner is used as the replenishment toner at the time of toner end. 6. A non-magnetic one-component electrostatic image forming method according to claim 1, wherein the developing method is performed by applying a toner having a smaller particle diameter than the toner on the developer carrying member to the electrostatic latent image. A developing method using an electrostatic latent image developer. 7. A developing device comprising: an electrostatic latent image holder for holding at least an electrostatic latent image; a developer carrier for supporting a non-magnetic toner provided between the electrostatic latent image holder and a developer supply hopper; 6. A developing device comprising the non-magnetic one-component electrostatic latent image developer according to claim 1 as a developer.