JP2001265063A - Electrostatic charge image developing yellow toner and method for development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonmagnetic single component developing yellow toner showing little decoloration and stable charge amounts during continuous printing with small fluctuation and maintaining high picture quality for a long time. SOLUTION: The nonmagnetic single component developing yellow toner contains a compound expressed by chemical formula I as a coloring agent, polyester resin as a binder resin, first inorganic fine particles having <=20 nm average primary volume particle size and second inorganic fine particles having 30 nm to 1 μm average primary volume particle size and preferably containing silica subjected to the surface treatment with silicone oil or silane coupling agent. The polyester resin is obtained by condensation polymerization of ethylene oxide added bisphenol A preferably by >=30%, and more preferably by >=95% and a polyvalent carboxylic acid component selected from bivalent or higher valent carboxylic acid, bivalent or higher valent carboxylic acid anhydride and lower alkyl ester of bivalent or higher valent carboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a yellow toner for developing an electrostatic image for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like.

[0002]

2. Description of the Related Art Many methods are known as a developing method in electrophotography, but when roughly classified, fine particles (20 to 500 .mu.m) of iron powder, ferrite, nickel, glass and the like.
There is a two-component developing method using a mixture of a carrier consisting of a toner and a toner as a developer, and a one-component developing method using a developer consisting of only a toner. In either method, generally, charge is injected into the toner in a triboelectric manner.

Representative examples of the two-component developing method include a cascade method described in US Pat. No. 2,618,552 and a magnetic brush method described in US Pat. No. 2,874,063. According to these methods, a good image can be obtained relatively stably, but on the other hand, the quality of the image due to a change in the triboelectric charging property due to contamination of the carrier surface by the toner or the like and a change in the mixing ratio of the carrier and the toner, etc. Deterioration and the like are likely to occur, and various devices and materials need to be devised as measures to prevent such deterioration.

The magnetic brush one-component developing method avoids such a problem of the two-component developing method. For example, in US Pat. No. 4,336,318, an electrically insulating magnetic toner is used. It describes a method for developing. In these methods, charge is injected into the toner by frictional charging between the toner particles and the toner carrier and the toner thinning member or by frictional charging between the toner particles, and the electrostatic latent on the photoreceptor is charged. Electrostatically adheres to the image. Since this developing method does not use a carrier and does not require a device for controlling the mixing ratio between the carrier and the toner, the problems of the two-component developing method can be avoided and the developing device can be reduced in size. However, there is a disadvantage that it is difficult to obtain a clear color image because the magnetic material is not colorless or white.

In recent years, a non-magnetic one-component developing method which does not require magnetic properties of toner has been proposed. Various devices have been studied as a non-magnetic one-component developing method.
In many cases, toner is applied to a developing sleeve or the like as a developer carrier by electrostatic force, and the toner is transported to an electrostatic latent image surface on an electrostatic latent image carrier such as a photoconductor and developed. In comparison with the conventional magnetic one-component developing method, there is a great difference in that the magnetic material is not an essential component in the structure of the toner used, and it is expected that various problems caused by the magnetic material content can be avoided. is there. Various methods have been proposed for the non-magnetic one-component developing method. Among them, toner is passed between the developing sleeve and a charging member such as a blade pressed against the developing sleeve, and the toner is frictionally charged. The method is generally used. However, in this case, the charging of the toner is mainly performed during a short time when the toner passes through the blade, and a technique for instantaneously and uniformly charging the toner to an appropriate level is required. Further, there is a disadvantage that the toner is easily deteriorated when passing between the developing sleeve and the charging member pressed and pressed, and it is difficult to obtain a stable image for a long period of time. Therefore, in the non-magnetic one-component developing method,
In particular, even in the formation of a color image, it was actually extremely difficult to obtain an image having a high image density and less fogging, and to maintain it in continuous printing.

[0006] On the other hand, as a toner composition for obtaining a visible image corresponding to various electrophotographic methods, generally, a composition in which a black colorant such as carbon black is dispersed in a binder resin is often used. ing. In recent years, color toners made by dispersing cyan, magenta, and yellow colorants in a binder resin have been used in order to obtain a multicolor image by an electrophotographic method.

Conventionally, many techniques have been disclosed for such color toners. In particular, magenta (red)
Regarding the toner, JP-A-51-24234, JP-A-59-1
Japanese Patent No. 65069 discloses a technique relating to a magenta toner using a quinacridone pigment or various monoazo pigments.

On the other hand, benzidine yellow is generally used as a pigment for yellow toner. However, benzidine yellow was inferior in light fastness and faded in color over time, and lacked reliability. Non-magnetic 1
When used for component development, there is a disadvantage that it is difficult to maintain stable charge for a long period of time.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a non-magnetic one-component developing yellow toner which has little color fading as a yellow toner, has little variation in charge amount during continuous printing, and has stable image quality.

[0010]

Means for Solving the Problems The present inventors have conducted various studies to solve the above problems, and as a result, completed the present invention.

That is, the inventors contain a compound represented by the chemical formula 1 as a coloring agent, and an ethylene oxide adduct of bisphenol A and a divalent or higher carboxylic acid and a divalent or higher carboxylic anhydride as a binder resin. And a polyester resin obtained by condensation polymerization of a polyvalent carboxylic acid component selected from lower alkyl esters of divalent or higher carboxylic acids, and first inorganic fine particles having an average primary volume particle size of 20 nm or less as an external additive. , Average primary volume particle size 30nm ~ 1μ
By producing a non-magnetic one-component developing yellow toner containing m second inorganic fine particles, there is no fading of the toner,
It has been found that the change in charge amount during continuous printing is small. The yellow pigment represented by the compound of the chemical formula 1 is a pigment having excellent fading resistance per se, but when used together with the binder resin having the above composition, the amount of toner adhered to the developer carrying member during continuous running can be reduced. Stable changes over time, combined with a small change in the amount of charge, realizes stable image quality with no change in hue after color mixing when used in multicolor continuous printing in combination with multicolor toner. be able to.

The binder resin has an acid value of 5.0-2.
It is preferable to use a polyester resin of 0.0 mgKOH / g. In the case of a negatively chargeable toner that occupies most of the non-magnetic one-component developing toner, the acid value is preferably 5.0 or more in terms of charging polarity, and the acid value is 20 or more in terms of long-term charging stability and environmental stability. 0.0 or less is preferable.

Further, as for the resin, it is preferable that 30 to 100% of the alcohol component of the polyester resin is an ethylene oxide adduct of bisphenol A,
It is further preferred that 95% to 100% is an ethylene oxide adduct of bisphenol A. When such a resin is used, the hardness of the resin can be increased without deteriorating other properties such as fixability, and therefore, the embedding of the external additive in the toner particles during running is suppressed. The fluidity is maintained, the change in the amount of charge is reduced, and multicolor printing can be performed stably for a long time.

The average primary volume particle size used in the present invention is 20 n.
m or less, and an average primary volume particle size of 30 nm.
The second inorganic fine particles having a thickness of 1 μm give good fluidity to the toner particles and are essential for maintaining charge stability and good image quality over a long period of time. In particular, by using such two kinds of inorganic fine particles such as silica having different particle diameters, the fine particles having a large particle diameter can effectively suppress the embedding of the fine particles having a small particle diameter into the toner particles. Even during printing, good fluidity and uniform chargeability can be maintained.

As the inorganic fine particles to be added, it is preferable to use colloidal silica hydrophobized with silicone oil. ,
Long-term weathering storage stability can be realized, and long-term stability of color development of the color toner can be realized.

Further, in the non-magnetic one-component developing method, when aluminum is used for the material of the developing sleeve and urethane resin is used for the material of the charging blade in contact with the developing sleeve, the efficiency of charging performance is good and the charging amount is low. stable.

Next, the present invention will be described in detail. The yellow toner for electrostatic charge development of the present invention essentially comprises an organic pigment having the structure of Chemical Formula 1, an ethylene oxide adduct of bisphenol A, a divalent or higher carboxylic acid, a divalent or higher carboxylic anhydride, and It is only necessary to contain a polyvalent carboxylic acid component selected from lower alkyl esters of carboxylic acids having a valency of at least one and a polyester resin obtained by polycondensation, and may be used in combination with other pigments, dyes and resins. It is possible.

Further, as the binder resin, any known and commonly used binder resin can be used in combination.
For example, polystyrene, styrene- (meth) acrylate copolymer, styrene-butadiene copolymer,
Epoxy resins, butyral resins, xylene resins, chromanindene resins, and the like are included. Two or more of these binder resins may be used in combination.

In the non-magnetic one-component developing system, toner particles are charged by frictional charging with a charging member such as a film thickness regulating blade. At this time, stress is applied to the toner particles, so that the toner particles themselves need to have durability. Is done. Therefore, it is preferable to use a resin having relatively high hardness as the binder resin that can be used in the present invention. The acid value of the polyester resin is 5.0 from the viewpoints of chargeability, image density, and fog characteristics.
To 20.0 mgKOH / g, preferably 10.0 to 15.
0 mg KOH / g is particularly preferred.

That is, the composition of the polyester resin in the present invention is preferably a thermoplastic crystalline aromatic polyester composed of an aromatic dicarboxylic acid, an aromatic diol, or a derivative thereof, particularly, phthalic acid and bisphenol A. It is particularly desirable to use a thermoplastic crystalline aromatic polyester comprising an ethylene oxide adduct of the formula (1). Bisphenol A contained in the binder resin
The content of the ethylene oxide adduct is preferably 30 mol% or more of the total alcohol component,
More preferably, it is 1% or more. Since the higher the content of the ethylene oxide adduct of bisphenol A, the higher the charge stability of the toner particles during continuous operation is, the total amount of the ethylene oxide adduct of bisphenol A is particularly desirable.

The aromatic dicarboxylic acid used to obtain the polyester resin used in the present invention includes, for example, phthalic anhydride, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and derivatives thereof.

Similarly, aromatic diols include:
Examples of the ethylene oxide adduct include polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane and derivatives thereof, and examples of other aromatic diols include polyoxypropylene- (2 .
0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.2) -polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, poly Oxypropylene- (6)-
2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.2) -2,2-bis (4-
(Hydroxyphenyl) propane, polyoxypropylene- (2.4) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (3.3)-
Examples include 2,2-bis (4-hydroxyphenyl) propane and its derivatives.

As the other components constituting the polyester according to the present invention, the following compounds can be used as required.

Examples of the dicarboxylic acid component include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic acid, malonic acid, glutaric acid, adipine Acids, azelaic acid, sebacic acid and the like. Examples of the trivalent or higher carboxylic acid component include trimellitic acid, pyromellitic acid and anhydrides thereof.

In the present invention, other diol components that can be used to obtain a polyester resin include:
For example, hydrogenated bisphenol A, ethylene glycol, diethylene glycol, triethylene glycol, 1,2
-Propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, cyclohexanedimethanol, and the like.

Sorbitol, 1,2,3,6-hexanetetraol, 1,1
4-sorbitan, pentaerythritol, 1,2,4-
Butanetriol, 1,2,5-pentanetriol,
Examples include glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trimethylolbenzene.

The linear polyester resin obtained by using only a dihydric carboxylic acid and a dihydric alcohol is
This is preferable because the transparency of the OHP image and the glossiness of the image are superior, but in this case, depending on the fixing device, sufficient fixing characteristics (such as offset resistance) and durability may not be obtained. O
When importance is placed on fixing characteristics (such as offset resistance) and durability over transparency and gloss of the HP image, trivalent or higher carboxylic acids and alcohols may be used.

In the non-magnetic one-component developing system, a thin layer of toner particles is formed on a carrier called a developer carrier, a developing sleeve, or a developing roller, and then transferred to a photoreceptor. However, in order to form a uniform thin layer,
The fluidity and uniformity of charge of the toner particles are important. For this purpose, inorganic fine particles are externally added to the surface of the toner particles. Further, in the non-magnetic one-component developing method, stress is easily applied to the toner particles during the charging process of the toner particles by frictional charging, and the external additive is easily buried in the toner surface. Cause. In order to prevent this, in the present invention, two or more external additives having different average particle diameters are used in combination. Specifically, one is first inorganic fine particles having an average particle diameter of 20 nm or less, and the other is second inorganic fine particles having an average particle diameter of 30 nm to 1 μm. In this case, the former mainly works to secure liquidity, and the latter plays a role in preventing the former from being buried.

Normally, when external addition is performed only with the former inorganic fine particles, the fine particles are buried in the toner particles, and the original function of imparting fluidity is not achieved.

The inorganic fine particles are preferably silica that has been subjected to a hydrophobic treatment, particularly preferably a hydrophobic silica having a hydrophobicity of 80 or more. The degree of hydrophobicity of the external additive in the present invention can be measured by the following method.

50 ml of pure water is placed in a 200 ml beaker, and 0.2 g of an external additive is further added. Then, with gentle stirring with a magnetic stirrer, add methanol from the burette whose tip was immersed in water at the time of dropping, and the floating external additive began to sink, reading the number of ml of dropped methanol when completely sinking, and making it hydrophobic. Degree. In this case, methanol acts as a surfactant, and the external additive floating with the dropwise addition of methanol is dispersed in water via methanol, so the larger the amount of methanol added, the higher the degree of hydrophobicity of the external additive. .

As such silica, for example, silica which is surface-treated with various silicone oils or silane coupling agents, etc., is preferable, and silica is particularly preferable. Examples of the silica surface-treated with a silicone oil or a silane coupling agent include, for example, those commercially available under the following trade names.

AEROSIL R972, R974, R202, R805, R812, RX200, RY200, R809, RX50, RY50, RA200HS, RA200H (Nippon Aerosil Co., Ltd.) WACKER HDK H2000, H1018, H2050EP HDK H3050EP, HVK2150 Nipsil SS-10, SS-15, SS-20, SS-50, SS-60, SS-100, SS-50B, SS-50F, SS-10F, SS-40, SS-70, SS -72F, [Nippon Silica Industry Co., Ltd.] CABOSIL TG820F, TS-530, TS-720 [Cabot Specialty Chemicals, Inc.]

The silica includes those having a relatively large average particle diameter and those having a relatively small average particle diameter. In the present invention, these are used in combination. Considering the application of the required amount of charge, the effect on the photosensitive drum, the environmental characteristics of the toner, and the like, 0.1 to 5.0 parts by weight per 100 parts by weight of the toner particles is practically suitable.

As a component of the toner matrix, a negative charge control agent is suitably used, particularly in the case of the non-magnetic one-component developing toner of the present invention, and a substance conventionally known as a so-called charge control agent, for example, an organic boron compound, A colorless or white one such as a salicylic acid metal complex and a quaternary ammonium salt can be used, and among them, an organic boron compound is particularly desirable.

The release agent is used to enhance the release effect, for example, in heat roll fixing applications, for the purpose of preventing troubles due to toner particles adhered to the heat roll (offset), and various kinds of metal soaps, Waxes are used as needed. For example, natural wax such as montanic acid ester wax, polyethylene,
Polyolefin waxes such as polypropylene can be listed.

An external additive may be used in addition to the first inorganic fine particles and the second inorganic fine particles for surface modification of the toner base such as improvement of fluidity of toner particles and improvement of charging characteristics. As the external additive, inorganic fine powders such as silicon dioxide, titanium oxide, and alumina, those obtained by surface-treating them with a hydrophobizing agent such as silicone oil, resin fine powders, and the like are used. The proportion of these external additives is usually 0.05 to 5% by weight, preferably 0.1 to 5% by weight, based on the toner base.
３3% by weight.

The production method for obtaining the toner of the present invention is as follows.
It can be obtained by any known and common means. For example, after melt-kneading a resin, a colorant and, if necessary, various additives at or above the melting point (softening point) of the resin, pulverizing and classifying the mixture. Can be obtained. Of course, a wet method such as a polymerization method or a microencapsulation method may be used.

Specifically, for example, the above-mentioned resin and colorant are mixed as essential components, and mixed by a kneading means such as a two-roll, three-roll, pressure kneader, or a twin-screw extruder to obtain a kneaded material. Get. At this time, the colorant may be uniformly dispersed in the resin, and the conditions for the melt-kneading are not particularly limited, but are generally at 80 to 180 ° C. for 10 minutes to 2 hours.

The colorant is previously subjected to a flushing treatment or a two-roll method so that the colorant is easily dispersed uniformly in the resin.
It is preferable to use a masterbatch kneaded with the resin at a high concentration using a three-roll, pressure kneader, extruder or the like.
This improves pigment dispersion compared to direct kneading,
An image with high color reproducibility can be obtained for both reflection and transmission.

Next, there is a method in which the kneaded material is cooled, finely pulverized by a pulverizer such as a jet mill, and classified by an air classifier or the like. The toner particles preferably have an average particle diameter of 1 to 15 μm. Further, in the present invention, by adding externally inorganic fine particles such as silica, powder fluidity is improved and long-term stability of charging is secured.

As a method for externally adding the inorganic fine particles such as silica to the toner particles, for example, a conventional powder mixer such as a Henschel mixer or a so-called surface modifier such as a hybridizer may be used. it can. The external addition may be such that silica adheres to the surface of the toner particles, or a part of the silica may be embedded in the toner particles. However, it is necessary to appropriately control the external addition time, the stirring conditions at the time of external addition, and to set the external addition conditions so that the burial does not occur.

At the time of external addition, by using the above-mentioned two kinds of inorganic fine particles such as silica having different average primary volume particle diameters, the burial of silica corresponding to the first inorganic fine particles is suppressed, and even during long-term continuous use. Since the silica is not buried in the toner particles, the fluidity of the toner particles can be secured for a long time, and long-term charging stability can be realized.

As the non-magnetic one-component developing method, a known and commonly used method can be adopted. For example, the toner conveyed by the toner carrier is frictionally charged by a layer thickness regulating member and its layer thickness is regulated. A method of developing an electrostatic latent image by thinning the film on a carrier and contacting or non-contacting the electrostatic latent image carrier is provided. Various metals (aluminum, SUS, etc.), polyurethane resin, silicone rubber, and the like are used for the toner carrier and the layer thickness regulating member. In this case, it is preferable that at least one of the toner carrier and the layer thickness regulating member is made of metal (aluminum, SUS, etc.) in terms of chargeability and durability, and aluminum is used for the toner carrier and polyurethane resin is used for the layer thickness regulating member. It is particularly desirable to use

[0045]

BEST MODE FOR CARRYING OUT THE INVENTION In order to obtain the toner for electrostatic charge development of the present invention, a compound (CI Pigment Yellow 155) represented by the chemical formula 1 is used as a colorant as it is or kneaded with a binder resin in advance. And use it as a master batch. The following aromatic polyester resins are used as the binder resin.

The colorant or its master batch, the binder resin, and the charge control agent are melt-kneaded in the following mass ratio. Coloring agent 1 to 10 parts Binder resin 85 to 100 parts Charge control agent 0.1 to 5 parts

Here, the binder resin having the following composition is used together with the colorant represented by the chemical formula 1.
That is, the ethylene oxide adduct of bisphenol A is condensed with a divalent or higher carboxylic acid, a divalent or higher carboxylic acid anhydride, and a polyvalent carboxylic acid component selected from divalent or higher carboxylic acid lower alkyl esters. Use of a polymerized polyester resin component, preferably an acid value of 5.0 to 2
0.0mg KOH / g of a polyester resin, and preferably the content of ethylene oxide adduct of bisphenol A is 50 mol% or more of the total alcohol component,
More preferably, 95% or more of the polyester resin is used. If necessary, 0.5 to 5 parts of an offset preventing agent such as a wax may be added.

This kneaded material is pulverized and classified, and the first inorganic fine particles having an average primary volume particle size of 20 nm or less and the second inorganic fine particles having an average primary volume particle size of 30 nm to 1 μm are mixed with 0.1 to 5% by weight of toner particles. Externally added to the surface, toner particles of about 5 to 15 μm are obtained.

The present invention includes the following inventions and embodiments.

1. An electrostatic image developing toner containing a colorant and a binder resin as main components, a compound represented by Formula 1 as a colorant, and an ethylene oxide adduct of bisphenol A and a divalent or higher valent as a binder resin. A polyester resin obtained by polycondensation of a carboxylic acid, a divalent or higher carboxylic anhydride, and a polyvalent carboxylic acid component selected from lower alkyl esters of divalent or higher carboxylic acids,
A yellow toner for non-magnetic one-component development, comprising: first inorganic fine particles having an average primary volume particle size of 20 nm or less, and second inorganic fine particles having an average primary volume particle size of 30 nm to 1 μm.

2. The acid value of the polyester resin is 5.0 to 2
2. The yellow toner for non-magnetic one-component development according to the above 1, wherein the amount is 0.0 mgKOH / g.

3. 3. The non-magnetic one-component developing yellow toner according to any one of the above items 1 and 2, wherein 30 to 100% of an alcohol component used in the polyester resin is an ethylene oxide adduct of bisphenol A.

4. 3. The yellow toner for non-magnetic one-component development as described in the above items 1 and 2, wherein 95 to 100% of an alcohol component used in the polyester resin is an ethylene oxide adduct of bisphenol A.

5. 5. The yellow toner for non-magnetic one-component development according to any one of the above items 1, 2, 3, and 4, wherein the first inorganic fine particles and the second inorganic fine particles are silicon oil or colloidal silica surface-treated with a silane coupling agent. .

6. 6. The yellow toner for non-magnetic one-component development according to the above item 5, wherein the silica has a hydrophobicity of 80 to 200.

7. In the non-magnetic one-component developing method, aluminum is used as a material of a developing sleeve, and urethane resin is used as a material of a charging blade in contact with the developing sleeve.
A non-magnetic one-component developing method using the toner described in 2, 3, 4, 5, or 6.

[0057]

The present invention will be more specifically described below with reference to examples and comparative examples. The present invention is not limited to the following examples unless it exceeds the gist. Hereinafter, “parts” and “%” in Examples and Comparative Examples represent “parts by mass” and “% by mass”, respectively.

(Resin Synthesis Example) Resin A Polyoxyethylene- (2,0) -2,2-bis (4-hydroxyphenyl) propane 5 mol Isophthalic acid 2.5 mol Terephthalic acid 2.5 mol Polyester resin A was obtained by charging 0.05% of dibutyltin oxide based on the mass into a flask and reacting at 220 ° C. (Acid value = 12 Mw = about 10,
000)

Resin B Resin B was obtained by the same composition and method as Resin A, except that the acid value of Resin A was changed to 6. Resin C Resin C was obtained by the same composition and method as Resin A, except that the acid value of Resin A was changed to 18. Resin D Resin D was obtained by the same composition and method as Resin A, except that the acid value of Resin A was changed and adjusted to 3.

Resin E Polyoxypropylene- (2,0) -2,2-bis (4-hydroxyphenyl) propane 3 mol Polyoxyethylene- (2,0) -2,2-bis (4-hydroxyphenyl) Propane 2 mol Isophthalic acid 2.5 mol Terephthalic acid 2.5 mol Resin E was obtained from the above raw materials by the same synthesis method as resin A. (Acid value = 11 Mw = about 9000)

Resin F Polyoxypropylene- (2,0) -2,2-bis (4-hydroxyphenyl) propane 2 mol Isophthalic acid 1 mol Terephthalic acid 1 mol I got (Acid value = 13 Mw = about 10,000)

(Example 1) 50 parts of a polyester resin A and a coloring agent represented by a chemical formula 1 (CI Pigment)
50 parts of Yellow 155) were kneaded using a two-roll mill to obtain Pigment Master A. The following toner composition (1) containing the pigment master A was melt-kneaded by an extruder, pulverized by a jet mill, and obtained by a pneumatic classifier to obtain a toner base having an average particle size of about 8 μm.

(Toner Composition 1) Polyester Resin A 89% Pigment Master A 10% Charge Control Agent LR-147 (manufactured by Nippon Carlit) 1% First inorganic fine particles Hydrophobic silica fine powder ATS720 (Cabot) (Manufactured by Nippon Aerosil Co., Ltd.) (manufactured by Nippon Aerosil Co., Ltd.) 0.5% second inorganic fine particles BRY50 (manufactured by Nippon Aerosil Co., Ltd.) (average primary volume particle size: 40 nm) 1.0% was added to obtain a yellow toner (1). Hereinafter, the abbreviations of the first inorganic fine particles as the external additive A and the second inorganic fine particles as the external additive B are used together.

(Evaluation of coloring power) A non-magnetic one-component developing type commercially available color printer having a yellow toner (1) having a developing sleeve made of aluminum and a layer thickness regulating member in which urethane rubber is adhered to a stainless steel plate (hereinafter referred to as A machine) To obtain a yellow print. When the image density of the image portion where the toner adhesion amount was 1 mg / cm ² was measured using a Macbeth densitometer, the image density was 1.83.

(Evaluation of fading) The yellow toner (1) was placed in the machine A to obtain a yellow print. About this printed matter, an accelerated light fastness tester (SUN TEST, manufactured by Heraeus)
(CTS) for 10 hours, and the density of the printed matter after the exposure was measured by a Macbeth densitometer. Residual rate (%) = (density after exposure / density before exposure) × 100

(Evaluation of chargeability at initial stage and after running)
The toner charge amount on the developing sleeve of the machine A at the initial stage and after running 2,000 sheets was measured by a suction-type charge amount measuring device to be -25 μC / g and -18 μC / g.

(Evaluation of the Amount of Toner Adhered on the Developing Roll at Initial and After Running) The toner charge on the developing sleeve of the machine A at the initial stage and after running 2,000 sheets was measured by a suction type charge amount measuring apparatus. .52 mg / cm ² ,
It was 0.45 mg / cm ² .

(Evaluation of Image Density and Fog at Initial Stage and After Running) The yellow toner (1) was placed in machine A and a printing test was carried out. As a result, an image having sufficient image density and low fog was obtained. Further, even after printing 2000 sheets, the image quality was little deteriorated, the image density was sufficient, and an image with little fog was obtained.

Example 2 An average particle diameter of about 8 μm was obtained in the same manner as in Example 1 except that the polyester resin A was changed to the polyester resin B in the toner composition 1.
Was prepared, and external additives A and B were added to obtain a yellow toner (2). When the same evaluation as in Example 1 was performed using this toner using the machine A, the coloring power and the fading evaluation were almost the same as those in Example 1. Initial charge and 2000
At -22 μC / g and −15 μC / g after the single-sheet running, the level was slightly lower than that in Example 1, but at a level that did not cause any problem in use. The image density was slightly higher than that of Example 1 in the initial stage even after printing 2000 sheets. Fog was slightly worse than that of Example 1, but was at a level that was not problematic in use.

Example 3 An average particle diameter of about 8 μm was obtained in exactly the same manner as in Example 1 except that the polyester resin A was changed to the polyester resin C in the toner composition 1.
Was manufactured, and external additives A and B were added to obtain a yellow toner (3). When the same evaluation as in Example 1 was performed using this toner using the machine A, the coloring power and the fading evaluation were almost the same as those in Example 1. Initial charge and 2000
After the sheet running, the attenuation in the running was slightly higher than that in Example 1 at -27 μC / g and −16 μC / g, but at a level that did not cause any problem in use. The initial image density is 2000
Even after the printing of one sheet, the number slightly decreased from that in Example 1. Fog was slightly worse than that of Example 1, but was at a level that was not problematic in use.

(Example 4) An average particle size of about 8 µm was obtained in exactly the same manner as in Example 1, except that the polyester resin A was changed to the polyester resin D in the toner composition 1.
Was manufactured, and external additives A and B were added to obtain a yellow toner (5). When the same evaluation as in Example 1 was performed using this toner using the machine A, the coloring power and the fading evaluation were almost the same as those in Example 1. Initial charge and 2000
After the sheet running, it was slightly lower than that of Example 1 at -21 μC / g and -16 μC / g, but there was no problem in durability. The image density was slightly higher than that of Example 1 in the initial stage even after printing 2000 sheets. However, fog is worse than in Example 1.

Example 5 An average particle size of about 8 μm was obtained in exactly the same manner as in Example 1 except that the polyester resin A was changed to the polyester resin E in the toner composition 1.
Was prepared, and external additives A and B were added to obtain a yellow toner (6). When the same evaluation as in Example 1 was performed using this toner using the machine A, the coloring power and the fading evaluation were almost the same as those in Example 1. Initial charge and 2000
After the sheet running, the attenuation width was larger than that of Example 1 at -26 μC / g and -15 μC / g, but there was no problem in durability. The image density is almost the same as in Example 1 at the initial stage and after printing 2000 sheets. The fog was slightly worse than in Example 1, but was at a level that was not problematic in use.

(Example 6) A printer A for evaluation in Example 1 was replaced with a commercially available non-magnetic one-component color printer (hereinafter referred to as B) having a developing sleeve made of silicon rubber and a layer thickness regulating member made of stainless steel. The yellow toner (1) was evaluated in exactly the same manner as described above except that the evaluation was carried out.
The coloring power and the evaluation of fading were almost the same as those in Example 1. The charge amount is -20 μC / g and −13 μC / g at the initial stage and after running 2000 sheets, which is lower than that in Example 1, but there is no problem in durability. The initial image density is 200
Even after printing 0 sheets, the value slightly increased from that in Example 1. However, fog is worse than in Example 1.

Comparative Example 1 The pigment used for the pigment master A in Example 1 was C.I. I. PigmentYell
ow 17 was used in place of the pigment master A in the toner composition (1), except that the pigment master A was used in the toner composition (1) to produce a toner base having an average particle size of about 8 μm. The addition treatment gave a yellow toner (4). When the same evaluation as in Example 1 was performed using this toner using the machine A, the coloring power was higher than that of Example 1, but the evaluation of fading was inferior to that of Example 1. The charge amount was −26 at the initial stage and after running 2000 sheets.
The levels were almost the same as in Example 1 at μC / g and −19 μC / g. The fog was almost the same as in Example 1 at the initial stage after printing 2000 sheets, and was at a level without any problem. However, the toner adhesion amount on the developing roll was 0.60 mg / cm2 and 0.41 mg / cm2 after printing 2000 sheets.
Y. The amount of change is larger than other toners using 155. For this reason, the image density also fluctuates greatly at the initial stage, after printing 2000 sheets, at 1.7 and 1.2.

Comparative Example 2 An average particle diameter of about 8 μm was obtained in exactly the same manner as in Example 1 except that the polyester resin A was changed to the polyester resin F in the toner composition 1.
Was prepared, and external additives A and B were added to obtain a yellow toner (7). When the same evaluation as in Example 1 was performed using this toner using the machine A, the coloring power and the fading evaluation were almost the same as those in Example 1. The charge amount is initial and 200
At -24 μC / g and -11 μC / g after the zero-sheet running, the attenuation width is particularly larger than in Example 1, and there is a problem in durability. The image density is almost the same as in Example 1 at the initial stage and after printing 2000 sheets. Fog was worse than in Example 1.

Comparative Example 3 A yellow toner (8) was obtained in exactly the same manner as in Example 1, except that the addition process was carried out using 1.5 parts of only A among the external additive silicas A and B. .
When the same evaluation as in Example 1 was performed using this toner using the machine A, the coloring power and the fading evaluation were almost the same as those in Example 1. The charge amount is -2 at the initial stage and after running 2000 sheets.
At 5 .mu.C / g and -8 .mu.C / g, the attenuation width is particularly large as compared with the first embodiment, and there is a problem in durability. The image density is initially 20
After printing 00 sheets, the charge amount becomes 1.5 and 1.7, and the charge amount decreases.
The image density increased, contrary to the others, by the increase in the amount of the developing roll attached. Fog was particularly bad after printing 2000 sheets. Table 1 summarizes the results of Examples and Comparative Examples as described above.

[0077]

[Table 1]

[0078]

The yellow toner for non-magnetic one-component development of the present invention contains a compound represented by the formula 1 as a colorant as described above, and a diol comprising a bisphenol derivative or a substituted product thereof as a binder resin. A polyester resin obtained by co-condensation of a component and a polyvalent carboxylic acid component selected from a divalent or higher carboxylic acid, a divalent or higher carboxylic acid anhydride, and a lower alkyl ester of a divalent or higher carboxylic acid; and It contains first inorganic fine particles having an average primary volume particle size of 20 nm or less, and second inorganic fine particles having an average primary volume particle size of 30 nm to 1 μm, and has excellent color reproducibility, image stability, light fastness, and Charging stability can be achieved. Further, the resin preferably has an acid value of 5.0 to 20.0 mgKOH / g. As for the resin, the content of the ethylene oxide adduct of bisphenol A in the polyester resin is 30 mol% or more of the total alcohol component. ,
More preferably, it is 95 mol% or more, and the charging stability in long-term continuous operation increases, and long-term stable image quality can be realized. Further, when aluminum is used for the material of the developing sleeve and urethane resin is used for the material of the charging blade in contact with the developing sleeve in the developing method, the above-described improvements in the characteristics are more remarkably exhibited.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/08 501 G03G 15/08 504A 504 9/08 361 331 F term (Reference) 2H005 AA01 AA06 AA08 AA21 CA08 CA12 CA21 CB13 EA05 EA07 EA10 FA07 2H077 AD06 AD13 AD17 AE03 AE04 BA10 EA14 EA24 FA22 FA26 GA12

Claims (7)

[Claims] 1. A toner for developing an electrostatic image containing a colorant and a binder resin as main components, a compound represented by the following chemical formula 1 as a colorant, and addition of ethylene oxide of bisphenol A as a binder resin. A polyvalent carboxylic acid component selected from lower alkyl esters of divalent or higher carboxylic acid, divalent or higher carboxylic acid, and divalent or higher carboxylic acid, and a polyester resin, A yellow toner for non-magnetic one-component development, comprising: first inorganic fine particles having an average primary volume particle size of 20 nm or less, and second inorganic fine particles having an average primary volume particle size of 30 nm to 1 μm. Embedded image 2. The polyester resin having an acid value of 5.0 to 20.
2. The yellow toner for non-magnetic one-component development according to claim 1, wherein the amount is 0 mgKOH / g. 3. The polyester of the total alcohol component 3
3. The yellow toner for non-magnetic one-component development according to claim 1, wherein 0 to 100% is an ethylene oxide adduct of bisphenol A. 4. The polyester of the total alcohol component 9
3. The yellow toner for non-magnetic one-component development according to claim 1, wherein 5 to 100% is an ethylene oxide adduct of bisphenol A. 5. The non-magnetic material according to claim 1, wherein the first inorganic fine particles and the second inorganic fine particles are silicon oil or colloidal silica surface-treated with a silane coupling agent. Yellow toner for one-component development. 6. The yellow toner for non-magnetic one-component development according to claim 5, wherein the hydrophobicity of the silica is 80 to 200. 7. A non-magnetic one-component developing method, wherein aluminum is used for a material of a developing sleeve, and urethane resin is used for a material of a charging blade in contact with the developing sleeve.
A non-magnetic one-component developing method using the toner described in 2, 3, 4, 5, or 6.