JPH03221967A - Electrostatic charge image developing toner and image forming method using the same - Google Patents

Abstract

PURPOSE:To stabilize triboelectrification occurring between a toner and a charge giving member and to form a sharp and uniform triboelectrification distribution and to prevent too high rise of triboelectrifiability by incorporating a specified chromium compound as a negative charge controlling member. CONSTITUTION:The toner comprising at least a binder resin and a colorant contains as the negative charge controller at least one of the compounds represented by formulae I - V in which each of R1 - R9 and R11 - R18 and R21 - R70 is H, alkyl, or alkoxy; (n) is 1 or 2; and X is K, Ca, Ba, Zn, or the like. The content of the charge controller in the toner is not simply defined but usually 0.1 - 20wt.% of the binder resin, preferably 0.2 - 10wt.%, is used, and as the colorant, conventionally used pigments and dyes are used and as the binder resin, conventionally used resins are used.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a dry 1-ner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc., and an image forming method using the same. More specifically, the present invention relates to a 1-ner for developing electrostatic images containing a specific chromium compound as a negative charge control agent and an image forming method using the same.

[Conventional technology]

There are two methods for developing electrostatic images formed on electrophotographic photoreceptors and electrostatic recording materials: a method using a liquid developer (wet development method), and a method using a colorant dispersed in a binder resin. A method (dry development method) using a one-component type or two-component type dry developer in which toner or one hener is mixed with a solid carrier is generally adopted. Although each of these methods has its own advantages and disadvantages, the dry developing method is currently widely used.

By the way, in the above-mentioned toner (developer powder), if a coloring agent such as a dye or pigment is simply dispersed in a binder resin, the desired flF conductivity cannot be obtained, so an appropriate amount of a charge control agent is added to the toner. It is usually added. Typical examples of conventional charge control agents include (i) those that impart a positive charge to the toner, such as nigrosine oil-soluble dyes, quaternary ammonium salts, azine dyes having an alkyl group, and basic dyes, basic dye lakes, etc.; (ii) substances that impart a negative charge to the toner, such as chromium-containing monoazo complexes, chromium-containing salicylic acid compound complexes, chromium-containing organic dyes (copper phthalocyanine green, chlorine-containing monoazo dyes); ) and metal-containing dyes. However, although toners containing conventional charge control agents exhibit good development characteristics initially, they have a short lifespan, and therefore, when used for long periods of time, they often cause inconvenient phenomena such as filming on the photoreceptor. It recognized. This is due to the fact that the properties of conventional charge control agents are inconsistent and lack stability. In addition, many of these conventional charge control agents are easily dispersed during thermal kneading during toner production, or easily decomposed or deteriorated due to mechanical impulses, friction, changes in temperature and humidity conditions, etc. This is making the phenomenon of decline even stronger. Furthermore, there is a tendency that many of the conventional charge control agents change depending on the environment. especially,
In a one-component process that includes at least an I/toner transport member and an I/toner layer 8-thickness regulating member and in which a thin toner layer is formed on the toner transport member and development is performed, fluctuations in toner chargeability may affect the thickness of the toner thin layer. This may greatly affect formability and cause image deterioration. In any case, most of the charge control agents that have been proposed so far cannot maintain appropriate chargeability over a long period of time.

[Problem to be solved by the invention]

Therefore, the present invention overcomes the drawbacks of the above-mentioned prior art, and provides stable frictional charging that occurs between toner particles or between a toner and a charge-imparting member such as a developing sleeve or blade in a component-based development system. Our primary objective is to provide a 1~ner with a sharp and uniform triboelectric charge distribution, which can be controlled to a charge amount suitable for the developing method used, and which can be used for a long period of time without becoming too excessive in triboelectric chargeability. A second object of the present invention is to provide a toner in a one-component type dry developing material whose charge is controlled to be negative over a period of time. Furthermore, the third object of the present invention is to provide a 1-sheet that not only provides stable images at all times but also has durability, and is free from stains and toner scattering, even during continuous use. A fourth object is to provide a toner that allows a large number of high-quality images equivalent to the initial images to be obtained.

[Means to solve the problem]

As a result of extensive research, the present inventors have found that a toner containing a specific chromium compound as a negative charge control agent is suitable for the above purpose, and have completed the present invention.

That is, according to the present invention, a toner comprising at least a binder resin and a colorant contains at least one chromium compound represented by the following general formulas (I) to (V) as a negative charge control agent. A characteristic I toner for developing electrostatic images is provided.

(In the formula, R1-R3, X and n each represent the following.

Or an alkyl group or alkoxy group having 1 to 18 carbon atoms.

+13 The base is a methyl group, ethyl group, tert-buchi group, nitro group, halogen atom or hydroxyl A substituent such as a group may be attached.

Or an alkyl group or alkoxy group having 1 to 18 carbon atoms.

The H3 group may have a substituent such as a methyl group, an ethyl group, a tert-butyl group, a nitro group, a halogen atom, or a hydroxyl group.

X: K, Ca, Ba, Mg, Na
, H, Li or Zn atoms.

n: l or 2° depending on the valence of X) (In the formula, R, ~R111, X and n each represent the following.

R□1 to R4 = one of them is R,9-NH-1 and the others are 11 atoms or an alkyl group or alkoxy group having 1 to 18 carbon atoms.

The -''1- 11:l group may have a substituent such as a methyl group, an ethyl group, a tert-butyl group, a nitro group, a halogen atom, or a hydroxyl group.

R15-”1.+1: One of them is R2o-Nl+-
1 and others are H atoms or alkyl groups or alkoxy groups having 1 to 18 carbon atoms.

The l'+3 group may have a substituent such as a methyl group, ethyl group, tert-butyl group, nitro group, halogen atom or hydroxyl group.

X: Ca, Ba, Mg, Na, ) I, Li or Zn
atom.

n: 1 or 2° depending on the valence of X) (wherein, R21 to R4°, X and n each represent the following.

R21 to R4, :l (atom or alkyl group or alkoxy group having 1 to 18 carbon atoms).

X8 is a Ca, Ba, Mg, Na, H, Li or Zn atom.

n: 1 or 2° depending on the valence of x) (In the formula, R41 to RGo, X and n each represent the following.

R6,1 to R5°: 11 atoms or an alkyl group or alkoxy group having 1 to 18 carbon atoms.

X: Ca, Ba, Mg, Na, It, L] or Zn
atom.

n: 1 or 2° depending on the valence of x) (wherein RGI to R7°, X and n each represent the following.

R6□ to R7, HH atom or an alkyl group or alkoxy group having 1 to 18 carbon atoms.

X: Ca, Ba, Mg+Na, H, Li or Zn atom.

n: 1 or 2 degrees depending on the valence of 15- There is provided an image forming method characterized by using the following.

In the 1-nate of the present invention, the chromium compounds represented by the general formulas (I) to (V) used as negative charge control agents are synthesized by known means. These negative charge control agents may be used alone or in combination of two types. Moreover, other negative charge control agents can also be used together.

The toner of the present invention includes a binder resin, a colorant, and the negative charge control agent as essential components. The content of the negative charge control agent in the toner is determined by the toner manufacturing method, including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. Although not necessarily limited, it is usually in the range of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the binder resin. 0
．． If it is less than 1 part by weight, the negative chargeability of the toner will be insufficient and it is not practical; if it exceeds 20 parts by weight, the negative chargeability of the I-toner will become too large, resulting in decreased fluidity, poor transferability, and poor image quality. This is not preferable because it causes a decrease in concentration.

16- As the colorant used in the present invention, all pigments and dyes conventionally used as colorants for toners can be used. Specifically, carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline blue, calco oil blue DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6C lake, chromium. yellow, quinacridone, benzidine yellow, malachite 1-green, malachite green hexare-1-, oil black, azo oil black, rose bengal, monoazo dyes and pigments, disazo dyes and pigments, trisazo dyes and pigments, and mixtures thereof. Can be mentioned.

Further, as for the binder resin used in the present invention, all the binder resins that have been used hitherto as binder resins for toners can be used, similarly to the colorant described above. Specifically, polystyrene,
Monopolymers of styrene and its substituted products such as poly p-chlorostyrene and polyvinyltoluene: styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methacrylic acid copolymer Methyl copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-
Glor methyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinylethyl ether copolymer,
Styrenes such as styrene-vinylmethylketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, and styrene-ma monotonic acid ester copolymer System copolymers: polymethyl methacrylate, polybutyl methacrylate-1-, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin , terpene resins, phenolic resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes, etc., and these may be used alone or in combination of two or more.

Note that additives may be mixed with the toner of the present invention as necessary. Examples of additives include lubricants such as tetrafluoroethylene resin and zinc stearate, abrasives such as cerium oxide and silicon carbide, fluidizing agents such as colloidal silica and aluminum oxide, anti-caking agents, and carbon. Examples include conductivity imparting agents such as black, tin oxide, and fixing aids such as low molecular weight polyethylene.

The toner of the present invention is particularly useful for image formation using a one-component development method in electrophotography, and the image forming method of the present invention will be described next.

The image forming method of the present invention is an image forming method using a one-component development method in electrophotography in which a thin layer of toner is supplied to a latent image carrier to develop a latent image, and the image forming method contains the above-described negative charge control agent. It is characterized by using toner. Note that the thinning of 1-hener usually requires a toner conveying member, a toner layer thickness regulating member, and an I/toner supplying member, and a toner supplying member, a toner conveying member, a toner layer thickness regulating member, and a toner conveying member, respectively. This is done using an abutting device.

The image forming method of the present invention will be explained in more detail with reference to the drawings.

The drawing is a schematic cross-sectional view of an example of a developing device using a non-magnetic-component toner useful in carrying out the method of the present invention. In the drawing, one of the present invention built in the toner tank 7 is shown.
The toner 6 is forcibly brought to the toner supply member (sponge roller) 4 by the stirring blade (toner supply auxiliary member) 5, and the toner is supplied to the toner supply member 4. The I-ner taken into the I-ner supplying member 4 is )-
When the toner supply member 4 rotates in the direction of the arrow, the toner is carried to the toner transport member 220-, is rubbed, and is electrostatically or physically attracted to the toner.
1- The toner conveying member 2 rotates strongly in the direction of the arrow, and a uniform thin layer of toner is formed by the toner layer thickness regulating member (elastic blade) 3 made of steel, and is charged by friction. Thereafter, the toner is transported to the surface of the electrostatic latent image carrier 1 that is in contact with or in close proximity to the toner transport member 2, and the latent image is developed. The electrostatic latent image is created by charging the organic photoreceptor with a negative DC charge of 800 V and then exposing it to light to form a latent image and developing it. Note that developing devices suitable for the toner of the present invention are not limited to those described above.

In such an image forming method using a one-component development method in electrophotography, fluctuations in the chargeability of the toner greatly affect the ability to form a thin layer of l-toner, but the toner of the present invention has a stable negative polarity. Since it exhibits triboelectrification properties and has excellent environmental stability, it is possible to control the appropriate amount of charge during implementation, and the method of the present invention allows high-quality images to be obtained over a long period of time. .

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts represent parts by weight.

Example 1 In the general formula (I), R11. 3 parts of a compound in which R2, R4, R2H, and Lo are phenyl groups, and X is a hydrogen atom, and n = 1, 1.00 parts of styrene/r+-butyl methacrylate copolymer, and 10 parts of carbon black. After sufficiently stirring and mixing the mixture consisting of
The mixture was melted by heating at a temperature of .degree. C. for about 30 minutes, and then cooled to room temperature. The obtained kneaded product was pulverized and classified to obtain 1-ner with a particle size of 5 to 10 μm. This toner]. 0.2 parts of colloidal silica was added and mixed to obtain a toner of the present invention.

When the obtained 1-ner was used to produce an image using a developing device as shown in the drawing, a good image was obtained.
That image remained unchanged even after 10,000 copies were printed.

In addition, when the charge amount of the toner was measured by the suction method, the initial charge amount was -15.5 μC/g, and the charge amount of the toner after running 100,000 sheets was -15.2 μC/g.
was almost unchanged from the initial value.

Furthermore, under a high temperature environment of 35℃ and 90% RH and at 10℃
Even in a low humidity environment of 15% RI+, an image equivalent to that obtained in a normal humidity environment was obtained, and no toner filming on the photoreceptor was observed.

Example 2 Instead of the compound represented by the general formula (1) in Example 1, R1, R
2. Proceed as in Example 1 except that R4, R5, R8 and R9 are hydrogen atoms, R3 is a phenyl group with a thyl group, and X is a lithium atom, and a compound where n = 1 is used. A toner of the present invention was obtained.

When an image was produced using the obtained toner in the same manner as in Example 1, a good image was obtained, and the image remained unchanged even after running 100,000 copies.

In addition, when the toner charge amount was measured using a suction method, the initial charge amount was -16.2 μC/g, and the toner charge amount after running 100,000 sheets was -15.9 μC/g, which was almost the initial value. It didn't change.

Furthermore, under a high humidity environment of 35°C, 190% R11 and ]O
Even under the low humidity environment of 'C515%RH, an image equivalent to that obtained when copying at room temperature was obtained, and no toner filming on the photoreceptor was observed.

Example 3 In place of the compound represented by the general formula (1) in Example 1, in the general formula (II), R12, R1
4, R15 and R17 are hydrogen atoms, R□□ and R□9 are methyl groups, La is R19-NH-1Ln is R2o-N)
A toner of the present invention was obtained in the same manner as in Example 1, except that a compound in which l-1Ri, 9, and R2[+ were phenyl groups, X was a potassium atom, and n:1 was used.

When an image was produced using the obtained toner in the same manner as in Example 1, a good image was obtained, and the image did not change even after running 100,000 copies and remained unchanged for 24 hours.

In addition, when the toner charge amount was measured using a suction method, the initial charge amount was -12.7 μC/g, and the toner charge amount after running 100,000 sheets was -11.8 μC/g, which was almost the initial value. It didn't change.

Furthermore, under a high humidity environment of 35°C and 190% RH, and at 10°C.
Even in a low humidity environment of 15% R14, an image equivalent to that obtained in a normal temperature environment was obtained, and no 1-ner filming on the photoreceptor was observed.

Example 4 Instead of the compound represented by the general formula (1) in Example 1, in the general formula (II), R-1, R1
, l], RIL4, R15, L+, and Le are all hydrogen atoms, R1,2 are R1, -N11-1R17 is R,o
-NH-1Ft□s and R20 are naphthyl groups, and
A toner of the present invention was obtained in the same manner as in Example, except that a compound in which n was a calcium atom and n = 2 was used.

When an image was produced using the obtained toner in the same manner as in Example 1, a good image was obtained, and the image did not change even after running 100,000 copies.

Furthermore, when the toner charge amount was measured using a suction method, the initial charge amount was -11.3 μC/g, and the toner charge amount after running 100,000 sheets was -10.9 μC/g, which was almost the initial value. It didn't change.

Furthermore, in a high temperature environment of 35°C 190% R1 (+o
Even in a low humidity environment of 15% RH, an image equivalent to that obtained in a normal temperature environment was obtained, and no toner filming on the photoreceptor was observed.

Example 5 Instead of the compound represented by the general formula (1) in Example 1, in the general formula (Ti), n=2, n=
3, R engineering R15, L, c and R engineering are hydrogen atoms, R1
A toner of the present invention was obtained in the same manner as in Example 1, except that a compound in which 0 squares were lithium atoms and n=1 was used.

When an image was produced using the obtained toner in the same manner as in Example, a good image was obtained, and the image did not change even after running 100,000 copies.

In addition, when the amount of charge on the toner was measured using a suction method, the initial amount of charge was -12.1 μC/g, and the amount of charge on the toner after 100,000 sheets of printing was -11.7 μC/g.
was almost unchanged from the initial value.

Furthermore, under a high humidity environment of 35°C 190% R1+ and 10
Even in a low humidity environment of 15% R1+ at 15% R1+, an image equivalent to that obtained in a normal humidity environment was obtained, and no toner filming on the photoreceptor was observed.

Example 6 In place of the compound represented by the general formula (I) in Example 1, in the -maximum (m), R21R,. A toner of the present invention was obtained in the same manner as in Example 1, except that a compound in which all of the above were hydrogen atoms, X was a potassium atom, and n=l was used.

When an image was produced using the obtained toner in the same manner as in Example 1, a good image was obtained, and the image remained unchanged even after running 100,000 sheets.

In addition, when the toner charge amount was measured using a suction method, the initial charge amount was -10.8 μC/g, and the toner charge amount after running 100,000 sheets was -10.2 μC/g, which was almost the initial value. It didn't change.

Furthermore, under a high humidity environment of 35°C 190% R)l and 10
Even under the low humidity environment of 'C115%Rh+, an image equivalent to the original copy in a normal humidity environment was obtained, and no 1~ner filming on the photoreceptor was observed.

Example 7 Instead of the compound represented by the general formula (I) in Example 1, R22, RZl in the -maximum (m)
l, R33 and R39 are tert-butyl groups, and the other R
A toner of the present invention was obtained in the same manner as in Example 1, except that a compound in which all of were hydrogen atoms, X was a barium atom, and n:2 was used.

When an image was produced using the obtained toner in the same manner as in Example 1, a good image was obtained, and the image did not change even after running 100,000 copies.

28- Also, when the toner charge amount was measured by the suction method, the initial charge amount was -9.8 μC/g, and the toner charge amount after running 100,000 sheets was -9.2 μC/g, the initial value. There was almost no difference.

Furthermore, under a high temperature environment of 35°C 190% RH and 10°C
Even in a low humidity environment of 15% RH, an image equivalent to the original copy in a normal humidity environment was obtained, and no toner filming on the photoreceptor was observed.

Example 8 In place of the compound represented by the general formula (I) in Example 1, in the -max (I[[), R23, R
29, R3□ and R3+1 are ethyl groups, the other I( are all hydrogen atoms, and X is a zinc atom, T1=
A toner of the present invention was obtained in the same manner as in Example 1, except that Compound No. 2 was used.

When an image was produced using the obtained toner in the same manner as in Example 1, a good image was obtained, and the image did not change even after running 100,000 copies.

In addition, when the toner charge amount was measured using a suction method, the initial charge amount was -12.1 μC/g, and the toner charge amount after running 100,000 sheets was -11.9 μC/g, which was almost the initial value. It didn't change.

Furthermore, under a high humidity environment of 35℃, 90% R11 and 10℃
Even in a low humidity environment of 15% l'tH, an image equivalent to the original copy in a normal humidity environment was obtained, and no toner filming on the photoreceptor was observed.

Example 9 Instead of the compound represented by the general formula (I) in Example 1, in the -maximum (IV), R4, RGI
Examples 1 to 1 of the present invention were obtained in the same manner as in Example 1, except that a compound in which all of I was a hydrogen atom, X was a hydrogen atom, and n=1 was used.

When an image was produced using the obtained toner in the same manner as in Example 1, a good image was obtained, and the image did not change even after running 100,000 copies.

In addition, when the toner charge amount was measured by the suction method, the initial charge amount was -14.5 μC/g, and the toner charge amount after running 100,000 sheets was -13.8 μC/g, which was the same as the initial value. Not much changed.

Furthermore, under a high humidity environment of 35°C and 90% RH, and at 10°C,
Even in a low-humidity environment of 15% RH, an image equivalent to that obtained in a normal-humidity environment was obtained, and no toner filming on the photoreceptor was observed.

Example 10 Instead of the compound represented by the general formula (I) in Example 1, R43, R4 in the -maximum (IV)
11+ Proceed in the same manner as in Example 1, except that a compound in which R53 and RSa are tert-butyl groups, all other R are hydrogen atoms, X is a lithium atom, and n = 1 is used. A toner of the present invention was obtained.

When an image was produced using the obtained toner in the same manner as in Example 1, a good image was obtained, and the image did not change even after running 100,000 copies.

In addition, when the charge amount of the toner was measured by the suction method, the initial charge amount was -13.4 μC/g, and the charge amount of the toner after running 100,000 sheets was -12.6 μC/g.
was almost unchanged from the initial value.

31- Furthermore, under a high temperature environment of 35°C and 90% RH and 10°C,
Even in a low humidity environment of 15% R11, an image equivalent to that obtained in a normal temperature environment was obtained, and no toner filming on the photoreceptor was observed.

Example 11 Instead of the compound represented by the general formula (I) in Example 1, R43 and R
The toner of the present invention was produced in the same manner as in Example 1, except that a compound in which Sa is a tert-butyl group, all other R's are hydrogen atoms, X is a zinc atom, and n=2 was used. I got it.

Using the obtained I-ner, an image was produced in the same manner as in Example 1, and a good image was obtained, and the image did not change even after the [0-angle] was removed.

Furthermore, when the toner charge amount was measured using a suction method, the initial charge amount was -12.2 μC/g, and the toner charge amount after running 100,000 sheets was -11.7 μC/g, which was almost the initial value. It didn't change.

Furthermore, under a high humidity environment of 35°C and 90% RH, and at 10°C,
Even in a low humidity environment of 132-5% RH, an image equivalent to that obtained in a room temperature environment was obtained, and no toner filming on the photoreceptor was observed.

Example 2 Instead of the compound represented by the general formula (I) in Example 1, in the -maximum (V), 1tei and R
The toner of the present invention was produced in the same manner as in Example] except that a compound in which GII is a tert-butyl group, all other R's are hydrogen atoms, X is a potassium atom, and n= ] was used. I got it.

When the obtained toner was used to produce an image in the same manner as in Example, a good image was obtained, and the image did not change even after running 100,000 sheets. When measured by a method, the initial charge amount was -12.2 μC/g, and the charge amount of the toner after running 100,000 sheets was -11.9 μC/g, which was almost unchanged from the initial value.

Furthermore, under a high humidity environment of 35°C and 90% RH, and at 10°C,
Even in a low humidity environment of 15% RH, an image equivalent to that obtained in a room temperature environment was obtained, and no 1-ner filming on the photoreceptor was observed.

Example 13 Instead of the compound represented by the general formula (I) in Example 1, in the general formula (V), all LIR70 are hydrogen atoms, and X is a calcium atom,
A toner of the present invention was obtained in the same manner as in Example 1 except that a compound in which n=2 was used.

Got it! - When an image was produced in the same manner as in Example 1 using a dye, a good image was obtained, and the image did not change even after running 100,000 sheets.

Furthermore, when the toner charge amount was measured using a suction method, the initial charge amount was -10.5 μC/g, and the toner charge amount after running 100,000 sheets was -10.2 μC/g, which was the same as the initial value. Not much changed.

Furthermore, under a high humidity environment of 35℃ and 90% RH and ]00℃
Even in a low humidity environment of 15% RH, an image equivalent to that obtained in a room temperature environment was obtained, and no toner filming on the photoreceptor was observed.

Example]-4 Instead of the compound represented by the general formula (1) in Example 1, in the general formula (V), RG3 and R1
The toner of the present invention was obtained in the same manner as in Example 1, except that a compound in which is an ethyl group, all other R's are hydrogen atoms, X is a hydrogen atom, and n=1 was used. .

When an image was produced using the obtained toner in the same manner as in Example 1, a good image was obtained, and the image did not change even after running 100,000 copies.

In addition, when the toner charge amount was measured using a suction method, the initial charge amount was -11.2 μC/g, and the toner charge amount after running 100,000 sheets was -11.1 μC/g, which was almost the initial value. It didn't change.

Furthermore, under a high humidity environment of 35℃, 90% R)l and 10℃
Even in a low-humidity environment of 15% RH, an image equivalent to that obtained in a normal-humidity environment was obtained, and no toner filming on the photoreceptor was observed.

Comparative Example 35 - Except that copper phthalocyanine green was used instead of the compound represented by the general formula (1) in Example 1,
A comparative toner was obtained in the same manner as in Example 1.

When an image test was conducted using the obtained toner in the same manner as in Example 1, a clear image with no fog was obtained at the beginning, but after about 5,000 copies, the image became unclear with fog, and the photosensitive Toner filming was observed on the body surface. Furthermore, under high temperature and high humidity conditions, the image density was as low as 0.9. When the charge amount was measured in the same manner as in Example 1, the initial charge amount was 1]0.0 μC/g, which was sufficient, but after running 5,000 sheets, it decreased to -3.9 μC/g. Ta.

〔Effect of the invention〕

The toner for developing an electrostatic image according to claim (1) contains at least one of the chromium compounds represented by the general formulas (I) to (V) as a negative charge control agent, so that the toner and the developing sleeve or Frictional charging with a charge imparting member such as a blade can be maintained at a stable negative polarity.

36- Further, the I-ner does not change its various performances such as triboelectric charging properties even if the environment such as mechanical impact, friction, temperature and humidity conditions changes.

Therefore, with the image forming method of claim (2), it is possible to obtain a high-quality image equivalent to the initial image even after continuous copying without background smudge or toner scattering.

Further, in this method, stable high-quality black images can be obtained even under various environments, and there is no filming on the photoreceptor even after long-term use.

[Brief explanation of drawings]

The drawing is a schematic sectional view showing an example of a developing device using the non-magnetic component toner of the present invention useful for carrying out the method of the present invention. 1... Electrostatic latent image carrier, 2... Toner transport member, 3
Toner thickness regulating member, 4. Toner supply member, 5. Stirring blade, 6. Toner, 7. Toner tank.

Claims (2)

[Claims] (1) In a toner consisting of at least a binder resin and a colorant, the following general formulas (I) to (V) are used as a negative charge control agent.
A toner for developing an electrostatic image, comprising at least one chromium compound represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formulas, R_1 to R_9, X and n each represent the following. R_1 to R_4: One of them is ▲There are mathematical formulas, chemical formulas, tables, etc.) , Others are H atoms or alkyl groups or alkoxy groups with 1 to 18 carbon atoms. R_5: Phenyl group, naphthyl group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼
. In addition, a substituent such as a methyl group, an ethyl group, a tert-butyl group, a nitro group, a halogen atom, or a hydroxyl group may be attached to the phenyl group and the naphthyl group. R_6 to R_9: One of them has a ▲mathematical formula, chemical formula, table, etc.▼, and the others are H atoms or alkyl groups or alkoxy groups having 1 to 18 carbon atoms. R_1_0: Phenyl group, naphthyl group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. In addition, a substituent such as a methyl group, an ethyl group, a tert-butyl group, a nitro group, a halogen atom, or a hydroxyl group may be attached to the phenyl group and the naphthyl group. X: K, Ca, Ba, Mg, Na, H, Li or Zn atom. n: 1 or 2 depending on the valence of X. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R_1_1 to R_1_8, X and n each represent the following. R_1_1 to R_1_4: One of them is R_1_9-
NH-, and others are H atoms or alkyl groups or alkoxy groups having 1 to 18 carbon atoms. R_1_9: Phenyl group, naphthyl group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. In addition, a substituent such as a methyl group, an ethyl group, a tert-butyl group, a nitro group, a halogen atom, or a hydroxyl group may be attached to the phenyl group and the naphthyl group. R_1_5 to R_1_8: one of them is R_2_0-
NH-, and others are H atoms or alkyl groups or alkoxy groups having 1 to 18 carbon atoms. R_2_0: Phenyl group, naphthyl group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. In addition, a substituent such as a methyl group, an ethyl group, a tert-butyl group, a nitro group, a halogen atom, or a hydroxyl group may be attached to the phenyl group and the naphthyl group. X: K, Ca, Ba, Mg, Na, H, Li or Zn atom. n: 1 or 2 depending on the valence of X. ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, R_2_1 to R_4_0, X and n each represent the following. R_2_1 to R_4_0: H atom or an alkyl group having 1 to 18 carbon atoms, or Alkoxy group. X: K, Ca, Ba, Mg, Na, H, Li or n: X
1 or 2 depending on the valence of. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (In the formula, R_4_1 to R_6_0, X and n each represent the following. R_4_1 to R_6_0: H atom or an alkyl group having 1 to 18 carbon atoms, or Alkoxy group. X: K, Ca, Ba, Mg, Na, H, Li or n: X
1 or 2 depending on the valence of. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, R_6_1 to R_7_0, X and n each represent the following. R_6_1 to R_7_0: H atom or an alkyl group having 1 to 18 carbon atoms, or Alkoxy group. X: K, Ca, Ba, Mg, Na, H, Li or Zn atom. n: 1 or 2 depending on the valence of X.) (2) An image forming method using a one-component development method in electrophotography, in which a thin layer of toner is supplied to a latent image carrier to develop a latent image, characterized by using the toner according to claim (1). image forming method.