JPS638652A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To obtain the titled toner which does not have too much triboelectrifiability and has positive electrifiability and is not affected to temp. and humidity by incorporating a specific compd. to the titled toner as a polarizing controller. CONSTITUTION:The titled toner comprises at least one of the compds. shown by the formula (fulfate, sulfonate or tetraphenylborate compd). In the formula, R<1> is hydrogen atom or alkyl group, R<2> and R<5> are each hydrogen or halogen atom, etc. R<2> and R<5> are each the same or different with each other, R<6> is hydrogen atom or alkyl group, X- is R<7>SOm- group (R<7>X is 1-30C aliphatic or aromatic org. group, (m) is an integer of 3 or 4). The compounding amount of the electric charge controller contd. in the toner is preferably 0.1-10 wt.% on the basis of the total weight of the toner. Thus, the toner having a suitable triboelectrifiability and environmental stability is obtd.

Description

[Detailed Description of the Invention] The present invention relates to a dry toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc.
The present invention relates to a dry toner for developing electrostatic images, which contains at least one specific compound as a charge control agent (polar control agent).

Conventional Technology Methods for developing electrostatic images formed on electrophotographic photoreceptors, electrostatic recording materials, etc. include 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 toner or a one-component or two-component dry developer in which the toner 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), desired charging properties cannot be obtained if colorants such as dyes and pigments are simply dispersed in a binder resin, so an appropriate amount of a charge control agent is added to the toner. It is normal to have Typical examples of conventional charge control agents include (i) nigrosine dyes, which impart a positive charge to toner, and (ii)
Examples of things that impart a negative charge to the toner include metal-containing dyes such as chromium-containing monoazo complexes, chromium-containing salicylic acid compound complexes, and chlorine-containing organic dyes (copper phthalocyanine green, chlorine-containing monoazo dyes). However, although toners containing such conventional charge control agents exhibit good development characteristics initially, they have the disadvantages of short lifespan and poor environmental stability (degree of stability against changes in temperature and humidity).

In addition, many of these conventional charge controls.

There is a problem in that the charging property (frictional charging property) imparted to the toner tends to be excessive. Therefore, for example, when a two-component dry developer is used with a relatively small amount of toner mixed into the carrier, the image obtained by development will have a low image density and will be unclear and prone to density unevenness. This is because the excessive triboelectricity imparted to the toner increases the electrostatic holding force that acts between the toner and the carrier, and as a result, during development, the toner is attracted to the electrostatic latent image on the photoreceptor. This is thought to be because it is less likely to be

Conventionally, therefore, a method has been adopted in which the triboelectricity imparted to the toner is reduced by increasing the mixing ratio of the toner to the carrier. In other words, when the mixing ratio of toner to carrier is increased, the frequency of contact between individual toners and the carrier surface is reduced, and the triboelectric charge that should be applied to each toner is reduced. The electrostatic holding force becomes weaker, and the image quality decreases by 1 degree.
A proper image with no unevenness etc. can be obtained.

However, in such a method, problems such as adhesion and contamination of a few particles contained in the toner onto the carrier, and furthermore, a phenomenon in which the toner adheres to the carrier due to frictional heat generated by mixing and stirring the developer in the developing device, etc. The developing ability of the developer decreases, making it difficult to maintain the developing ability of the developer stably over a long period of time.

In any case, most of the charge control agents that have been proposed so far cannot maintain adequate charging properties over a long period of time. Regarding these conventional charge control agents (
i') JP-A-49-51951, JP-A No. 52-10141
No. 52-92726, No. 52-113739, No. 54-124731, No. 54-134441,
No. 55-18620, No. 56-11461, No. 56-46248, No. 56-544446, No. 57-54953.

No. 57-63550, No. 57-119364, No. 58-9154, No. 58-150969, No. 60-
Publications such as No. 107654 and No. 60-123849;
No. 26784, Special Publication No. 49-20225.

JP-A-50-140137, JP-A-50-14203
No. 7, JP-A-50-142038, JP-A-46-43
No. 440, Special Publication No. 1973-30899, Special Publication No. 49-4
No. 6423, Japanese Patent Publication No. 49-26909, Japanese Patent Publication No. 1973
This method is disclosed in publications such as No.-51949 and Japanese Unexamined Patent Publication No. 134303/1983.

A first object of the present invention is to provide a toner that is effective for one-component to two-component dry developers, especially two-component type, in which the triboelectric chargeability is positively controlled over a long period of time without becoming excessively high. It provides: The second object of the present invention is to provide an electrostatic image developing device that not only provides stable images at all times, but also has durability and is highly stable even in environments where relative humidity changes significantly. It provides positive polarity toner.

Structure The dry toner for developing electrostatic images of the present invention has the following general formula (I
)(If)(m)(IV)(V)(VI)(■)
It is characterized by containing at least one of the compounds represented by (■), (■) and (X) (sulfate compound, sulfonate compound, or tetraphenylborate compound) as a charge control agent.

General formula (I) [However, R1 represents hydrogen or an alkyl group. R2゜R'
, R', and Rs represent hydrogen, halogen, an alkyl group, an amino group, an alkylamino group, or an acetoxy group, and R'', R', R', and R' may be the same or different at the same time.

RG is hydrogen, an alkyl group, an acetoxy group, an alkyl fatty acid group, an alkyl fatty acid ester group.

Indicates a phenyl group or a substituted phenyl group. X- is B'-K
)4 or R' S Om- (R' is an aliphatic or aromatic organic group having 1 to 30 carbon atoms. Typical examples of aliphatic groups include alkyl sulfates and sulfonates, such as methyl sulfate and methyl sulfone. Examples of aromatic acids include P-toluenesulfonate, naphthalene-α-sulfonate, naphthalene-β-sulfonate,
Examples include anthracene sulfonate. m is an integer of 3 or 4. ) is shown. ] A compound represented by the general formula (II) [However, R", Rs, R10 and R" represent, and this R
m, R5, R16, RlL may be the same or different at the same time. R'S Om- has the general formula (I
) is the same as that of ] A compound represented by the general formula (m) (However, LR", R', R", R11, R12 and R
13 The same as the general formula (■), these R', R
'.

Rto, R11, R'', R'' may be the same or different at the same time, R'SOm- is represented by the general formula (I
) is the same as that of ] A compound represented by the general formula (IV) [However, R'', R', R', Rs and R7S Om
- is the same as in general formula (I). ] A compound represented by the general formula (V) [However, R1 is the same as above. R14 and Rls represent hydrogen, halogen, an alkyl group, an alkoxy group, or an alkyl fatty acid ester group, and these R'' and R'' may be the same or different at the same time. Both R'' and R17 are the same as R1, and these Rus and R'' may be the same or different at the same time. R18 represents a substituted amino group or a substituted phenyl group. ] A compound represented by the general formula (Vl) [However, R2, R3, R4, Rs, Rm and X- are the same as those of the general formula (I), and among these, R2゜R
3, R4, and R5 may be the same or different at the same time. ] A compound represented by the general formula (■) [However, R'', R3, R', R', R' and X- are the same as those in the general formula (I), and among these, Rz.

R3, R4, and R5 may be the same or different at the same time. Both R" and R" are the same as R2, and R" and R20 may be the same or different at the same time.] A compound represented by the general formula (■) (However, LR", Rj, R' , R', R', R", R" and
19, R2G and HX- are the same as the above general formula (■). R
"and R" are both the same as R2 above, and these R", R
" may be the same or different at the same time." and general formula (X) [However, L/R2, R'
, R', R', R', Rlg, R''.

X- is the same as the general formula (■) above. ] Incidentally, the present inventors have conducted various studies and studies regarding the charge control of dry toners, and have found that if the compound represented by the above general formula is added to the toner as a positive charge control agent, appropriate triboelectric charging properties and It was confirmed that a toner with environmental stability etc. could be obtained. The present invention has been made based on such knowledge.

Typical specific examples of the compound represented by the general formula (I) used as a charge control agent in the present invention include the following (from NQl to Nα16). In addition, X- here is the above-mentioned R75O1,l- or BQ+o
) is the same as 4 (margin below).

Na1. C, 1,46000 (Acriflavin) N
α2. C, 1,46005 (Pasic Orange 1
4) Nα3. C01,46065 (Benzoflavin) Nα4. C, L46070 Nα5. C, 1,46080 Na6. C, 1,46040 (Pasic Yellow 9)■ Nα7. C, 1,46045 (phosphine E) N
α8. C, 1,46050 (Flavophosphine Brands) ■ 1JQ9. C, 1,46055 (acridine orange R) ear Na1O, C91,46060 (flaveosin) Nα1
1. C, 1,46010 Nn12. C, 1, 46015 (Acridine Scarlet 5) List 13. C01,46020 (Acridine Orange R) Roof Nα14. C, 1,46025 (Acridine Yellow G and T) Nα15. C, 1,46035 Nn16. CJ, 46075 ■ Typical specific examples of the compound represented by the general formula (II) or (III) are as follows (Nα17 to Na
(up to 26). R'SOm- is as described above.

Nn17. C, 1,5107O Nα18. C, 1,51170 Blood 19. C:, 1.51175 Na20. C, L51180 Shame 21. C, 1,51185 Nα22. C, 1,5119O N(CH, 2 Nα23. C, 1,51195 Nα24. C, 1,5120O Nl125. C, I, 51205Nα26.
C, 1,51210 Representative specific examples of the compound represented by the general formula (IV) include the following (Nα27 to Nα35), R780m- is as described above.

Na27. C,1,5ZOOO Nα2g, C,1,52002 Nn29. C, 1, 52005 NQ30. C, 1,5201O Nα31. C, 1, 52015 NQ32. C,1,5202O Nα33. C, 1,52025 Nα34. C, 1,52030 to 35. C, 1,52040 Representative specific examples of the compound represented by the general formula (V) include the following (N(I36 to N(I48))
can be given. X- is R'S Om- or B's Om- as described above.

Nα36. C, 1,48013 Na31. C, 1,48015 NL138. C, 1,4802ONα39.
C,1,48025 CH,C:Ha Nα40. C, 1,4803O Nα41. C, 1,48035 Nα42. C, 1,48035 Nα43. C01,48055 NQ44. C,1,4806O N(I45,C,1,48065 &46.C,1,4807O Na47.C,1,48075 to H3CH3N1148.C,1,48080The above general formula (V
l) (vn) (■) Typical specific examples represented by (■) or (X) include the following (Nn49 to 82). X- is R'SO as mentioned above
m- or B”i)J.

Na49. C, 1,50000 (flavindrin○
)Nn50. C, 1,50030 (nee eutral violet) Nα52. C, 1,50040 Nα53. C, 1,50045 Na54. C, 1,50050 (safranizole)
Nα55. C, 1,50055 Nα56. C, 1,50080 (indoline scarlet) Nα57. C, 1,50150 (neutral blue) Na5g, C,1,50155 (Azine Green GB) Na59. C,'1.50160
(Pacele Blue R) Nα60. C, 1,501
65 (Basle Green BB) Nα61. C,1
, 50200 (Safranin B Extra) & 62.
C,1,50204(Indamine Blue-B)Na6
3. C, 1,50205 Nα64. C, 1,50206 Nα65. C,1,50210 +, C, 1,50221 and Nα70. C, 1,50225 (Heliotrope
B) Kan71. C, I, 50235 Nα72. C, 1,50240 (Safranin T) N
α73. C, 1,50245 Nn74. C, 1,5025O Nn75. C, 1,50255 (metaphenylene
Blue B) N1176, C, 1,50260 (tanran heliotrope) Nα77, C, 1,502
65 (ethyl blue BD) Na78. C,1,5
0305 and N (C, upper 1.)2 Nα79. C, 1,50306 Nα80. C, 1,50370 and Nα81. C, 1,50375 and these charge control agents for toner according to the present invention are synthesized by known means. These charge control agents may be used alone or in combination of two or more.

The toner of the present invention is produced using such a charge control agent, a colorant, and a binder resin as essential components. However, when the charge control agent also serves as a coloring agent, the coloring agent may or may not be added.

In the present invention, the amount of the charge control agent contained in the toner is preferably in the range of about 0.1 to 10% by weight based on the total amount of the toner. If it is less than 0.1% by weight, the toner will not be positively charged and is not practical, and if it exceeds 10 parts by weight, the toner will become too charged and the electrostatic attractive force with the carrier will increase.

All the pigments and dyes conventionally used as toner colorants can be used as the colorant used in the present invention.

Specifically, carbon black, nigrosine dye, aniline blue, calco oil blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite greens xalate, lamp black, oil black, and azo. Mention may be made of oil black, rose bengal and mixtures thereof.

Further, as for the binder resin used in the present invention, all of the binder resins that have been used hitherto as binder resins for toners can be used as well as the above-mentioned colorants. Specifically, styrenes such as styrene and parachlorostyrene, vinylnaphthalene, vinyl ester acids such as vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, etc. Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloro-ethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, α such as ethyl methacrylate, butyl methacrylate, etc.
-esters of methylene aliphatic monocarboxylic acids, acrylonitrile, methacrylonitrile, acrylamide,
For example, vinyl metal ether, vinyl isobutyl ether.

Vinyl ethers such as vinyl ethyl ether; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; polymers obtained by polymerizing monomers, copolymers obtained by copolymerizing two or more of these monomers, or mixtures thereof, such as rosin-modified phenol-formalin resins, oil-modified epoxy resins, polyurethane resins, and cellulose resins. , non-vinyl resins such as non-vinyl thermoplastic resins such as polyether resins, or mixtures of these and vinyl resins as described above.

In particular, when the toner is for pressure fixing, the binder resin used is polyolefin (low molecular weight polyethylene,
low molecular weight polypropylene, polyethylene oxide, polytetrafluoroethylene, etc.), epoxy resin, polynystyl resin (
acid value 10 or less), styrene-butadiene copolymer (monomer ratio 5-30:95-70), olefin copolymer (ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer, ethylene-methacrylic acid copolymers, ethylene-methacrylic acid ester copolymers, ethylene-vinyl chloride copolymers, ethylene-vinyl acetate copolymers, ionomer resins, etc.), polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymers,
It is advantageous to use maleic acid-modified phenolic resins, phenol-modified terpene resins, and the like.

In addition to the above-mentioned components, the toner of the present invention contains various plasticizers (dibutyl phthalate, dioctyl phthalate, etc.), resistance adjusters ( It is also possible to add auxiliary agents such as tin oxide, lead oxide, antimony oxide, etc.).

The dry toner of the present invention is particularly effective when used as a two-component developer, but is not limited thereto, and may be used as a one-component magnetic toner by containing a magnetic material.

As the magnetic material contained in the magnetic toner, it is desirable to use a material that is chemically stable and can easily be obtained in the form of fine particles with a particle size of 1 μm or less, so magnetite (triiron tetroxide) is optimal. . Typical magnetic or magnetizable materials include cobalt, iron, and gold such as nickel.
aluminum, cobalt, copper, iron, lead, magnesium,
Alloys and mixtures of metals such as nickel, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium: aluminum oxide, iron oxide, copper oxide,
Metal compounds including metal oxides such as nickel oxide, zinc oxide, titanium oxide, magnesium oxide; refractory typhides such as vanadium nitride and chromium nitride; carbides such as tungsten carbide and silica carbide; ferrites and the like; Examples include mixtures of the following.

These ferromagnetic materials preferably have an average particle size of about 0.1 to 1 μm, and are contained in the toner in an amount of about 10 to 140 parts by weight based on 100 parts by weight of the resin component, particularly preferably about 100 parts by weight of the resin component. The amount is 20 to 70 parts by weight.

Furthermore, in the present invention, after producing toner particles (5 to 20 μm), fine powders such as Tie, Al2O, and Sin are added to the toner particles (addition in the range of 0.1 to 1% by weight based on the toner). It is also effective to modify the fluidity of the toner by coating the surface of the toner particles with these materials, and to prevent the deterioration of the photoreceptor by adding zinc stearate, phthalic acid, etc. .

As described above, the dry toner of the present invention can be used as a touchdown type one-component developer, or can be used as an ordinary one-component toner by adding and dispersing a magnetic material (such as magnetite powder). However, it is especially useful as a toner component of a two-component developer mixed with a carrier and used in so-called dry development methods such as the cascade method and the magnetic brush method.

As a carrier, a core material with a particle size of about 50 to 300 μm (
iron powder, nickel powder, ferrite powder, glass beads, etc.)
on the surface of styrene-acrylic ester copolymer, styrene-methacrylic ester copolymer, acrylic ester polymer, methacrylic ester polymer, silicone resin, polyamide resin, ionomer resin, polyphenylene sulfide resin, etc., or a combination of these resins. A coated mixture is used.

Next, examples and comparative examples will be shown. All parts herein are parts by weight.

Example 1 Styrene-2-ethylhexyl acrylate copolymer 100 parts Carbon black 13 parts Charge control agent (toluene sulfonate of the above compound Nα1) 1 part were melt-kneaded in a hot roll mill, cooled, and coarsely ground using a hammer mill. It was pulverized using an air jet type pulverizer. The obtained fine powder was classified to have a particle size of 5 to 20 μm to produce a toner according to the present invention. A two-component dry developer was prepared by mixing 25 parts of this toner with 975 parts of a carrier (spherical ferrite powder with a particle size of about 100 μm and having a silicone resin coat layer with a thickness of about 1 μm).

The charge amount ((Q/M) hereinafter the same) of the toner in this developer by the blow-off method was measured to be 15 μc/g.

Further, toners and two-component type dry developers according to the present invention were prepared in the same manner as above except that the charge control agent was changed in various ways, and the amount of charge of these was measured. The results are shown in Table-1.

(Margin below) Table 1 Using these developers, 10°C 15% RH 120°C 60
%RH, an organic photoconductive photoreceptor sensitive to negative charges was used for development in an electrophotographic copying machine that repeated the electrophotographic process at a rate of 30 times per minute. A clear black toner image was obtained. Furthermore, no deterioration in copy quality was observed even when 500 sheets were continuously copied. Furthermore, although too many sheets were continuously copied under an environment of 30° C. and 90% RH, the image quality did not change and good quality was maintained.

For comparison, a comparative toner was prepared and a two-component type dry developer was prepared in exactly the same manner as above except that the charge control agent was changed to Nigrosine Base EX (manufactured by Orient Chemical Co., Ltd.).

By the toner blow-off method in this comparative developer?
The iF charge was measured to be 38 μc/g.

Subsequently, when development was carried out in the same manner as above using this comparative developer, the resulting copy had a low image density because the amount of charge was too high.

When additional comparison toner was added to increase the image density, the image became foggy.

Example 2 A toner having a particle size of 5 to 20 μm according to the present invention was produced in exactly the same manner as in Example 1, except that the toner components were replaced with those shown below, and a two-component dry developer was produced.

Carbon black 13 parts The charge amount of the toner in this developer by the blow-off method was 16.
It was measured to be 3μc/g.

Further, toners and two-component type dry developers according to the present invention were prepared in the same manner as above except that the charge control agent was changed in various ways, and the amount of charge of these was measured. The results are shown in Table-2.

Table 2 Subsequently, when these developers were used for development in the same manner as in Example 1, many clear black copies without fog were obtained.

Example 3 A black toner having a particle size of 5 to 20 μm according to the present invention was prepared in exactly the same manner as in Example 1, except that the toner components were replaced with those shown below, and a two-component dry developer was prepared.

Carbon black 13 parts The charge amount of this developer by toner blow-off method is 12μ
c/g.

Further, toners and two-component type dry developers according to the present invention were prepared in the same manner as above except that the charge control agent was changed in various ways, and the amount of charge of these was measured. The results are shown in Table-3.

Table 3 Subsequently, when these developers were used for development in the same manner as in Example 1, many clear black copies without fog were obtained.

Example 4 A toner having a particle size of 5 to 20 μm according to the present invention was prepared in exactly the same manner as in Example 1, except that the toner components were replaced with those shown below, and a two-component dry developer was prepared.

Polystyrene resin 100 parts Carbon black 13 parts Hydrophobic silica
0.2 parts The charge amount of the toner in this developer by the blow-off method was 11 μc/g.

Further, toners and two-component type dry developers according to the present invention were prepared in the same manner as above except that the charge control agent was changed in various ways, and the amount of charge of these was measured. The results are shown in Table 4.

(The following is a margin) Table 4 Subsequently, development was carried out in the same manner as in Example 1 using these developers, and a large number of clear black copies without fog were obtained in all cases.

Example 5 A toner having a particle size of 5 to 20 μm according to the present invention was prepared in exactly the same manner as in Example 1, except that the toner components were replaced with those shown below, and a two-component dry developer was prepared.

Bisphenol type epoxy resin 100 parts Carbon black 15 parts The charge amount of this developer by toner blow-off method is 17 μc/g
Met.

Furthermore, toners and two-component type dry developers according to the present invention were prepared in the same manner as above except that the charge control agent was changed, and the band'; li amounts of these were measured. The results are shown in Table-5.

When these developers were used for development in the same manner as in Example 1, clear black images without fog were obtained. Furthermore, no deterioration in copy quality was observed even after 20,000 copies were made continuously.

Example 6 A toner having a particle size of 5 to 20 μm was prepared in the same manner as in Example 1, except that the toner components were replaced with those shown below, and a two-component dry developer was prepared.

Styrene-butadiene copolymer 50 parts Chlorinated paraffin (degree of chlorination approximately 70) 40 parts Polystyrene 10 parts Carbon black
Part 12 again. Toners and two-component type dry developers according to the present invention were prepared in the same manner as above except that the charge control agent was changed, and the amount of charge of these was measured. The results are shown in Table-6.

Table 6 The charge amount of the toner in this developer by the blow-off method was 13 μc/g.

When these developers were used for development in the same manner as in Example 1, clear black images without fog were obtained. Furthermore, no deterioration in copy quality was observed even after 30,000 copies were made continuously.

Example 7 20 parts of polyvinyl butyral resin and 10 parts of carbon black were melt-kneaded using a hot roll mill, cooled, and coarsely ground using a hammer mill.
It was pulverized using an air jet type pulverizer. The obtained fine powder was classified to have a particle size of 5 to 20 μm to produce a toner according to the present invention. 25 parts of this toner and 975 parts of iron powder carrier (particle size: about 100 μm) were mixed to prepare a two-component dry developer.

The charge amount of the toner in this developer by the blow-off method was measured to be 15 μc/g.

Also, 'I! ! Toners and two-component dry developers according to the present invention were prepared in the same manner as above except that the load control agent was changed, and the amount of charge was measured. Table 7 of the results
Shown below.

Table 7 When copies were made in the same manner as in Example 1 using these developers, many clear black copies were obtained on plain paper.

Example 8 A toner having a particle size of 5 to 20 μm was prepared in the same manner as in Example 1, except that the toner components were replaced with those shown below, and a two-component dry developer was prepared.

Maleic acid resin 100 parts The charge amount of the toner in this developer by the blow-off method is 12
It was μc/g.

Further, toners and two-component type dry developers according to the present invention were prepared in the same manner as above except that the charge control agent was changed in various ways, and the amount of charge of these was measured. The results are shown in Table-8.

Table 8 When copies were made in the same manner as in Example 1 using these developers, clear red images were obtained in all cases.

Example 9 A toner having a particle size of 5 to 20 μm was prepared in the same manner as in Example 1, except that the toner components were replaced with the following toner components, and a two-component dry developer was prepared.

Styrene-ethyl acrylate copolymer 80 parts Polyester resin 20 parts Carbon black 10 parts The charge amount of the toner in this developer by blow-off method was 19 μc/g.

Further, toners and two-component type dry developers according to the present invention were prepared in the same manner as above except that the charge control agent was changed, and the amount of charge was measured.

Subsequently, when copies were made in the same manner as in Example 1 using these developers, clear black images were obtained in all cases.

Furthermore, when we measured the amount of charge after leaving these developers in an environment of 30°C and 90°C RH for 5 hours, we found that even if the relative humidity changed? It was confirmed that almost no change was observed in the iF electric characteristics. In addition, when 30,000 sheets were continuously copied using the developer left for 5 hours under this high humidity and high temperature,
Table 9 summarizes the results of these experiments in which no deterioration in copy quality was observed.

Table 9 (Note) The rate is the amount of charge after being left in an environment of 30°C and 90°C RH for 5 hours. The toner of the present invention containing a tetraphenyl borate compound (a tetraphenyl borate compound) as a polarity control agent is positively charged without becoming excessively triboelectric, is almost unaffected by temperature and humidity, and is also effective in producing a large number of copies. It is something.

Claims (1)

[Claims] 1. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼...(I) [However, R^1 represents hydrogen or an alkyl group. R^2, R^3, R^4 and R^5 are hydrogen, halogen,
It represents an alkyl group, an amino group, an alkylamino group, or an acetoxy group, and these R^2, R^3, R^4, and R^5 may be the same or different at the same time. R^6 represents hydrogen, an alkyl group, an acetoxy group, an alkyl fatty acid group, an alkyl fatty acid ester group, a phenyl group, or a substituted phenyl group. X^- is R^7SO_m^- (R^7 is an aliphatic or aromatic organic group having 1 to 30 carbon atoms, m is an integer of 3 or 4) or Yes ▼ indicates. ] Compound represented by general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) [However, R^8, R^9, R^1^0 and R^1^1 are hydrogen , an alkyl group, an amino group, an acetoxy group, an alkyl fatty acid group, an alkyl fatty acid ester group, a phenyl group or a substituted phenyl group, and these R^8, R^9, R^1^0,
R^1^1 may be the same or different at the same time. R^7SO_m^- is the same as that of general formula (I). ] Compound represented by general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) [However, R^8, R^9, R^1^0, R^1^1, R ^
1^2 and R^1^3 are the same as those in general formula (II),
These R^8, R^9, R^1^0, R^1^1, R^
1^2 and R^1^3 may be the same or different at the same time. R^7SO_m^- is the same as that of general formula (I). ] Compound represented by general formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(IV) [However, R^2, R^3, R^4, R^5 and R^7SO
_m^- is the same as that in general formula (I). ] Compound represented by general formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(V) [However, R^1 is the same as that of general formula (I). R^1^4 and R^1^5 represent hydrogen, halogen, an alkyl group, an alkoxy group, or an alkyl fatty acid ester group, and these R^1^4 and R^1^5 may be the same or different at the same time. Good too. Both R^1^6 and R^1^7 are the same as R^1, and these R^1^6 and R^1^7 may be the same or different at the same time. R^1^8 represents a substituted amino group or a substituted phenyl group. X^- is the same as that in general formula (I). ] Compound represented by general formula (VI) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(VI) [However, R^2, R^3, R^4, R^5, R^6 and X
^- is the same as that of general formula (I), and among these, R^2, R^3, R^4, and R^5 may be the same or different at the same time. ] Compound represented by general formula (VII) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(VII) [However, R^2, R^3, R^4, R^5, R^6 and X
^- is the same as that of general formula (I), and among these, R^2, R^3, R^4, and R^5 may be the same or different at the same time. Both R^1^9 and R^2^0 are the same as R^2 above, and these R^1^9 and R^2^
0 may be the same or different at the same time. ] Compound represented by general formula (VIII) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(VIII) [However, R^2, R^3, R^4, R^5, R^6, R ^
1^9, R^2^0 and X^- are the above general formula (VII)
Same as. ] Compounds represented by the general formula (IX) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(IX) [However, R^2, R^3, R^4, R^5, R^6, R ^
1^9, R^2^0 and X^- are the same as in the general formula (VII), R^2^1 and R^2^2 are both the same as R^2, and these R^2^1, R^2^2 may be the same or different at the same time. ] Compounds represented by and general formula (X) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(X) [However, R^2, R^3, R^4, R^5, R^6, R ^
1^9, R^2^0, and X^- are the same as in the general formula (VII). ] A toner for developing an electrostatic image, characterized by containing a compound represented by the following.