JPH01298366A - Positively charged toner for development of electrostatic image - Google Patents

Abstract

PURPOSE:To obtain a toner providing picture images of same quality as an initial picture image even after continuous copy and having stable chargeability of frictional electricity of positive polarity by incorporating a hydrazone compd. as a positive charge controlling agent into a toner. CONSTITUTION:A hydrazone compd. is incorporated as a positive charge controlling agent into a toner consisting of a binder resin and a colorant, wherein a compd. expressed by the formula I, II, or III is suitable as the hydrazone compd. for the positive charge controlling agent. In the formula I, and III, each R1-R4, and R6-R9, is H, 1-3C alkyl, 1-3C alkoxy group, etc.; R5 is an alkyl group or a benzyl group. In the formula II, Ar is naphthalene or a naphthalene homologue, anthracene ring, styryl group or a substituted product thereof; R is an alkyl group or a benzyl group. Thus, a toner having stable chargeability for frictional electricity, sharp and uniform distribution of frictional electric charge, controllability to an amt. of electric charge suited to a developing system to be used, providing picture images of high faithfulness as good as an initial picture image even after continuous use without generating contamination of comming nor scattering of toner, is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to an electrostatic image developing toner used in electrophotography, electrostatic printing, etc., and particularly relates to a positively chargeable developing toner.

[Prior Art] Methods for developing electrostatic images using toner are broadly divided into methods using a so-called two-component developer in which toner and carrier are mixed, and methods using toner alone without being mixed with carrier. The method using a one-component developer is criticized.

The former method involves stirring the toner and carrier to charge them with different polarities, and the charged toner visualizes an electrostatic charge image with opposite polarity. Depending on the type, there are magnetic brush methods using iron powder carriers, cascade methods using bead carriers, fur brush methods, etc.

The latter one-component development method includes the powder cloud method, in which toner particles are sprayed, and the contact development method (also known as touchdown development), in which 1 to 4 particles are brought into direct contact with the electrostatic latent image surface. There is a dielectric development method in which a magnetic conductive material is brought into contact with the surface of an electrostatic latent image.

As 1 hener applied to these various developing methods, a fine powder in which a colorant such as carbon black is dispersed in a binder resin made of a natural resin or a synthetic resin is used. For example, particles obtained by dispersing a colorant in a binder resin such as polystyrene and pulverizing the particles to about 1 to 30 μm are used as the toner. Further, a toner in which these components contain a magnetic material such as magnetite is used as a magnetic toner.

The toners used in various developing methods, such as those shown in the previous section, are either made to carry a positive or negative charge depending on the polarity of the electrostatic charge image being developed, or in order to make the toner carry a charge, the toner is Although it is also possible to utilize the triboelectricity of the resin required by the component, since the toner has low chargeability in this method, the image obtained by development is likely to be foggy and unclear. Therefore, in order to impart desired triboelectric chargeability to the toner, dyes, pigments, or charge control agents that impart chargeability are added to the toner.

Conventionally, positive charge control agents include nigrosine-based oil-soluble dyes, azine-based dyes with alkyl groups, basic dyes, and basic dye lakes, but these dyes have complex structures and properties. It is inconsistent and lacks stability. Furthermore, during thermal kneading, it is likely to be decomposed or altered due to decomposition, mechanical impact, friction, changes in temperature and humidity conditions, etc., and the charge controllability is likely to deteriorate. Furthermore, the charging properties of many materials change depending on the environment.

Furthermore, when a toner containing the conventional charge control agent is used for a long time, filming may occur on the photoreceptor due to poor charging.

[Object 1] The object of the present invention is to ensure that frictional charging between toner particles, between toner and carrier, or between toner and a charge imparting member such as a phenomenon sleeve or blade in the case of component development is stable, and that the charge amount is stable. The object of the present invention is to provide a toner that has a sharp and uniform distribution and can be controlled to have a charge amount suitable for the developing system used.

Another object of the present invention is to provide a toner that does not cause background smear or toner scattering and can provide images with high fidelity equivalent to the initial image even during continuous use.

F Configuration] According to the present invention, there is provided a positively chargeable toner for developing an electrostatic image, which is characterized in that the toner comprises at least a binder resin and a colorant and contains a hydrazone compound as a positive charge control agent in the toner. It is something that will be done. .

Preferred specific examples of the hydrazone compound as a positive charge control agent include compounds represented by the following general formulas (A), (B) and (C).

General formula (A) (wherein RI, R2, R3, and R4 are hydrogen and have 1 to 1 carbon atoms)
3 represents an alkyl group, an alkoxy group having 1 to 3 carbon atoms, a dialkylamino group or a dibenzylamino group, and R5 represents an alkyl group or a benzyl group. ) (In the formula, Ar represents a naphthalene, an anthracene ring, suchyryl group, or a substituent thereof, or necessarily a pyridine ring, a furan ring, a thiophene ring, and R represents an alkyl group or a hensyl group.) General 2 (C ) (wherein Rs, R7, R8, R9 are hydrogen atoms, alkyl groups having 1 to 3 carbon atoms, alkoxy groups having 1 to 3 carbon atoms, substituted or unsubstituted dialkylamino groups, dibenzylamino groups, or halogen atoms) As a result of repeated various experiments, the present invention has demonstrated that by using the above-mentioned compound in the materials 1 to 2, a high positive charge can be obtained and good copies can be made 1 q. This is based on the knowledge that jTf met.

Next, specific examples of the compound represented by -Fukudai (A) will be shown.

General formula (A) No, RI R2R3R4ll5A-1-
tl -H-11-tl -CII3A-
2-tl -tl -CH3-11-CI
I3A-3-tl-H-C2t15-It
-C1bA-4-CH3-11-C113-11-
CII3A-5-CI+3-H-fl-
C1la -Ct13A-6-II publication f -0Ctb -11-CI13
A-7-II -0CH3-H-It -
Ct]3A-8-0CH3-H-tl-It
-CI13NO, R7Rz R3R4R
5 A-9-0CII:+-0CII3-H-II
-ClbA-10-LIC113-H-0Ctb
-tl ~CH3A-11-OCt13-
t(-11-OCH3-ClbA-12~H-0Cl1
3-OClb-It-C113
8-13-11-DCTo”-11-0CI+3
-C113A-14-0CI+3 -0C1+
3 -0C113-II -C1bAi5
-11-OCH3-OCH13-DC1+3 -C1
13A-16-II -11-0C2)+5-
1l-C113A-17-0C2115-II
-II -It -C113A
-18-It -0Czl-15-OC2H5
-11-C113A-23-H-+1-Cl13-11
-Cu2@A-24-HH-C2115-
11-CII2-@No, RI R2
R3Ra R5A-26-CH3-HH-C
H3-CI42@A-27-H-H-0CH3-H-C
H2@A-28-H-0CH3-H-H-CH2-@A
-29-0CH3-H-H-H-c++z@A-30-
0C113-0CH3-H-11-CH2@A-31-
0CH3-H-0C113-11-CH2@A-32-
0CH3-H-H-0CH3-C112@A-33-1
1-0CH3-0CH3-H-Cl12 [phase] A-34
-tl -0CH3-H-0CH3-CHz@A-
35-0CH3-0CH3-0CH3-H-CHz@A
-36-H-0CH3-0CH3-0CH3-CH2-
@A-37-H-H-0C2H5-H-CH2-@A-
38-0C2H5-H-H-H-CH2-@No,
RI R2R3R4Rs Next general formula (B)
A specific example of the hydrazone compound represented by is shown below.

General formula (B) B-6<5CH=CH--CH3 Next, specific examples of the hydrazone compound represented by the general formula (C) will be shown.

General formula (C) C-1-H-H-H-H C-2-H-H-CH5-H C-3-H-CH3-H-H C-4-CH3-H-H-H C -5-H-H-CzHs -HC-6-CH3
-H-CH3-H C-7-CH3-H-tl -Ctl:+C
-8-H-H-0CR3-tl C-9-H-0CH3-H-H C-10-0CH3-H-If -HC-1
1-0CH3-0CH3-H-1tC-+2 -DC
)+3 -H-OC113-HC-13-OCH3-H
-H-0CH3C-14-H-0Cth -0CH
3-HC-15-H-0CH3-H-0CH3C-16
-0CH3-0CH3-0CH3-HC-17-H-0
CH3-0CH3-0CH3C-18-II
-H-0C2H5-HC-19-0CzHs -H-
H-IIC-20-H-0C2H5-0C2H5-HC
-26-H-H-CI -HC-27-H
-CI-H-HC-28-CI-
H-H-11C-29-H-H-Br
-HC-30-H-Br -It
-HC-31-Br -H-H-H The amount of the compound of the present invention to be used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner manufacturing method including the dispersion method. Although not specifically limited, it is preferably used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the binder resin. 0.
If it is less than 1 part by weight, the toner will not be positively charged and is not practical. On the other hand, if the amount exceeds 20 parts by weight, the chargeability of the toner is too large and the electrostatic attraction force with xerium increases, resulting in a decrease in the fluidity of the developer and a decrease in image density.

The binder resin used in the present invention includes polystyrene,
Monopolymers of styrene and its substituted products such as polychlorostyrene and polyvinyl 1-toluene; styrene-p-chlorostyrene copolymers, styrene-propylene copolymers,
Styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-edyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-ocdylene acrylate copolymer copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, Styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, Subolene-based J4 polymers such as styrene-maleic acid copolymer and styrene-maleic acid ester copolymer: polymethyl methacrylate-1~, polystyl methacrylate-1~, polyvinyl chloride, polyvinyl acetate, polyethylene, Polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, Examples include paraffin wax, which can be used alone or in combination.

In particular, as binder resins suitable for pressure fixing, the following can be used alone or in combination.

Polyolenoin (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, polytetrafluoroethylene, etc.), epoxy resin, polyester resin, styrene-butadiene copolymer (monomer ratio 5-30:95-7)
0), olefin copolymer (ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ionomer resin), polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid-modified phenol resin, phenol-modified terpene resin.

Colorants used in the present invention include carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6G, lake,
Any conventionally known dyes such as calco oil blue rom yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dyes, monoazo dyes, disazo dyes, dyes and pigments can be used alone or in combination.

Further, when the toner of the present invention is used as a two-component developer, it is used in combination with a carrier powder.

As the carrier that can be used in the present invention, any known carrier can be used, such as iron powder, fly powder,
Examples include magnetic powder such as nickel powder, crow beads, etc., and those whose surfaces are treated with resin or the like.

In general, the toner of the present invention can further contain a magnetic material and be used as a magnetic toner. Magnetic materials contained in the magnetic 1hener of the present invention include magnetite, hematite,
Iron oxide such as ferrite, iron cobal 1~, metals such as nickel, or these metals such as aluminum, cobalt,
Examples include alloys of metals such as copper, lead, magnesium, tin, zinc, antimony, beryllium, hismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

It is desirable that these ferromagnetic materials have an average particle size of about 0.1 to 2 μm, and the amount of ferromagnetic material to be contained in the 1 to 1 toner is about 20 to 200 parts by weight per 100 parts by weight of the resin component, particularly preferably about 20 to 200 parts by weight of the resin component. The amount is 40 to 150 parts by weight per 100 parts by weight.

Further, the 1-ner of the present invention may be mixed with additives as required. Examples of additives include lubricants such as Teflon 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 black and tin oxide. and fixing aids such as low molecular weight polyethylene.

[Example] Next, the present invention will be explained with reference to Examples. Note that "parts" are based on weight.

Examples] Styrene-n-butyl methacrylate-1 to 100 parts Carbon black 10 parts Exemplary compound A
-1 2 parts The mixture having the above composition was thoroughly mixed in a Henschel mixer, then melted by heating at a temperature of 130 to 140°C for about 30 minutes in a roll mill, and after cooling to room temperature, the resulting kneaded product was pulverized. Classify, 5
1 q of toner with a particle size of ~10 μm.

For 2.5 parts of this toner, 100 to 250 meshes of ferrite coated with silicone resin 1 heki 1 noria 97
．． 5 parts were mixed in a ball mill, and the developer was added (2).

Next, apply the above developer to FT4060 made by our company.
When a reversal image was performed, a good image was obtained, and the image remained unchanged even after 200,000 images were printed.

Furthermore, when the charge amount of the toner was measured using the 10-off method, the initial charge amount was +17. Oμc/g, and the charge amount of the toner after running 200,000 sheets is +15.8μc
/g, there was almost no difference from the initial value.

In addition, under a high humidity environment of 35°C and 90% RTL, and at 10°
Even at a low humidity of C15% 1-11, images equivalent to those at normal humidity were obtained.

Further, there was no toner filming on the photoreceptor.

Comparative Example 1 A developer was obtained in the same manner as in Example 1 except that nigrosine dye was used instead of the compound of Example 1, and an image test was conducted. Initial images were clear with no fog, but after about 100,000 copies, the images became blurred with fog, and toner filming was observed on the surface of the photoreceptor. Also,
When image test 1~ was carried out under high humidity at 35 DEG C. and 90% RH, the image density was as low as 0.95, and an unclear image with fog was obtained.

Further, when the charge amount was measured in the same manner as in Example 1, the initial charge amount was +19.8 μc/g, and after 100,000 sheets, it was found to have decreased to +9.2 μc/g.

Example 2 Styrene-2-ethylhexyl acrylate copolymer
ioo part polypropylene
Part 5 car phone black
Part 7 Exemplary compound A-2
1.5 parts The mixture having the above composition is kneaded, pulverized and classified,
A toner with a particle size of 5 to 20 μm was obtained. This toner 100
1 part, 3 parts of silicon carbide (particle size: 2 µl, 1 liter) and 0.1 part of hydrophobic colloidal silica were sufficiently stirred and mixed in a speed kneader to obtain a 1 to 1 liter solution.

When this toner was loaded into a developing device as shown in the drawings and subjected to continuous copying, an image test was performed, and a good image was obtained. The image remained unchanged even after printing 50,000 images.

To explain this developing method, as shown in the drawing,
The l-toner 6 contained in the toner tank 7 is forcibly brought to the sponge roller 4 by the stirring blade 5, and the toner is supplied to the sponge roller 4. Then, as the sponge roller rotates in the direction of the arrow, the toner taken into the sponge roller 4 is transported to the toner conveying member 2, where it is rubbed, electrostatically or physically adsorbed, and the toner conveying member 2 It rotates strongly in the direction of the arrow, and a uniform thin layer of toner is formed by the elastic blade 3, 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 formed by charging the organic photoreceptor with a negative DC charge of 800 V, exposing it to light, forming a latent image, and developing it.

In addition, in order to measure the specific charge m:Q/M of the toner on the toner conveying member, the toner on the toner conveying member is sucked through a Faraday cage equipped with a filter layer on the exit side, and is trapped in the Faraday cage. When the Q/M was measured using an attraction charge measuring device for measuring the specific charge of the toner, it was confirmed that the toner was sufficiently charged at 1+-11.0 .mu.c/g.

Also, the amount of charge during running of 50,000 sheets is +10.8μ
There was almost no difference between c/g and the initial value.

In addition, image quality equivalent to that at normal humidity was obtained even in high humidity and low humidity conditions. Further, there was no toner filming on the photoreceptor.

Comparative Example 2 An image test was conducted in the same manner as in Example 2, except that nigrosine dye was used instead of the compound in Example 2.
Initially, a clear image without fogging was obtained, but after about 30,000 copies, the image became blurry with fogging, and toner filming was observed on the photoreceptor surface. Furthermore, under high temperature and high humidity conditions, the image density was as low as 0.92. Also, Example 2
When the amount of charge was measured in the same manner as above, the initial amount of charge was +1
Although it was sufficient at 0.7 μc/g, it decreased to +2.9 μc/g after running 50,000 sheets.

Example 3 Styrene-n-butyl methacrylate-1 to 100 parts Polyethylene 7 parts Carbon black 13 parts To exemplified compounds-52
The mixture having the above composition is kneaded, pulverized, and classified to form a powder with a particle size of 5 to 20 μm.
The particle size of toner is 17. For 100 parts of this toner,
Silicon carbide (2μm) 2.5 parts and titanium oxide fine powder 0
．． 4 parts were thoroughly stirred and mixed using a speed kneader to prepare a toner.

When this toner was subjected to an image test in the same manner as in Example 2, good images were obtained. The amount of charge is +10.2μc/g for Star 1~, and +9.4μc/g after 50,000 sheets.
There was almost no change, good images were obtained even under high humidity, and there was no toner filming on the photoreceptor surface.

Example 4 An image test was conducted in the same manner as in Example 1, except that Exemplified Compound A-9 was used instead of the compound in Example 1. The charging field is +10.0μC/(+10.0μC/(after 1 or 2 copies) at the start.
There was almost no change at 9.0 μc/g.

In addition, good images equivalent to those under normal humidity were obtained even under high humidity and low humidity. Further, there was no filming on the photoreceptor.

Examples 5 to 11 Toners were obtained in the same manner as in Example 2 using the developer compositions shown in the following table. The conclusions regarding the image characteristics and charging properties of these toners are shown below.

Composition of developer of Example 5] - Boo-sujirene rope tyl acrylate 100 parts polyethylene 4 parts carbon
5 parts Exemplary compound A-102, 5 parts External additive silicon carbide (3 μm) 5 parts Alumina oxide fine powder 0.6 parts Composition of developer of Example 6 Toner polyester 100 parts Polypropylene 4 parts Carbon
Part 7 Exemplary compound A-11
7 parts external additive silicon carbide (2 μm) 2 parts hydrophobic]
Roidal silica 0.1 parts Composition of active agent in Example 7 Toner epoxy resin 100 parts Polyethylene 7 parts Carbon
Part 6 Exemplary compound A-14
3 parts External additive silicon carbide (3 μm) 5 parts Titanium oxide fine powder 0.2 parts Composition of developer of Example 8 Toner Styrene-n-butyl acrylate 100 parts Polypropylene 5 parts Carbon
5 parts Exemplary compound A-162, 5 parts External additive silicon carbide (3 μm) 7 parts Zinc stearate 0.05 parts Composition of the developer of Example 9 1 to 1 Polyester 100 parts Polypropylene 7 parts Noj-bon
15 parts Exemplary compound A-182, 5 parts External additive silicon carbide (2 μm) 5 parts Hydrophobic]
Roidal silica 0.1 parts Developer composition of Example 10 Toner Styrene-〇-butyl methacrylate 100 parts Polyethylene 7 parts Carphone
10 parts Exemplary compound A-236 parts External additive Calcium carbonate (3 μm) 5 parts Hydrophobic colloidal silica 0.1 part Composition of the developer of Example 11 1 to 1 Polyester 100 parts Polyethylene 5 parts Carbon
5 parts Exemplary Compound A-365 parts External additive Hydrophobic colloidal silica 0.1 part Titanium oxide fine powder 0.3 parts Regarding the image properties of the toners with the above compositions, all of Examples 5 to 11 were black at the start. It's very clear, and even after 50,000 copies, it's still as good as it was in the beginning. In addition, under a high humidity environment of 35°C and 90% RH, and 1
Even under low humidity conditions of 0°C and 15% RH, the above Examples 5 to 1
Images equivalent to those obtained under normal humidity were obtained in all cases.

In addition, 1 to ner in Examples 5 to 11 are all 1 to 1 of the photoreceptor.
~ Didn't ner film.

Also, regarding the toner charging NQ/M, at the start, 5
The values after 10,000 copies were as shown in the table below.

Example 12 Styrene-〇-butyl methacrylate 100 parts Carbon black 10 parts Exemplary compound 8-1
Two parts of the mixture having the above composition were sufficiently stirred and mixed in a Henschel mixer, and then mixed with a roll mill for 13 minutes.
After heating and melting at a temperature of 0 to 140°C for about 30 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain particles of 1 to 100% particles having a particle size of 5 to 10 μm.

100 to 250 meshes of ferritexeria coated with silicone resin to 2.5 parts of 1 henna.
5 parts were mixed in a ball mill to obtain a developer.

Next, apply the above developer to our YRR4OSO.
When reversal development was performed, a good image was obtained, and the image did not change even after 200,000 images were printed.

In addition, when the toner charge amount was measured using the blow-off method, the initial charge amount was +15.8μC/g, and the toner charge amount after running 200,000 sheets was +14.3μC/g.
/g, there was almost no difference from the initial value.

Also, under a high humidity environment of 35°C and 90% RH, and at 10°C.
Even under the low humidity of 15%R11, the image equivalent to normal humidity is 1
It's q.

Also, there is no toner filming on the photoreceptor.

Example 13 Styrene-2-edylhexyl acrylate copolymer
100 parts polypropylene
Part 5 car phone rack
Part 7 Exemplary compound B-2
1.5 parts The mixture having the above composition is kneaded, pulverized and classified,
A toner with a particle size of 5 to 20 μm was obtained. This toner 100
3 parts of silicon carbide (particle size: 2 μm) and 0.1 part of hydrophobic colloidal silica were sufficiently stirred and mixed in a speed kneader to prepare a toner.

When these toners No. 1 to No. 1 to No. 1 were placed in the developing device shown in FIG. 1 for continuous copying and an image test was conducted, good images were obtained. The image remained unchanged even after printing 50,000 images.

In addition, when the specific charge amount: Q/M of the toner on the toner conveying member was measured using the above-mentioned suction method specific charge measurement device, +
It was confirmed that sufficient charging was achieved at 10.1 μC/g.

Also, the amount of charge during running of 50,000 sheets is +9.8μC/
There was almost no difference between g and the initial value.

Further, even under high humidity and low humidity, an image amount v1 equivalent to that under normal humidity was obtained. Further, there was no toner filming on the photoreceptor.

Example 14 Styrene-〇-butyl methacrylate 100 parts Polyethylene 7 parts Carbon black 13 parts Exemplary compound B-82 parts A mixture of the above composition was kneaded, pulverized, and classified to a particle size of 5 to 20 μm.
A toner having a particle size of . To 100 parts of this toner, 2.5 parts of silicon carbide (2 μm) and 0.0 parts of fine titanium oxide powder.
4 parts were thoroughly stirred and mixed using a speed kneader to prepare a toner.

When this toner was subjected to an image test in the same manner as in Example 2, good images were obtained. The charge ω starts at +
10.9μc/q, +10.2μc/g after 50,000 sheets
There was almost no change, good images were obtained even under high humidity, and there was no toner filming on the photoreceptor surface.

Example 15 An image test was carried out in the same manner as in Example 12, except that Exemplary Compound 8-9 was used instead of the compound in Example 12.

The charge amount was +11.6 μc/g at the start and +10.9 μc/g after 200,000 sheets, showing almost no change.

In addition, even under high humidity and low humidity, the image quality is as good as under normal humidity.
It was done. Further, there was no toner filming on the photoreceptor.

Examples 16 to 22 1 q of toner was prepared in the same manner as in Example 13 using the developer composition shown in the table. The results regarding the image characteristics and charging properties of these toners are shown below.

Composition of developer of Example 16 Toner Styrene-rope tyl acrylate 100 parts Polyethylene 4 parts Carbon
5 parts Exemplary compound B-102, 5 parts External additive silicon carbide (3 μm) 5 parts Alumina oxide fine powder 0.6 parts Composition of the developer of Example 17 l ~ Luna-Reester 100 parts Polypropylene 4 parts Carbon
Part 7 Exemplary compound B-12
7 parts External additive silicon carbide (2 μm) 2 parts Hydrophobic colloidal silica 0.1 part Composition of developer of Example 18 Toner epoxy resin 100 parts Polyethylene 7 parts Carbon
6 parts Exemplary compound B - 73 parts External additive silicon carbide (3 μm) 5 parts Titanium oxide fine powder 0.2 parts Composition of the developer of Example 19: 1 - Nurse styrene-rope tyl acrylate 100 parts Polypropylene 5 parts Carphone
5 parts Exemplary Compound B-1325 parts External additive Silicon carbide (3 μm) 7 parts Zinc stearate 0.05 parts Composition of the developer of Example 20 l ~ Luna-Reester 100 parts Polypropylene 7 parts Carbon
15 parts Exemplary compound B-142, 5 parts External additive silicon carbide (2 μm) 5 parts Hydrophobic colloidal silica 0.1 part Composition 1 of the developer of Example 21 - Nurse styrene-n-butyl methacrylate 100 parts Polyethylene 7 parts carbon
10 parts Exemplary compound B - 166 parts External additive Calcium carbonate (3 μm) 5 parts Hydrophobic chloride 0.1 part Composition of the developer of Example 22 ~ Lunaryester 100 parts Polyethylene 5 parts Carbon
5 parts Exemplary compound B-185 parts External additive Hydrophobic rolloidal silica 0.1 part Titanium oxide fine powder 0.3 parts The image quality of the toners with the above compositions was 1 star in all of Examples 16 to 22. The black color was clear, and even after 50,000 copies, it was the same as the initial color. In addition, even under a high humidity environment of 35°C, 90% R11, and a low humidity environment of 10°C, 15% R11, the toners of Examples 16 to 22 above all produced images equivalent to those at normal humidity. In Examples 16 to 22 of 1-Boo, there was no toner filming on the photoreceptor.

In addition, regarding the toner charge fa Q/M, Star Example 23 Styrene-n-butyl methacrylate 100 parts Carphone black 10 parts Exemplary compound C-
12 parts The mixture having the above composition was sufficiently stirred and mixed in a Henschel Miquilly, then heated and melted in a roll mill at a temperature of 130 to 140'C for about 30 minutes, and after cooling to room temperature, the resulting kneaded product was pulverized and classified. , 111 toner with a particle size of 5 to 10 μm
is.

For 2.5 parts of this toner, 100 to 250 mesh ferrite carrier coated with silicone resin 97.5
Mix the parts in a whole mill and add 19 parts of the developer.

Next, the above developer was set in F14060 manufactured by our company and reversal development was performed, and a good image was obtained, and the image did not change even after printing 200,000 images.

In addition, when the toner charge amount was measured using the blow-off method, the initial charge amount was +19.6 μC/g, and the toner charge amount after running 200,000 sheets was +20.1 μC.
/g, there was almost no difference from the initial value.

Also, under a high humidity environment of 35°C and 90% RH, and at 10°C.
Even at a low humidity of 15%1 (11), images equivalent to those at normal humidity were obtained.

Further, there was no toner filming on the photoreceptor.

Example 24 Polymer of styrene-2-ethylhexyl acrylate 1~100 parts polypropylene 5 parts carphone black
Part 7 Exemplary compound C-2
1.5 parts A mixture having the above composition was kneaded, pulverized, and classified to obtain a toner having a particle size of 5 to 20 μm. This 1~Na1
To 00 parts, 3 parts of silicon carbide (particle size: 2 μm) and 0.1 part of hydrophobic silicon carbide were sufficiently stirred and mixed in a speed kneader to prepare t)-.

When this toner was loaded into a current apparatus as shown in FIG. 1, continuous copying was carried out, and image printing was performed, 1q good images were obtained. The image remained unchanged even after printing 50,000 images.

In addition, when the specific electric charge rate: Q/M of the toner on the toner conveying member was measured using the above-mentioned suction method specific charge rate measuring device, +
It was confirmed that the battery was sufficiently charged at 12.3 μC/(].

Also, the amount of charge during running is +11.4μ for 50,000 sheets.
There was almost no difference between C/g and the initial value.

In addition, even under high humidity or low humidity, the image amount 'i! is equivalent to that under normal humidity! 1
or obtained. Further, there was no toner filming on the photoreceptor.

Example 25 Styrene-〇-butyl methacrylate + ioo parts Polyethylene 7 parts Carbon black 13 parts Exemplified Compound C-12 parts A mixture of the above composition was kneaded, pulverized, and classified to a particle size of 5 to 20 μm.
A toner having a particle size of . To 100 parts of this toner, 2.5 parts of silicon carbide (2 μm) and 0.0 parts of fine titanium oxide powder.
4 parts were thoroughly stirred and mixed using a speed kneader to prepare a toner.

When this toner was subjected to an image test in the same manner as in Example 2, good images were obtained. The amount of charge starts from +
11.3μC/g, after 50,000 sheets there was almost no change to +10.2μC/g, and good images were obtained even under high humidity.
There was also no toner filming on the photoreceptor surface.

Example 26 Exemplary compound C-5 instead of compound C-1 in Example 23
Image test l~ was performed in the same manner as in Example 23, except that . The amount of charge is +10.9μc/g at the start, 20
After 10,000 sheets, there was almost no change at +9.7 μc/g.

In addition, even under high humidity or low humidity, the image quality is as good as under normal humidity.
It was done. Further, there was no filming on the photoreceptor.

Examples 27 to 33 Toners were obtained in the same manner as in Example 24 using the developer compositions shown in Table 1. The results regarding the image characteristics and charging properties of these toners are not shown below.

Composition of developer of Example 27 Toner Styrene rope tyl acrylate 100 parts Polyethylene 48 [S carbon
Part 5 Exemplary compound C-42,
5 parts External additive silicon carbide (3 μm) 5 parts Alumina oxide fine powder 0.6 parts Composition of developer of Example 28 Toner polyester 100 parts Polypropylene 4 parts Carbon
7 parts Exemplary compound C-67 parts External additive silicon carbide (2 μm) 2 parts Hydrophobic colloidal silica 0.1 part Composition of developer of Example 29 Toner epoxy resin 100 parts Polyethylene 7 parts Carbon
Part 6 Exemplary compound C-9
3 parts External additive silicon carbide (3 μm) 5 parts Titanium oxide fine powder 0.2 parts Composition of the developer of Example 30 Toner dylene rope tyl acrylate 100 parts Polypropylene 5 parts Carbon
5 parts Exemplary compound C-202, 5 parts External additive Silicon carbide (3 μm) 7 parts Zinc stearate 0.05 parts Composition of developer of Example 37 Toner polyester 100 parts Polypropylene 7 parts Carbon
155 parts Exemplified product C-112, 5 parts External additive Silicon carbide (2 μm) 5 parts Hydrophobic colloidal silica 0.1 part Composition of developer of Example 32 Toner Styrene-n-butyl methacrylate 100 parts Polyethylene 7 parts Carbon
100 parts Exemplified product C-126 parts External additive Calcium carbonate (3 μm) 52B Hydrophobic colloidal silica 0.1 part Composition of developer of Example 33 Toner polyester 100 parts Polyethylene 5 parts Carbon
5 parts Exemplary Compound C-185 parts External additives Hydrophobicity] Roidal silica 0.1 part Titanium oxide fine powder 0.3 parts The image quality of the toners with the above compositions is that all of Examples 27 to 33 are black at the start. It was as clear as the initial image even after 50,000 copies. In addition, the above example 27 was
All of the toners No. 3 to 33 produced images equivalent to those of 1 Shinyuki. In addition, none of the toners of Examples 27 to 33 caused toner filming on the photoreceptor.

Also, regarding the toner charging mQ/M, at the start, 5
The values after 10,000 copies were as shown in the table below.

[effect] The effects of the present invention are listed below.

(1) Images with the same quality as the initial image can be obtained even after continuous copying.

(2) A toner exhibiting positive and stable triboelectric charging properties can be obtained.

(3) Good dispersibility in binder resin.

(4) A toner with excellent environmental stability can be obtained.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of the current apparatus used in the embodiment of the present invention.

Claims (2)

[Claims] (1) A positively chargeable toner for developing electrostatic images, characterized in that the toner comprises at least a binder resin and a colorant and contains a hydrazone compound as a positive charge control agent in the toner. (2) The electrostatic charge image developing positive according to claim 1, wherein the hydrazone compound is a hydrazone compound selected from the group of compounds represented by the following general formulas (A), (B) and (C). Chargeable toner. General formula (A) ▲ Numerical formulas, chemical formulas, tables, etc.
represents a dialkylamino group or dibenzylamino group,
R_5 represents an alkyl group or a benzyl group. ) General formula (B) ▲ Numerical formulas, chemical formulas, tables etc. (Represents an alkyl group or a benzyl group.) General formula (C) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ (In the formula, R_6, R_7, R_8, R_9 are hydrogen atoms,
It represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a substituted or unsubstituted dialkylamino group, a dibenzylamino group, or a halogen atom. )