JP2000172015A - Positive charge type black toner, cyan toner, magenta toner and yellow toner for one-component development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain black, cyan, magenta and yellow toners for one-component development excellent in positive chargeability, having a long service life and excellent also in color mixability, glossiness and anti-offsetting property. SOLUTION: The black toner consists essentially of a bonding resin, a colorant, an electric charge controlling resin and a releasing agent. The bonding resin is a polyester resin having a weight average molecular weight of 10,000-50,000 and a number average molecular weight of 3,000-15,000. At least part of the hydroxyl groups of the polyester resin have been substituted by nitrogen-containing functional groups. The colorant is carbon black of >=pH 7. The electric charge controlling agent is a styrene-acrylic resin having a tri-substituted ammonio group in a side chain and the amount of the agent is 3-15 pts.wt. based on 100 pts.wt. bonding resin. The releasing agent is a polyolefin wax and the amount of the wax is 1-7 pts.wt. based on 100 pts.wt bonding resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black toner, a cyan toner, a magenta toner and a yellow toner for positively chargeable one-component development, and more particularly, to a toner having excellent positive chargeability, a long life, and color mixing property. The present invention relates to a toner excellent in glossiness and offset resistance.

[0002]

2. Description of the Related Art With the practical fixing of full-color machines in copying machines and the like in recent years, higher-quality full-color images have been demanded, and various improvements and developments have been made in terms of toner in order to meet such demands. ing. For example, in JP-A-3-163565, the volume average particle size is 4 to 10.
Micron, using a polyester resin in which at least a part of carboxylic acid groups are substituted with a functional group containing nitrogen as a binder resin, and having a fluidity improver whose triboelectric charge amount with a specific carrier is a specific value or less. Color toners have been proposed.

[0003] However, although the color toner can provide stable chargeability, it is still insufficient in terms of color mixing and gloss required for higher quality full-color images.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has an excellent positive charging property, a long life, and excellent color mixing properties, glossiness and offset resistance. An object of the present invention is to provide black, cyan, magenta, and yellow toners for component development.

[0005]

According to the present invention, there is provided a toner comprising at least a binder resin, a colorant, a charge control resin, and a release agent, wherein the binder resin has a weight average molecular weight of 1
A polyester resin having a number average molecular weight of 3,000 to 15,000 in a range of 0000 to 50,000, wherein at least a part of hydroxyl groups of the polyester resin is substituted by a nitrogen-containing functional group. The colorant is carbon black having a pH of 7 or more, and the charge control agent is a styrene-acrylic resin having a tri-substituted ammonium group in a side chain, and 3 to 100 parts by weight of the binder resin. 15 parts by weight, wherein the release agent is a polyolefin-based wax, and 1 to 7 parts by weight based on 100 parts by weight of the binder resin is contained. Provided.

According to the present invention, there is provided a toner comprising at least a binder resin, a colorant, a charge control resin and a release agent, wherein the binder resin has a weight average molecular weight of 10,000.
50,000 and a number average molecular weight of 3,000.
A polyester resin having a range of 0 to 15,000, wherein at least a part of hydroxyl groups of the polyester resin is substituted by a functional group containing nitrogen, the coloring agent is a copper phthalocyanine pigment, and the charge controlling agent is Is a styrene-acrylic resin having a tri-substituted ammonium group in a side chain, contained in an amount of 2 to 15 parts by weight based on 100 parts by weight of the binder resin, and a release agent is a polyolefin-based wax; There is provided a positively chargeable cyan toner for one-component development, wherein the cyan toner is contained in an amount of 0.5 to 7 parts by weight based on 100 parts by weight of the resin.

According to the present invention, there is further provided a toner comprising at least a binder resin, a colorant, a charge control resin and a release agent, wherein the binder resin has a weight average molecular weight of 10,000.
50,000 and a number average molecular weight of 3,000.
A polyester resin having a range of 0 to 15,000, wherein at least a part of the hydroxyl groups of the polyester resin is substituted by a functional group containing nitrogen, and the colorant is a naphthol or quinacridone pigment; The control agent is a styrene-acrylic resin having a trisubstituted ammonium group in a side chain, and 3 to 16 parts by weight based on 100 parts by weight of the binder resin, and the release agent is a polyolefin-based wax, There is provided a positively chargeable magenta toner for one-component development, wherein the content is 0.5 to 7 parts by weight based on 100 parts by weight of the binder resin. From the viewpoint of environmental resistance, the colorant is preferably a compound represented by the following general formula (1).

[0008]

Embedded image According to the present invention, there is provided a toner comprising at least a binder resin, a colorant, a charge control resin and a release agent, wherein the binder resin has a weight average molecular weight in the range of 10,000 to 50,000, and A polyester resin having a number average molecular weight in the range of 3,000 to 15,000, wherein at least a part of hydroxyl groups of the polyester resin is substituted by a functional group containing nitrogen, and the colorant is a condensed azo pigment. The charge controlling agent is a styrene-acrylic resin having a trisubstituted ammonium group in a side chain, and is contained in an amount of 4 to 17 parts by weight based on 100 parts by weight of the binder resin, and the release agent is a polyolefin-based wax. The positively chargeable one-component developing yellow toner is provided in an amount of 0.5 to 7 parts by weight based on 100 parts by weight of the binder resin. From the viewpoint of environmental resistance, the colorant is preferably a compound represented by the following general formula (2).

[0009]

Embedded image

[0010]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A major characteristic of the black toner for positively chargeable one-component development according to the first aspect of the present invention is that the weight average molecular weight of the binder resin is 10,000 to 50,000.
00 and a number average molecular weight of 3,000 to 15,
The use of a polyester resin having a range of 000, wherein at least a part of hydroxyl groups of the polyester resin is substituted by a functional group containing nitrogen.

That is, in order to obtain a high-quality full-color image, it is necessary to use a toner having good color mixing and gloss. In order to obtain a toner having such characteristics, generally, the molecular weight of the binder resin may be reduced. However, simply lowering the molecular weight of the binder resin causes a problem that the melting point of the binder resin is lowered, so that the toner composition is fused to a blade, a photoconductor, or the like. Therefore, in the present invention, by setting the weight average molecular weight and the number average molecular weight of the binder resin to the above specific ranges, while preventing fusion of the binder resin to a blade or the like, it achieves good color mixing and gloss. -ing When the weight average molecular weight of the binder resin is less than 10,000, problems such as fusion of the toner to the blade and filming of the toner composition on the drum occur. On the other hand, when the weight average molecular weight exceeds 50,000, the gloss Problems such as dropping and drum scraping occur. If the number average molecular weight of the binder resin is less than 3,000, problems such as fusion of the toner to the blade and filming of the toner composition to the drum occur. Problems such as scraping occur. More preferably, the weight average molecular weight is in the range of 15,000 to 30,000, and the number average molecular weight is in the range of 8,000 to 12,000.

The weight-average molecular weight and number-average molecular weight of the present invention are measured using "Gel Permeation Chromatograph" manufactured by Toyo Soda Co., Ltd.

The polyester resin used in the first aspect of the present invention is obtained mainly by polycondensation of a polyhydric carboxylic acid and a polyhydric alcohol.

The polycarboxylic acids used in the polyester resin include, for example, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid,
Aromatic polycarboxylic acids such as 2,4-naphthalene tricarboxylic acid and pyromellitic acid; maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, malonic acid, azelaic acid, mesaconic acid, citraconic acid, glutaconic acid, etc. Aliphatic dicarboxylic acids; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and methylmedic acid; anhydrides and lower alkyl esters of these carboxylic acids; one or more of these are used.

The content of the trivalent or higher valent component depends on the degree of crosslinking, and the amount of the component can be adjusted to obtain a desired degree of crosslinking. Generally, the content of the trivalent or higher valent component is preferably 15 mol% or less.

The polyhydric alcohols used in the polyester resin include, for example, ethylene glycol, 1,2
Alkylene glycols such as propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,4-butenediol, neopentyl glycol, 1,5-pentane glycol, 1,6-hexane glycol; diethylene glycol; Alkylene ether glycols such as triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol;
Alicyclic polyhydric alcohols such as cyclohexane dimethanol and hydrogenated bisphenol A; bisphenol A;
Examples thereof include bisphenols such as bisphenol F and bisphenol S and alkylene oxides of bisphenols, and one or more of these are used.

In the present invention, a monocarboxylic acid or a monoalcohol may be used if necessary for the purpose of adjusting the molecular weight or controlling the reaction. Examples of the monocarboxylic acid include benzoic acid, paraoxybenzoic acid, toluenecarboxylic acid, salicylic acid, acetic acid, propionic acid, and stearic acid. Examples of the monoalcohol include monoalcohols such as benzyl alcohol, toluene-4-methanol, and cyclohexanemethanol.

The polyester resin used in the present invention is produced by a usual method using these raw materials. For example,
An alcohol component and an acid component are charged into a reaction vessel at a predetermined ratio, and the reaction is started at a temperature of 150 to 190 ° C. in the presence of a catalyst while blowing an inert gas such as nitrogen. The by-product low-molecular compound is continuously removed to the outside of the reaction system. Thereafter, the reaction temperature is further raised to 210 to 250 ° C. to accelerate the reaction, and the desired polyester resin is obtained. The reaction can be performed under any of normal pressure, reduced pressure, and increased pressure, but after the reaction rate reaches 50 to 90%, 200 mmH
The reaction is preferably performed under reduced pressure of not more than g. The weight-average molecular weight and the number-average molecular weight of the polyester resin can be adjusted to the ranges specified in the present invention by controlling the reaction temperature.

Examples of the catalyst include tin, titanium,
Metals such as antimony, manganese, nickel, zinc, lead, iron, magnesium, calcium, and germanium; and compounds containing these metals.

The polyester resin used in the present invention preferably has a glass transition temperature in the range of 45 to 90 ° C. When the glass transition temperature is lower than 45 ° C., the toner may harden in a toner cartridge or a developing device. On the other hand, when the glass transition temperature exceeds 90 ° C., fixing of the toner to paper or the like may be insufficient.

As the binder resin used in the present invention, another resin may be used in combination with the above polyester resin, if necessary, as long as the effects of the present invention are not impaired.

Further, in the invention of claim 1 of the present application, stable toner chargeability is achieved by using a polyester resin in which at least a part of hydroxyl groups is substituted by a functional group containing nitrogen.

That is, in general, the charge amount of a polyester resin tends to decrease in a high-humidity environment, causing fogging and toner scattering. However, at least a part of hydroxyl groups of the polyester resin has a functional group containing nitrogen. By using the material replaced by the above, it is possible to suppress a decrease in the charge amount of the toner in a high-humidity environment, and to prevent the fog and toner scattering.

In order to replace the hydroxyl group of the polyester resin with a functional group containing nitrogen, an isocyanate group (NCO group)
And the like after the polyester polymerization reaction. As the functional group containing nitrogen,
Examples include isoamine. Examples of the modifier include isocyanates and compounds thereof.

Another major feature is that carbon black having a pH of 7 or more is used as a colorant for the black toner according to the first aspect of the present invention. That is, carbon black serves as a reinforcing agent for the resin by dispersing and containing the toner in the binder resin at the same time as coloring the toner black, thereby improving the mechanical strength of the toner and consequently improving the toner length. This contributes to a longer life. PH 7
As described above, that is, by using carbon black having many hydroxyl groups, it is possible to contribute to the positive charging property of the toner.

The carbon black that can be used in the present invention is not particularly limited, and examples thereof include carbon blacks such as thermal black, acetylene black, channel black, furnace black, run black, and aniline black. Although the particle size of the carbon black is not limited, the number average primary particle size is preferably in the range of 10 to 200 nm.

However, in proportion to the improvement in the mechanical strength of the toner by the carbon black, there is a problem that the surface of the photosensitive member is scraped. Such a problem is particularly remarkable when a contact developing method is used as a developing method and a photoreceptor having a low hardness such as an organic photoreceptor is used, and the life of the toner is reduced, but the life of the photoreceptor is shortened. A new problem arises that the life of the entire apparatus such as a developing unit or a copying machine cannot be extended.

Therefore, in the invention according to claim 1 of the present application, a polyolefin-based wax is used as a release agent,
The above problem is solved by adding 1 to 7 parts by weight with respect to parts by weight. That is, by incorporating a polyolefin wax into the toner, the wax is interposed at the contact point or contact surface between the surface of the photoreceptor and the toner to lower the contact resistance of the toner and suppress the abrasion of the surface of the photoreceptor. At the same time, the wax has the effect of suppressing the occurrence of fixing offset in the fixing step. When the content of the wax is less than 1 part by weight,
The contact resistance of the toner is not reduced, and the shaving of the photoreceptor surface cannot be suppressed. On the other hand, when the content of the wax exceeds 7 parts by weight, the charge amount of the toner is reduced, so that problems such as toner scattering and fog may occur.

The polyolefin wax usable in the present invention is not particularly limited. Examples thereof include polypropylene, polyethylene, propylene-ethylene copolymer, acid-modified polyethylene, acid-modified polyethylene, and graft-modified polyethylene with aromatic monomers. , Low-density polyethylene pyrolysis type, polypropylene pyrolysis type, and the like.
Polypropylene in the range of 2,000, especially 2,000 to 15,000 can be suitably used.

When the wax is contained in the toner, the charge amount of the toner generally tends to decrease. In the case of a one-component developer, the toner is charged in a short time when the toner passes between the developing sleeve and a doctor blade that is in contact with the developing sleeve. It is necessary to increase the charging ability of the toner. Therefore, in the invention of claim 1 of the present application, a styrene-acrylic resin having a trisubstituted ammonium group in a side chain is used as a charge control agent, and the resin is contained in an amount of 1 to 7 parts by weight based on 100 parts by weight of the binder resin. Thereby, the charging ability of the toner is improved. When the content of the styrene-acrylic resin is less than 1 part by weight, the toner charging ability cannot be improved, and when the content exceeds 7 parts by weight,
While the toner charging ability is saturated, there may be a problem that the styrene-acryl resin is released from the toner and adheres to the sleeve or the surface of the photoconductor.

Examples of the monomer serving as the base of the styrene-acrylic resin having a trisubstituted ammonium group in the side chain include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, p-chlorostyrene. Styrene, styrene derivatives such as hydroxystyrene; methacrylic acid,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth)
Acrylate, glycidyl (meth) acrylate, methoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofur Furyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol Di (meta)
(Meth) acrylic esters such as acrylate and trimethylolethane tri (meth) acrylate can be mentioned.

The mixture of the above-mentioned various monomers can be polymerized by any method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc. to obtain the binder resin used in the present invention. In such a polymerization, usable polymerization initiators include acetyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, A known polymerization initiator such as 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile can be used. These polymerization initiators are preferably used in the range of 0.1 to 15% by weight based on the total weight of the monomers.

As the trisubstituted ammonium group, those having the following general formula are preferred.

[0034]

Embedded image (In the formula, R ¹ , R ² and R ³ are the same or different, and are methyl, ethyl, n-propyl, isopropyl, n-
Butyl group, isobutyl group, t-butyl group, pentyl group,
X represents an alkyl group such as a hexyl group; X ^- represents molybdate ion, phosphomolybdate ion, chromium / molybdate ion, phosphotungstate ion, silicate tungstate ion, antimonate ion, bismuthate ion,
Chlorine ion, bromine ion, iodine ion, nitrate ion,
Sulfate, perchlorate, periodate, benzoate, naphtholsulfonate, benzenesulfonate, toluenesulfonate, xylenesulfonate, tetraphenylboron, tetrafluoroboron, tetrafluorophosphate ,
Shows hexafluorophosphate ion. In order to attach the trisubstituted ammonium group to the side chain of the styrene-acrylic resin, a monomer having a trisubstituted ammonium group in the side chain is used as a part of the repeating unit, or the side chain of the styrene-acrylic resin is used. In this case, a reactive group such as a hydroxyl group or a hydroxyl group may be made to exist, and a compound having a substituent capable of reacting with such a reactive substituent and a trisubstituted ammonium group may be reacted with the styrene-acrylic resin.

As described above, the black toner according to the first aspect of the present invention is a positively chargeable one-component black toner by optimizing the combination of the binder resin, the colorant, the charge control agent, and the release agent. It is.

Next, the cyan toner according to the second aspect of the present invention will be described. The cyan toner is a binder resin,
It is the same as the black toner of claim 1 in that each of the colorant, the charge control agent, and the release agent is characterized, and the binder resin, the charge control agent, and the release agent that are common to the black toner of claim 1 , And its working function is as described above.

One of the features of the invention of claim 2 is that a copper phthalocyanine pigment is used as a coloring agent. By using a copper phthalocyanine pigment, excellent color mixing can be obtained.

The copper phthalocyanine pigment which can be used in the present invention is not particularly limited. I. Pigme
nt Blue No. 15, No. 15-1;
15-2, no. 15-3, no. 15-4, no. 1
5-5, No. 5; 15-6, p. B. 68, p. G. FIG. 7,
P. G. FIG. 36 and the like.

The use of a polyolefin wax as a release agent is the same as that of the black toner of claim 1, but the content is 0.5 to 7 parts by weight, and the lower limit is smaller than that of the black toner. Is different. This is because the copper phthalocyanine pigment used in the cyan toner of claim 2 has a lower effect as a reinforcing agent for the binder resin than the carbon black used in the black toner of claim 1, and causes less drum scraping by the toner. Therefore, no problem occurs even if the content of the polyolefin-based wax is small. Further, due to the lower limit of the content of the polyolefin-based wax that lowers the toner charge amount, as a charge control agent, the content of a styrene-acrylic resin having a trisubstituted ammonium group in a side chain is also increased. Even if the lower limit is set to 2 to 15 parts by weight, which is smaller than the case of the black toner, no problem occurs.

Next, the magenta toner according to the third aspect of the present invention will be described. The magenta toner is similar to the black toner of claim 1 in that each of the binder resin, the colorant, the charge control agent, and the release agent is characterized. Are as described above.

One of the features of the third aspect of the present invention is that a naphthol or quinacridone pigment is used as a coloring agent. By using these pigments, excellent color mixing properties can be obtained.

The naphthol-based pigment which can be used in the present invention is not particularly limited. For example, PR170, PR184,
PR238, PR146, PR151, PR114, P
R187, PR243, PR245 and the like can be mentioned. Among these, the compound represented by the general formula (1) is preferable from the viewpoint of color mixing.

The quinacridone pigments usable in the present invention are not particularly limited. For example, PR122, PR2
07, PR202, PR209, PR206 and the like.

The reason that the lower limit of the content of the release agent is 0.5 to 7 parts by weight, which is lower than that in the case of the black toner, is the same as in the case of the cyan toner.

On the other hand, naphthol or quinacridone pigments have the effect of lowering the chargeability of the toner, so that the content of the styrene-acrylic resin having a trisubstituted ammonium group as a charge control agent in the side chain is 3 to 16%. The upper limit is set to be larger than that in the case of the weight part and the black toner, thereby avoiding problems such as insufficient charge amount of the toner.

Next, the yellow toner according to the fifth aspect of the present invention will be described. The yellow toner is the same as the black toner of claim 1 in that each of the yellow toner is characterized by a binder resin, a colorant, a charge control agent, and a release agent. And charge control agent,
The function and function of the release agent are as described above.

One of the features of the invention of claim 5 of the present application is that a condensed azo pigment is used as a coloring agent. By using a condensed azo pigment, excellent color mixing can be obtained.

The condensed azo pigments usable in the present invention are not particularly limited. For example, CI Pigment Yellow 93, C.I.
I. Pigment Yellow 94 and CI Pigment Yellow 95.

The reason why the content of the release agent is 0.5 to 7 parts by weight and the lower limit is smaller than that in the case of the black toner is the same as in the case of the cyan toner.

On the other hand, since the condensed azo pigment has an effect of lowering the chargeability of the toner, the content of the styrene-acrylic resin having a trisubstituted ammonium group as a charge control agent in the side chain is 3 to 16 parts by weight. In this case, the upper limit value is made larger than that in the case of the black toner to avoid problems such as a shortage of toner charge. (Production of Toner) Toner of each color of black, cyan, magenta, and yellow (hereinafter, referred to as “positive chargeable one-component development”) of the present invention.
Sometimes simply referred to as “toner”. ) Is the crush classification method,
Although it can be produced by a method known per se such as a melt granulation method, a spray granulation method, a suspension / emulsion polymerization method, etc., a pulverization classification method can be suitably used from the viewpoint of production equipment and productivity. The pulverization and classification method will be described below. First, the toner composition of the binder resin, the colorant, the charge control agent, and the release agent is premixed with a Henschel mixer or a V-type mixer, and then melt-kneaded using a melt-kneading apparatus such as a twin-screw extruder. . After cooling the melt-kneaded product, the mixture is coarsely and finely pulverized and, if necessary, classified to obtain toner particles having a predetermined particle size distribution. If necessary, the surface of the toner particles is treated with a surface treating agent to obtain the toner of the present invention.

The average particle size of the toner of the present invention is preferably in the range of 5 to 15 microns, and more preferably 7 to 12 microns in terms of volume average diameter measured by a Coulter counter.

Examples of the surface treatment agent include silica, alumina, and the like for improving the charge controllability and fluidity of the toner.
Inorganic fine powders such as titanium oxide, zinc oxide, magnesium oxide, calcium carbonate, magnetic powder; (meth) acrylate;
Organic fine powders such as methyl (meth) acrylate can be used, and one or more of these can be used in combination. The mixing of the surface treating agent and the toner particles can be performed using, for example, a Henschel mixer, a V-type mixer, a turbula mixer, a hybridizer, or the like.

Each color of the toner of the present invention can be suitably used for a full-color image, and of course, it can also be used for a mono-color image. (Developing Method) The developing method using the toner of the present invention is not particularly limited as long as it is a positively chargeable one-component development. May be any of the jumping developments that are not in contact with. Further, any of the regular development method and the reversal development method may be used.
When a negatively charged photoreceptor is used and development is performed by the reversal development method, it is necessary to use a positively charged photoreceptor. The photoreceptor to be used can obtain a good image regardless of whether it is an organic photoreceptor or an inorganic photoreceptor. However, an organic photoreceptor is more preferable in terms of environment and production cost. Such an organic photoreceptor may be a function-separated type photoreceptor comprising a charge generation layer and a charge transport layer, or a single-layer photoreceptor which generates and transports charges in a single layer. It is desirable that the toner for a color image is non-magnetic, and as the developing method for a non-magnetic one-component toner, contact development is desirable among the above. FIG. 1 shows a schematic sectional view of the developing device. The basic configuration of the developing device 1 includes a developing roller 11 that conveys a toner 12 to a developing area, and an elastic blade 13 that presses against the developing roller 11, and the toner 12 passes between the developing roller 11 and the elastic blade 13. By doing so, the toner 12 is charged and a thin layer of the toner 12 is formed. By bringing the thin toner layer into contact with the photosensitive drum 2, the positively charged toner 12 adheres to the electrostatic latent image (uncharged portion) formed on the photosensitive drum 2, and the latent image is visualized. .

The pressing force of the elastic blade is 50 to 200 g.
/ G is preferable, and if it is less than 50 g / cm, the toner may be insufficiently charged. If it exceeds 200 g / cm, the toner may not be sufficiently conveyed to the developing area, and the image density may be poor. The blade may be applied in either a trailing type along the rotating direction of the developing roller or a leading type in the rotating direction of the developing roller. The thin layer thickness of the toner is desirably 20 to 40 microns.

The material of the elastic blade used in the present invention is not particularly limited. However, since it is necessary to positively charge the toner, a material which is frictionally charged to a negative polarity is desirable.
Specifically, a blade made of a material such as stainless steel, glass, silicon rubber, and urethane rubber can be used.

The material of the developing roller is not particularly limited. However, since it is necessary to positively charge the toner as in the case of the elastic blade, a material which is negatively charged is preferable. Specifically, silicone resin or urethane is used. Desirable are resins and NBR.

As the transfer method for full-color images, 3
The three-color (or four-color) transfer method in which color (or four-color) toner images are sequentially transferred to transfer paper and three (or four) toner images are superimposed on the transfer paper, and the three-color (or four-color) transfer is performed on the photoconductor Any of the single transfer methods in which toner images of four colors are superimposed and then collectively transferred onto transfer paper may be used. From the viewpoint of copying speed and image clarity, the transfer method three times (four times) is preferable, and among them, the tandem method in which three or four developing devices are arranged in series and developed is preferable. FIG. 2 is a schematic cross-sectional view of a full-color image forming apparatus employing a quadruple tandem system. In the image forming apparatus P, a transport belt 3 for transporting the transfer paper 9 is disposed at the center, and yellow, magenta,
The image forming units 4Y, 4M, 4C, and 4B that form images of each color of cyan and black and transfer the images to the transfer paper 9
Are arranged sequentially at equal intervals along the transport direction. These image forming units form images corresponding to each color by an electrophotographic process. Specifically, in the image forming section 4Y for yellow, for example, the photoconductor 2 is uniformly charged by the charger 5, and an electrostatic latent image is formed on the photoconductor by the optical scanning device 6Y based on the yellow image information. It is formed. This electrostatic latent image is developed by the yellow toner in the developing device 1 to form a yellow toner image on the photoconductor. The yellow toner image is transferred to the transfer paper 9 on the transport belt 3 by the transfer roller 7. Similar operations are performed in the other image forming units 4M, 4C, and 4B, so that images of each color are sequentially transferred onto the transfer paper 9, and the fixing unit 8 fuses and fixes the full-color toner image on the transfer paper 9.

[0058]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" described in Examples and Comparative Examples are parts by weight and "%"
Represents "% by weight".

(Black Toner) Example 1 As a binder resin, 100 parts of a polyester resin having a weight average molecular weight of 10,500, a number average molecular weight of 3,100 and a part of hydroxyl groups being substituted by isocyanate groups, 5 parts of carbon black having a pH of 7 as a coloring agent, 3 parts of a styrene-acrylic resin having a trisubstituted ammonio group in a side chain as a charge controlling agent, and 1 part of low molecular weight polypropylene ("Biscol 550P" manufactured by Sanyo Chemical) as a releasing agent Was charged and mixed in a Henschel mixer, melt-kneaded with a twin-screw extruder, and cooled with a drum flaker. Next, after coarsely pulverized by a hammer mill, finely pulverized by a jet mill, and classified using an air classifier, toner particles having an average particle diameter of 8 microns were obtained.

A hydrophobic silica “RA200” (manufactured by Nippon Aerosil Co., Ltd.) 0.6 as a surface treating agent was added to the toner particles.
And a high-speed stirring and mixing with a Henschel mixer to obtain a positively charged static single-component developing toner of the present invention. Various properties of the toner were measured under the following conditions. Table 1 shows the measurement results.

(Image Density, Fogging Density) After using a commercially available laser printer (“LDC720” manufactured by Mita Kogyo Co., Ltd.) to improve the fixing unit, a 30,000-sheet printing durability test was performed.
The solid image density of each color is passed through each filter,
The image density was measured using a Macbeth densitometer “RD-918”. Similarly, the white paper portion after the 30,000-sheet printing test was determined as the fogging density using the densitometer. The image density is 1.60 or more, and the fog density is 0.30.
008 or less is used as a criterion of quality.

(Charge amount) The toner on the developing roller after printing 30,000 sheets is sucked into a Faraday gauge, and the specific charge is measured with an electrometer “TR-8652” manufactured by Advantest Co., and the charge amount per 1 g of toner is determined. Calculated.

(Fixing and Transparency) Solid images of cyan, magenta and yellow were fixed on OHP paper, and the fixing and translucency were visually evaluated according to the following criteria.

：: Good fixability and good color reproducibility.

Δ: Color reproducibility is good, but transparency is poor.

×: Poor color reproducibility and poor transparency due to poor fixing.

(Glossiness) The glossiness of the solid portion of each color was visually determined based on the following criteria.

：: Good gloss with sufficient gloss Δ: Gloss without gloss but without roughness ×: Gloss with no gloss and roughness (blade fusion) 30,000 The blade after sheet printing was observed using an optical microscope, and the degree of fusion was evaluated according to the following criteria.

：: no deposits Δ: thinly attached, but no effect of fusing appeared on the image.

×: The effect of fusion is visible in the image.

(Toner filming on photoreceptor) 30,
After printing 000 sheets, the surface of the photoreceptor was visually observed, and the degree of fixing (filming) of the toner was evaluated according to the following criteria.

：: No sticking (filming) Δ: Thinly attached, but does not affect the image.

×: The effect of sticking (filming) appears on the image.

(Abrasion amount of photoreceptor) Using an eddy current film thickness meter, the film thickness was measured at a total of 20 points at 4 points in the circumferential direction and 5 points in the axial direction, and before and after printing 30,000 sheets The average value of the difference in film thickness was determined as the scraping amount.

Example 2 As the binder resin, a polyester resin having a weight average molecular weight of 49,000 and a number average molecular weight of 14,500 was used, the charge control agent was used in an amount of 15 parts, and the release agent was used. A toner was manufactured in the same manner as in Example 1 except that the amount was changed to 10 parts, and the same evaluation was performed. Table 1 shows the evaluation results.

Example 3 As a binder resin, a polyester resin having a weight average molecular weight of 15,000 and a number average molecular weight of 5,000 was used.
A toner was manufactured in the same manner as in Example 1 except that the amount of the charge control agent used was 9 parts and the amount of the release agent used was 4 parts, and the same evaluation was performed. Table 1 shows the evaluation results.

Example 4 As the binder resin, a polyester resin having a weight average molecular weight of 30,000 and a number average molecular weight of 8,000 was used.
A toner was produced in the same manner as in Example 1 except that the amount of the charge control agent used was 4 parts and the amount of the release agent used was 4 parts, and the same evaluation was performed. Table 1 shows the evaluation results.

Comparative Example 1 As a binder resin, a polyester resin having a weight average molecular weight of 9,000, a number average molecular weight of 2,500, and a hydroxyl group not substituted with a nitrogen-containing functional group was used. A toner was produced in the same manner as in Example 1 except that the used amount was 7 parts and the used amount of the release agent was 4 parts, and the same evaluation was performed. Table 1 shows the evaluation results.

Comparative Example 2 A toner was produced in the same manner as in Comparative Example 1 except that a polyester resin having a weight average molecular weight of 51,000 and a number average molecular weight of 16,000 was used as a binder resin, and the same evaluation was performed. Was done. Table 1 shows the evaluation results.

Comparative Example 3 A polyester resin having a weight average molecular weight of 15,000 and a number average molecular weight of 5,000 was used as a binder resin.
A toner was manufactured in the same manner as in Comparative Example 1 except that the amount of the charge control agent used was changed to 2 parts and the release agent was not used, and the same evaluation was performed. Table 1 shows the evaluation results.

Comparative Example 4 A polyester resin having a weight average molecular weight of 15,000 and a number average molecular weight of 5,000 was used as a binder resin.
The charge control agent is used in an amount of 16 parts, and the release agent is used in an amount of 1 part.
A toner was manufactured in the same manner as in Comparative Example 1 except that the amount was 1 part, and the same evaluation was performed. Table 1 shows the evaluation results.

[0082]

[Table 1] (Cyan Toner) Example 5 As a binder resin, 100 parts of a polyester resin having a weight average molecular weight of 10,500, a number average molecular weight of 3,100, and a part of hydroxyl groups substituted by an isocyanate group was used as a colorant. 5 parts of a copper phthalocyanine pigment, 15 parts of a styrene-acrylic resin having a trisubstituted ammonio group in a side chain as a charge control agent, and 0.5 parts of low-molecular-weight polypropylene ("Biscol 550P" manufactured by Sanyo Chemical) as a release agent, respectively After charging and mixing in a Henschel mixer, the mixture was melt-kneaded with a twin-screw extruder and cooled with a drum flaker.
Next, after coarsely pulverized by a hammer mill, finely pulverized by a jet mill, and classified using an air classifier, toner particles having an average particle diameter of 8 microns were obtained.

A hydrophobic silica “R812S” (manufactured by Nippon Aerosil Co., Ltd.) 0.6 as a surface treatment agent was added to the toner particles.
And a high-speed stirring and mixing with a Henschel mixer to obtain a positively charged static single-component developing toner of the present invention. Various properties of the toner were measured under the following conditions. Table 2 shows the measurement results.

Example 6 A polyester resin having a weight average molecular weight of 49,000 and a number average molecular weight of 14,500 was used as the binder resin, the charge control agent was used in an amount of 9 parts, and the release agent was used. A toner was manufactured in the same manner as in Example 5 except that the amount was changed to 7 parts, and the same evaluation was performed. Table 2 shows the evaluation results.

Example 7 As a binder resin, a polyester resin having a weight average molecular weight of 15,000 and a number average molecular weight of 5,000 was used.
A toner was produced in the same manner as in Example 5 except that the amount of the charge control agent used was 7 parts and the amount of the release agent used was 3 parts, and the same evaluation was performed. Table 1 shows the evaluation results.

Example 8 A polyester resin having a weight average molecular weight of 30,000 and a number average molecular weight of 8,000 was used as a binder resin.
A toner was produced in the same manner as in Example 5 except that the amount of the charge control agent used was 2 parts and the amount of the release agent used was 3 parts, and the same evaluation was performed. Table 2 shows the evaluation results.

Comparative Example 5 A polyester resin having a weight average molecular weight of 9,000 and a number average molecular weight of 2,500 was used as a binder resin, 5 parts of a metal-free phthalocyanine pigment was used as a colorant, and a charge control agent was used. Was used in the same manner as in Example 5 except that the used amount of the toner was 7 parts and the used amount of the release agent was 3 parts, and the same evaluation was performed. Table 2 shows the evaluation results.

Comparative Example 6 As a binder resin, a polyester resin having a weight average molecular weight of 51,000 and a number average molecular weight of 16,000 and having a hydroxyl group not substituted by a nitrogen-containing functional group was used.
A toner was produced in the same manner as in Example 5 except that the amount of the charge control agent used was 7 parts and the amount of the release agent used was 3 parts, and the same evaluation was performed. Table 2 shows the evaluation results.

Comparative Example 7 A polyester resin having a weight average molecular weight of 15,000 and a number average molecular weight of 5,000 was used as a binder resin.
A toner was produced in the same manner as in Example 5 except that the amount of the charge control agent used was 1 part and the release agent was not used, and the same evaluation was performed. Table 2 shows the evaluation results.

Comparative Example 8 The charge control agent was used in an amount of 16 parts, and the release agent was used in an amount of 8 parts.
A toner was manufactured in the same manner as in Comparative Example 7 except that
The same evaluation was performed. Table 2 shows the evaluation results.

[0091]

[Table 2] (Magenta Toner) Example 9 As a binder resin, 100 parts of a polyester resin having a weight average molecular weight of 10,500, a number average molecular weight of 3,100, and a part of hydroxyl groups substituted by an isocyanate group was used as a colorant. 5 parts of a quinacridone pigment, 16 parts of a styrene-acrylic resin having a trisubstituted ammonio group in a side chain as a charge control agent, and 0.5 parts of low molecular weight polypropylene ("Biscol 550P" manufactured by Sanyo Chemical) as a release agent. After charging and mixing in a Henschel mixer, the mixture was melt-kneaded with a twin-screw extruder and cooled with a drum flaker.
Next, after coarsely pulverized by a hammer mill, finely pulverized by a jet mill, and classified using an air classifier, toner particles having an average particle diameter of 8 microns were obtained.

The toner particles were treated with a hydrophobic silica “R812S” (manufactured by Nippon Aerosil Co., Ltd.) 0.6 as a surface treating agent.
And a high-speed stirring and mixing with a Henschel mixer to obtain a positively charged static single-component developing toner of the present invention. Various properties of the toner were measured under the following conditions. Table 3 shows the measurement results.

Example 10 A polyester resin having a weight average molecular weight of 49,000 and a number average molecular weight of 14,500 was used as a binder resin, 5 parts of a naphthol pigment was used as a colorant, and a charge control agent was used. A toner was manufactured in the same manner as in Example 9 except that the used amount was 9 parts and the used amount of the release agent was 7 parts, and the same evaluation was performed. Table 3 shows the evaluation results.

Example 11 As a binder resin, a polyester resin having a weight average molecular weight of 15,000 and a number average molecular weight of 5,000 was used.
A toner was produced in the same manner as in Example 9 except that 5 parts of a naphthol-based pigment was used as a coloring agent, the amount of the charge control agent was 7 parts, and the amount of the release agent was 3 parts. An evaluation was performed. Table 3 shows the evaluation results.

Example 12 As a binder resin, a polyester resin having a weight average molecular weight of 30,000 and a number average molecular weight of 8,000 was used.
A toner was manufactured in the same manner as in Example 9 except that the amount of the charge control agent used was 3 parts and the amount of the release agent used was 3 parts, and the same evaluation was performed. Table 3 shows the evaluation results.

Comparative Example 9 A polyester resin having a weight average molecular weight of 9,000 and a number average molecular weight of 25,000 was used as a binder resin.
A toner was produced in the same manner as in Example 9 except that 5 parts of an oil-soluble azo pigment was used as a colorant, the amount of the charge control agent was 7 parts, and the amount of the release agent was 3 parts. The same evaluation was performed. Table 3 shows the evaluation results.

Comparative Example 10 As a binder resin, a polyester resin having a weight average molecular weight of 51,000 and a number average molecular weight of 16,000 and having a hydroxyl group not substituted by a nitrogen-containing functional group was used.
A toner was produced in the same manner as in Example 9 except that the amount of the charge control agent used was changed to 7 parts and the amount of the release agent used was changed to 3 parts, and the same evaluation was performed. Table 3 shows the evaluation results.

Comparative Example 11 A polyester resin having a weight average molecular weight of 15,000 and a number average molecular weight of 5,000 was used as a binder resin.
A toner was manufactured in the same manner as in Example 9 except that the amount of the charge control agent used was changed to 2 parts and the release agent was not used, and the same evaluation was performed. Table 3 shows the evaluation results.

Comparative Example 12 A polyester resin having a weight average molecular weight of 15,000 and a number average molecular weight of 5,000 was used as a binder resin.
A toner was produced in the same manner as in Example 9 except that 5 parts of a naphthol-based pigment was used as a coloring agent, the amount of the charge control agent was 17 parts, and the amount of the release agent was 8 parts. An evaluation was performed. Table 3 shows the evaluation results.

[0100]

[Table 3] Example 13 (Yellow Toner) Example 13 As a binder resin, 100 parts of a polyester resin having a weight average molecular weight of 10,500 and a number average molecular weight of 3,100, in which a part of hydroxyl groups was substituted by an isocyanate group, as a colorant 5 parts of condensed azo pigment, styrene-acrylic resin 1 having a trisubstituted ammonium group as a charge control agent in the side chain 1
7 parts and 0.5 part of a low molecular weight polypropylene ("Viscol 550P" manufactured by Sanyo Chemical Industries) as a mold release agent were respectively charged and mixed in a Henschel mixer, melt-kneaded with a twin-screw extruder, and cooled with a drum flaker. . Next, after coarsely pulverized by a hammer mill, finely pulverized by a jet mill, and classified using an air classifier, toner particles having an average particle diameter of 8 microns were obtained.

To the toner particles, hydrophobic silica “R812S” (manufactured by Nippon Aerosil Co., Ltd.) 0.6 as a surface treating agent was used.
And a high-speed stirring and mixing with a Henschel mixer to obtain a positively charged static single-component developing toner of the present invention. Various properties of the toner were measured under the following conditions. Table 4 shows the measurement results.

Example 14 A polyester resin having a weight average molecular weight of 49,000 and a number average molecular weight of 14,500 was used as a binder resin, 5 parts of a monoazo pigment was used as a colorant, and a charge control agent was used. A toner was manufactured in the same manner as in Example 13 except that the used amount was 9 parts and the used amount of the release agent was 7 parts, and the same evaluation was performed. Table 4 shows the evaluation results.

Example 15 As a binder resin, a polyester resin having a weight average molecular weight of 15,000 and a number average molecular weight of 5,000 was used.
A toner was produced in the same manner as in Example 13 except that the amount of the charge control agent was changed to 7 parts and the amount of the release agent was changed to 3 parts.
The same evaluation was performed. Table 4 shows the evaluation results.

Example 16 As the binder resin, a polyester resin having a weight average molecular weight of 30,000 and a number average molecular weight of 8,000 was used.
A toner was manufactured in the same manner as in Example 13 except that the amount of the charge control agent was changed to 4 parts and the amount of the release agent was changed to 3 parts.
The same evaluation was performed. Table 4 shows the evaluation results.

Comparative Example 13 As a binder resin, a polyester resin having a weight average molecular weight of 9,000 and a number average molecular weight of 25,000 was used.
Using 5 parts of a benzimidazolone pigment as a colorant,
A toner was produced in the same manner as in Example 13 except that the amount of the charge control agent was changed to 7 parts and the amount of the release agent was changed to 3 parts.
The same evaluation was performed. Table 4 shows the evaluation results.

Comparative Example 14 As a binder resin, a polyester resin having a weight average molecular weight of 51,000 and a number average molecular weight of 16,000 and having a hydroxyl group not substituted by a nitrogen-containing functional group was used.
A toner was produced in the same manner as in Example 13 except that the amount of the charge control agent was changed to 7 parts and the amount of the release agent was changed to 3 parts.
The same evaluation was performed. Table 4 shows the evaluation results.

Comparative Example 15 As a binder resin, a polyester resin having a weight average molecular weight of 15,000 and a number average molecular weight of 5,000 was used.
A toner was manufactured in the same manner as in Example 13 except that the amount of the charge control agent used was changed to 3 parts and the release agent was not used, and the same evaluation was performed. Table 4 shows the evaluation results.

Comparative Example 16 As a binder resin, a polyester resin having a weight average molecular weight of 15,000 and a number average molecular weight of 5,000 was used.
The charge control agent was used in an amount of 18 parts, and the release agent was used in an amount of 8 parts.
A toner was manufactured in the same manner as in Example 13 except that the toner was used as a part, and the same evaluation was performed. Table 4 shows the evaluation results.

[0109]

[Table 4]

[0110]

The toners of the present invention are excellent in positive chargeability, have a long service life, and are excellent in color mixing property, glossiness and offset resistance, and are suitable as toners for developing full-color images.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a developing device.

FIG. 2 is a schematic sectional view of a full-color image forming apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Developing device 2 Photoreceptor drum 3 Conveyor belt 4 Image forming part 5 Charger 6 Optical scanning device 7 Transfer roller 8 Fixing part 9 Transfer paper 11 Developing roller 12 Toner 13 Elastic blade 14 Supply roller

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kenyuki Matsui 1-2-28 Tamatsukuri, Chuo-ku, Osaka-shi Inside Mita Kogyo Co., Ltd. F-term in Industrial Co., Ltd. (Reference) 2H005 AA01 AA06 AA21 CA04 CA08 CA13 CA14 CA18 CA21 CB18 DA03 DA04 DA06 EA06 EA07 EA10

Claims (6)

[Claims] 1. A toner comprising at least a binder resin, a colorant, a charge control resin, and a release agent, wherein the binder resin has a weight average molecular weight of 10,000 to 50,
000 and a number average molecular weight of 3,000 to 1
A polyester resin having a molecular weight in the range of 5,000, wherein at least a part of hydroxyl groups of the polyester resin is substituted by a functional group containing nitrogen, the colorant is carbon black having a pH of 7 or more, and the charge control agent is A styrene-acrylic resin having a substituted ammonium group in a side chain, contained in an amount of 3 to 15 parts by weight based on 100 parts by weight of the binder resin, wherein the release agent is a polyolefin-based wax, 1 to 7 parts by weight per 100 parts by weight of a positively chargeable black toner for one-component development. 2. A toner comprising at least a binder resin, a colorant, a charge control resin and a release agent, wherein the binder resin has a weight average molecular weight of 10,000 to 50,000.
000 and a number average molecular weight of 3,000 to 1
A polyester resin having a molecular weight in the range of 5,000, wherein at least a part of hydroxyl groups of the polyester resin is substituted by a functional group containing nitrogen, the colorant is a copper phthalocyanine pigment, and the charge control agent is A styrene-acrylic resin having a substituted ammonium group in a side chain, which is contained in an amount of 2 to 15 parts by weight based on 100 parts by weight of the binder resin, wherein the release agent is a polyolefin wax; 0.5 to 7 parts by weight per 100 parts by weight of a positively chargeable one-component developing cyan toner. 3. A toner comprising at least a binder resin, a colorant, a charge control resin, and a release agent, wherein the binder resin has a weight average molecular weight of 10,000 to 50,000.
000 and a number average molecular weight of 3,000 to 1
A polyester resin having a molecular weight in the range of 5,000, wherein at least a part of hydroxyl groups of the polyester resin is substituted by a nitrogen-containing functional group, and the colorant is a naphthol-based or quinacridone-based pigment; Is a styrene-acrylic resin having a trisubstituted ammonio group in a side chain, contained in an amount of 3 to 16 parts by weight based on 100 parts by weight of the binder resin, wherein the release agent is a polyolefin-based wax; A positively chargeable magenta toner for one-component development, wherein the magenta toner is contained in an amount of 0.5 to 7 parts by weight based on 100 parts by weight of the resin. 4. The magenta toner according to claim 3, wherein the coloring agent is a compound represented by the following general formula (1). Embedded image (Wherein, R ^{1 to} R ⁵ are each a hydrogen atom, a halogen,
Represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, wherein at least one of R ^{1 to} R ⁵ is a halogen, and at least one of R ^{1 to} R ⁵ is a methoxy group. ) 5. A toner comprising at least a binder resin, a colorant, a charge control resin and a release agent, wherein the binder resin has a weight average molecular weight of 10,000 to 50,000.
000 and a number average molecular weight of 3,000 to 1
A polyester resin having a molecular weight in the range of 5,000, wherein at least a part of hydroxyl groups of the polyester resin is substituted by a nitrogen-containing functional group, the colorant is a condensed azo pigment, and the charge control agent is A styrene-acrylic resin having a substituted ammonium group in a side chain, which is contained in an amount of 4 to 17 parts by weight based on 100 parts by weight of the binder resin, wherein the release agent is a polyolefin-based wax; 0.5 to 7 parts by weight per 100 parts by weight of a positively chargeable one-component developing yellow toner. 6. The positively chargeable one-component developing yellow toner according to claim 5, wherein the colorant is a compound represented by the following general formula (2). Embedded image (Wherein, R ⁶ and R ⁷ are each halogen or carbon 1
And R ⁸ and R ⁹ each represent a hydrogen atom or a halogen, except when both are hydrogen atoms. )