JP3376170B2 - Toner for developing electrostatic images - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing toner for developing an electrostatic charge latent image in an image forming method such as electrophotography and electrostatic recording.

[0002]

BACKGROUND OF THE INVENTION Toners must have a positive or negative charge depending on the polarity of the electrostatic latent image being developed. Here, in order to make the toner retain an electric charge, it is possible to utilize the triboelectric charging property of the resin which is a constituent component of the toner, but in this method, the toner charging property is small, so the image obtained by development is fogged. Is likely to occur and becomes unclear. Therefore, in order to impart a desired triboelectric chargeability to the toner, a dye, a pigment or a charge control agent capable of imparting the chargeability is added.

Among the charge control agents known in the art today, examples of negative triboelectric charge control agents include metal complex salts of monoazo dyes, metal complex salts of salicylic acid, naphthoic acid, dicarboxylic acids, and copper. Phthalocyanine pigments, resins containing an acid component, etc. are known. As the positive triboelectric charge control agent, for example, nigrosine dye,
Known are azine dyes, triphenylmethane dyes and pigments, polymers having quaternary ammonium salts in their side chains, and the like. However, most of these charge control agents are colored and therefore cannot be used for color toners. On the other hand, there is a problem that none of the colorless, white, or light-colored charge control agents applicable to color toners have sufficient performance.

For example, a colorless or light-colored resin type charge control agent requires a certain period of time until it has an appropriate charge amount. Therefore, when copying after being stopped for a long period of time, or when copying after being left in a high humidity environment, the charge amount is likely to be insufficient, resulting in fog or obtaining an appropriate image density. In some cases, hundreds to hundreds of copies may be required. Moreover, especially when such a charge control agent is applied to a one-component developer (magnetic and non-magnetic), such a slow rise of charging is considered to contribute to the image memory (ghost). Be done.

In addition, some charge control agents have the following drawbacks. It is difficult to balance image density and fog. The charge amount gradually decreases after long-term copying. It is difficult to obtain sufficient image density in a high humidity environment. There is a problem in dispersibility in resin. There is a problem with storage stability and heat stability.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the above problems of the prior art, to obtain a high image density without fog and to obtain an image of good highlight reproduction. To provide a toner for developing a charge image. Another object of the present invention is to provide a toner for developing an electrostatic charge image, which is excellent in stability of charge amount in long-term durability. Another object of the present invention is to provide a toner for developing an electrostatic charge image, which has a rapid rise of charging and has an appropriate amount of charge very quickly.

Further, another object of the present invention is to stably obtain a high image density upon restarting, even if left in low humidity or high humidity, and to prevent toner scattering. An object of the present invention is to provide a toner for developing an electrostatic image that does not occur. Another object of the present invention is to provide a color toner for developing an electrostatic charge image having good color reproducibility by using a colorless or light color charge control agent.

[0008]

The above object can be achieved by the present invention described below. That is, the present invention has a linear main chain obtained by an acyclic polymerization reaction having a structure containing an ionized element as a repeating unit, and has a crosslinked structure.
A compound having a molecular weight of 600 or more, which is composed of an ion A that is a polymer that does not have and an ion B that has a polarity opposite to that of the ion A and has a volume of 0.40 nm ³ or more, is internally added. The toner for developing an electrostatic charge image is characterized by the following.

[0009]

As a result of intensive studies to solve the above-mentioned problems of the prior art, the inventors of the present invention include the above-mentioned specific compound in the toner to prevent fog at high image density and good reproduction of highlights. The present invention has been accomplished by finding that a toner that can form an image and that is excellent in the stability of the charge amount with long-term durability can be obtained. In particular, the image characteristic that an image with high image density and no fog and good highlight reproduction can be obtained has an important meaning when applied to a full-color toner.
The reason why such image characteristics are obtained is considered to be that the distribution of the charge amount becomes sharper by the addition of the specific compound. That is, if the charge amount distribution is sharp,
Since the toner particles have uniform electric charges, it becomes difficult for the Coulomb force to work between the toner particles. Therefore, each toner particle behaves independently, and highlight reproduction is improved. In addition, it is considered that the image density is increased because the undercharged toner is reduced and the fog is eliminated, and the excessively charged toner is reduced.

Another important effect of the present invention by containing a specific compound in the toner is that the toner is durable for a long period of time and the stability of the charge amount is excellent. Most of the conventionally known non-metal type charge control agents have a problem with stability in long-term durability. Generally, due to long-term durability, a carrier or a sleeve carrying a toner is contaminated with a component of the toner, so-called spent is generated, and there is a problem in stability in long-term durability. On the other hand, the present inventors have found that it is possible to make the toner less susceptible to the spent by including the specific compound in the toner. In other words, this characteristic, such compounds described above, considered are gills when it is due to be located in the triboelectric series to the negative than the spent product. That is, the compound used in the present invention has an ionic structure in which a structure containing an ionized element is used as a repeating unit, and the size of each anion and cation is set to a certain level or more, thereby causing the above problems. Achieve the solution of.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to preferred embodiments. The electrostatic image developing toner of the present invention has a linear chain obtained by an acyclic polymerization reaction having a structure containing an ionized element as a repeating unit .
Ion A, which is a polymer having a main chain and no crosslinked structure
And has a polarity opposite to that of the ion A and a volume of 0.40 n
It is characterized by containing a compound having a molecular weight of 600 or more and an ion B having a size of m ³ or more.

In the present invention, the molecular weight of a compound refers to a weight average molecular weight when a molecular weight distribution occurs. The molecular weight of the compound used in the present invention is 600 or more. It seems that the ionic charge is easily stabilized and the density of ion pairs in the molecular assembly of the compound is roughened by doing so. . As a result, it may be possible to obtain a high charge amount that cannot be achieved by the conventional charge control agents such as quaternary ammonium salts. Further, when the molecular weight is 1000 or more, the charge amount is further improved, which is preferable, and when it is 5000 or more, for example, most of the carrier coating agents in a two-component developer can be applied, and the developer is designed. It is more preferable because it becomes easier.
Speaking of the number average molecular weight, for example, the molecular weight is 400 to 200.
Everything is applicable. The molecular weight distribution of the compound used in the present invention is Mw / Mn of 1.5 to 5
Although those having a sharp distribution of Mw / Mn of about 2 to 10 are used, charging is also sharp, which is preferable.

The compound used in the present invention comprises an ion A and an ion B, and the ion A is a polymer obtained by an acyclic polymerization reaction having a structure containing an ionized element as a repeating unit. The number of repetitions of the repeating unit in the ion A may be 5 to several thousand or more in the present invention, and particularly, one having a repetition number of 10 to 1,000 is preferable in production.

When the ion A is obtained by a polymerization method in which a distribution of molecular weight is produced, it is preferable to use a component having a molecular weight of 3,000 or less, preferably 15% or less, more preferably 10% or less. . That is, when the ratio of such a low molecular weight component exceeds 15%, the yield in toner production tends to deteriorate, which is not preferable. The cause is considered to be as follows. First, in a polymerization method such as addition polymerization or polycondensation, a distribution of molecular weight may occur, and for example, a low molecular weight component having a molecular weight of several hundreds may occur. The presence of such a low molecular weight component makes the viscoelastic properties of the compound soft even at room temperature. For this reason, it is considered that the compound on the surface becomes tacky, and the toner particles are easily aggregated in the toner manufacturing process. In contrast, by reducing the molecular weight of 3,000 or less components also reduces molecular weight several hundred about ingredients, it is considered that prevention of toner aggregation Ru achieved.

The compounds used in the present invention include T
g is preferably 40 ° C. or higher, more preferably 50
Use a temperature above ℃. Even if Tg is lower than 40 ° C,
Similar to the case of the low molecular weight component described above, the yield in the toner production starts to deteriorate due to the aggregation of the toner fine particles, which is not preferable.

The compound used in the present invention has an ion A having the above-mentioned properties, a polarity opposite to that of the ion A, and a volume of 0. 40 nm
It is composed of ions B having a size of ³ or more .
By the size of the ion-B and 0.25 nm ³ or more, so good charge control property can be obtained. Furthermore,
When the volume is 0.30 nm ³ or more, the charge amount becomes high and it becomes easy to obtain stability in long-term durability.
When it is m ³ or more, it is easy to design a developer with sufficient image quality and image stability even in a high humidity environment where the charge amount is apt to become low, which is preferable.

Further, in the present invention, the polarity of the ion B is opposite to that of the ion A, and the polarity of the ion B is the same as that of the electrostatic image developing toner of the present invention. it is good preferable to. The inventors of the present invention have found that by predominantly controlling the polarity of the ions B in the toner for developing an electrostatic charge image of the present invention, a toner that can quickly reach the saturated charge amount can be obtained. Conventionally, there is a theory that a polymer type charge control agent causes a gradual movement of a polymer and the charging sites gradually move to the surface, so that the charge amount is not saturated easily. In fact, in conventional polymer type charge control agents where the polarity on the polymer side is dominant,
This is often the case. However, in the toner of the present invention, the polarity of the ion B is predominant not on the polymer side.
By and this, to mitigate this trend. In order to make the polarity of the ion B dominant, it is necessary to increase the size of the ion B, but this may be related to the fact that the charge is saturated quickly. For example, it is conceivable that this facilitates the movement of the charging site.

Further, in the present invention, the ion B is preferably an anion. As a result, the ion exchange rate is high, and if this is done, a stable charge amount with long-term durability can be obtained. In particular, when the ion B is used as an anion and a negatively chargeable charge control agent is used for a negative toner, it is possible to obtain a toner in which charging rises quickly and is excellent in charging stability in long-term durability. Among the conventionally known negatively chargeable charge control agents, compounds having such characteristics and light-colored to the extent applicable to color toners are very limited. Further, among them, it can be said that there is almost no compound when the compound has satisfactory properties such as thermal stability and dispersibility in resin. Therefore, the compounds used in the present invention are very useful.

One of the features of the toner for developing an electrostatic image of the present invention is that an appropriate charge amount can be quickly obtained. As a result, even when copying is performed immediately after the toner is put in the developing device, an image having a high image density can be obtained from the beginning. Also, when the toner is left at high temperature and high humidity and the image output is restarted, the charge amount temporarily decreases but returns to the proper charge amount quickly, so that the high image density is practically obtained immediately after the restart. can get. Further, the amount of charge does not become excessive due to continuous copying. Furthermore, although the detailed mechanism is unknown, the level of the ghost phenomenon is good,
It seems to have something to do with quick charging.

The following are specific examples of the compounds useful as the charge control agent having the above-mentioned characteristics, which are used in the toner for developing an electrostatic image of the present invention. It is an example and does not limit the present invention.

Compound Example (1) Polymer having the following repeating unit (ion B volume: 0.44 nm ³ ).

Compound Example (2) Copolymer having the following repeating unit (ion B volume: 0.44 nm ³ ).

Compound Example (3) (reference) A polymer having the following repeating unit (volume of ion B: 0.26 nm ³ ).

Compound Example (4) (reference) Polymer having the following repeating units (ion B volume: 0.35 nm ³ ).

Compound Example (5) Copolymer having the following repeating unit (ion B volume: 0.44 nm ³ ).

Compound Example (6) Copolymer having the following repeating unit (volume of ion B: 0.42 nm ³ ).

Compound Example (7) Polymer Having the Following Repeating Unit (Volume of Ion B: 0.63 nm ³ )

Compound Example (8) Polymer having the following repeating unit (ion B volume: 0.47 nm ³ ).

An example of the ion B is B as an anion.
(Aryl) ₄ ^-: For example, tetraphenyl - borate, tetra (fluorophenyl) borate, tetra (chlorophenyl) borate, Tetoranafuchiru - borate,
Tetra (methoxyphenyl) borate, tetrabiphenyl-borate, tetrabenzyl-borate, tetrapyridyl-borate, etc.], anion of a compound of aromatic hydroxycarboxylic acid and boron, silicon or metal: [eg,
A compound anion of hydroxynaphthoic acid and boron which may have a substituent, etc.], anion of a compound of aromatic diol and boron, silicon or metal, anion of compound of aromatic dicarboxylic acid and boron, silicon or metal Saturated or unsaturated aliphatic carboxylates or sulfonates,
Alicyclic carboxylates or sulfonates or aromatic carboxylates or sulfonates: [eg, lauryl sulfate, benzylic acid, etc.], perfluorinated saturated or perfluorinated unsaturated, aliphatic carboxylates or sulfonates,
Alicyclic carboxylates or sulfonates or aromatic carboxylates or sulfonates, saturated or unsaturated,
Aliphatic di-carboxylate or tricarboxylate, alicyclic di-carboxylate or tricarboxylate or aromatic di-carboxylate or tricarboxylate, di or trisulfonate, phosphoric acid, tungstic acid, molybdic acid, or Examples thereof include heteropolyacid anions (phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid or silicotungstic acid). Among these, it is particularly preferable to use the anion represented by the following general formula (1). In particular, an anion in which M in the formula is boron and R is aryl is preferable in terms of ease of synthesis and high charge amount.

General formula (1) (Wherein, R _1, R _2, R ₃ and R ₄ is an organic group independently of one another, each may be the same, Alternatively, R ₁ and R ₂
And R ₃ and R ₄ may each form a ring containing M.
M represents boron, silicon or aluminum, and n is 1
Or 2. )

As the cation in the present invention, an ammonium ion, for example, a trialkylbenzylammonium ion, a tetraalkylammonium ion or the like, or a picolinium ion, a pyridinium ion,
Examples thereof include quinolinium ion, imidazolium ion, phosphonium ion and sulfonium ion.

As the polymerization method for obtaining the compound used in the present invention, any polymerization method other than cyclopolymerization can be applied. That is, for example, a thermal polymerization method, a catalytic polymerization method using a catalyst, an addition polymerization method, for example, a chain polymerization method (free radical polymerization, cationic polymerization, anionic polymerization), polycondensation, polyaddition, etc. may all be applied. Is possible. In contrast,
Obtaining the ion A by cyclopolymerization is not preferable because it tends to be insufficient in uniformity of charging and rise of charging. The reason for this is not clear, but it is thought that the number of atoms forming the ring may not be constant, the flexibility of the molecule may be insufficient due to the size of the ring, or a portion that does not form the ring may be formed. .

In contrast to the compound used in the present invention as described above, the compound known from Japanese Patent Publication No. 4-261549 discloses a case where the toner surface becomes tacky when contained in the toner. As a result, the fluidity of the toner may be deteriorated, the image quality may be deteriorated, and the yield in production may be deteriorated. The reason for this is unknown, since this compound is produced by cyclic polymerization reaction, the properties of the resin might be due to hard to appropriately control. It can also be considered that when ion exchange is performed to obtain the compound as the charge control agent, the ion exchange rate does not sufficiently increase due to the cyclic structure.

As a method of incorporating the above compound used in the present invention into the toner, a method of adding it to the inside of the toner is used . In this case, the amount added is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the binder resin . The compound of the present invention can also be used in combination with a conventionally known charge control agent as described in the section of the prior art.

The toner for developing an electrostatic charge image of the present invention comprises at least a binder resin and a coloring material in addition to the above compounds, and may contain inorganic fine powder in addition to these. As the inorganic fine powder used at this time, for example, inorganic oxides such as silica, alumina, and titanium oxide, carbon black, carbon fluoride, and the like are preferable because it is easy to form fine particles.

Further, in the present invention, among the inorganic fine powders described above, the electronegativity of the metal ion in the oxide (χ
_An inorganic oxide having _i ) of 8 to 15 is preferable, and further,
Those having an electronegativity of 10 to 14 are preferably used. That is, since such an inorganic oxide is electrostatically neutral, the attractive force acting on the particles is weak, so that when it is dispersed on the toner surface, it has excellent dispersibility and high fluidity imparting ability. Have. Regarding the metal in the oxide, Pauling's electronegativity is χ ₀ and the valence of the metal ion is Z.
Then, the electronegativity (χ _i ) of the metal ion in the oxide can be calculated by the following equation. χ _i = (1 + 2 × Z) χ ₀

Among the inorganic oxides having electronegativity (χ _i ) of metal ions in the oxide of 8 to 15, for example, titanium oxide, alumina, Fe ₂ O ₃ , Fe ₃ O ₄ , strontium titanate, etc. It is particularly preferable in terms of dispersibility in toner and effect on charging. The electronegativity in the case of a complex oxide such as strontium titanate is calculated by weighted averaging. Further, among these, titanium oxide and alumina are particularly preferable because they have good environment dependence and excellent fluidity imparting ability. In addition, these may be used together, including silica fine powder.

When the surface of the toner is covered with such an inorganic fine powder, a preferable area ratio is 30 to 80%. Also, when dispersed on the toner surface, finer particles are preferable because the fluidity is enhanced. In the present invention,
The average particle size is preferably 5 to 100 nm, and BE
The specific surface area by nitrogen adsorption measured by T method is 80 m ² /
g or more, particularly preferably in the range of 100 to 400 m ² / g is preferable as the base fine powder, and in the fine powder treated as described below, 50 m ² / g or more (especially 8
It is preferably in the range of 0 to 350 m ² / g). The applied amount of these inorganic fine powders is based on the toner base weight.
An appropriate area ratio is obtained when about 0.03 to 5% by weight is added.

The degree of hydrophobicity of the inorganic fine powder used in the present invention is preferably 30% or more. As the hydrophobic treatment agent used in this case, a silane coupling agent and a silicone oil, which are silicon-containing surface treatment agents, are preferable. For example, dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethylchlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane. , Divinylchlorosilane, dimethylvinylchlorosilane and the like. or,
Positively chargeable silicon-containing surface treatment agents include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane. Examples thereof include silane coupling agents such as silane and amino-modified silicone oil.

Further, the electrostatic image developing toner of the present invention is
It can be mixed with a carrier and used as a two-component toner. The current value of the carrier at this time is 20 to 200 by adjusting the degree of unevenness of the carrier surface and the amount of resin to be coated.
It is better to set it to about μA. Here, as the resin coating the carrier surface, for example, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, acrylic acid ester copolymer, methacrylic acid ester copolymer, silicone resin, fluorine Examples thereof include resins, polyamide resins, ionomer resins, polyphenylene sulfide resins, etc., and mixtures thereof.

As the magnetic material for the carrier core, for example, oxides such as ferrite, iron-excessive ferrite, magnetite and γ-iron oxide, metals such as iron, cobalt and nickel, and alloys thereof are used. Can be mentioned.
Examples of the elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead,
Magnesium, tin, zinc, antimony, beryllium,
Examples thereof include bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium.

Examples of the binder resin used as a constituent component of the toner for developing an electrostatic image of the present invention include homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and their substitution products; Styrene-p
-Chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethylmethacrylate copolymer Polymer, 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-based copolymers such as styrene-acrylonitrile-indene copolymer; Others, polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin , Polje Ether resins, polyurethane, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resin, coumarone-indene resins, petroleum resins and the like. A crosslinked styrene copolymer is also one of the preferable binder resins.

Examples of the comonomer for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate,
Dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc. Monocarboxylic acid having a heavy bond or a substituted product thereof; Dicarboxylic acid having a double bond such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate and the like; a substituted product thereof; vinyl chloride, vinyl acetate, benzoic acid Vinyl esters such as vinyl; ethylene-based olefins such as ethylene, propylene and butylene; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; vinyl methyl ether, vinyl ethyl ether, vinyl Such ether and Seo ether; vinyl monomer can be mentioned, these can be used singly or two or more.

Here, as the crosslinking agent, a compound having two or more polymerizable double bonds is mainly used. Specifically, for example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; and two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and 1,3-butanediol dimethacrylate. Examples thereof include carboxylic acid esters; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups; these may be used alone or as a mixture.

When the binder resin is a styrene-acrylic resin material, the toner has a molecular weight distribution of 3,000 to 50,000,000 which is a THF (tetrahydrofuran) soluble component by GPC. A binder resin having at least one peak in a region, at least one peak in a region having a molecular weight of 100,000 or more, and having a molecular weight distribution of 100,000 or less in a proportion of 50 to 90% is used. Is preferred.

When the binder resin is a polyester resin material, the toner has the same molecular weight distribution as described above, and at least one peak exists in the molecular weight range of 3,000 to 50,000. 000 or less ingredients are 60 ~
It is preferable to use a binder resin so as to be 100%. More preferably, it is preferable to use a binder resin having at least one peak in the molecular weight range of 5,000 to 20,000.

Among the above binder resins, the polyester resin is excellent in fixability and suitable for color toners.
In particular, a bisphenol derivative represented by the general formula (2) is used as a diol component, and a carboxylic acid component composed of a divalent or higher carboxylic acid, or an acid anhydride thereof, or a lower alkyl ester thereof (for example, fumaric acid, maleic acid, It is preferable to use a polyester resin obtained by copolycondensation of maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as a binder resin because it has good charging characteristics as a color toner.

General formula (2) (In the formula, R is an ethylene or propylene group, and X,
Y is an integer of 1 or more, and the average value of X + Y is 2 to 10. )

In the present invention, a magnetic material may be contained in the toner to form a magnetic toner. The average particle size of the magnetic fine powder used at this time is preferably 0.
05-0.5 μm, more preferably 0.1-0.4 μm
It is good to set the degree. The variation coefficient of particle size is preferably 30% or less. The amount of the magnetic material contained in the magnetic toner is 40 to 120 with respect to 100 parts by weight of the resin component.
It is preferable that the amount is about parts by weight.

Examples of the magnetic material used in the present invention include iron oxides such as magnetite, γ-iron oxide, ferrite and iron-excess type ferrite; metals such as iron, cobalt and nickel; or these metals and aluminum. , Cobalt, copper, lead, magnesium, tin, zinc, antimony,
Examples thereof include alloys with metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof; and the like.

In the present invention, the inclusion of a wax component in the toner is also one of the preferred embodiments. The hydrocarbon wax used in this case is, for example, an alkylene polymer obtained by radically polymerizing alkylene under high pressure, an alkylene polymer polymerized by a Ziegler catalyst under low pressure, or an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer. , A synthetic hydrocarbon obtained by hydrogenating the distillation residue of the hydrocarbon obtained by the Arge process from a synthetic gas consisting of carbon monoxide and hydrogen.
Among these hydrocarbon waxes, a hydrocarbon wax obtained by extracting and fractionating a specific component is particularly suitable. For example, those having a low molecular weight component removed by a method such as a press sweating method, a fractional crystallization method utilizing a solvent method or vacuum distillation, one having a low molecular weight component extracted, and one having a further low molecular weight component removed therefrom, etc. Is preferred. In addition to these, microcrystalline wax, carnauba wax, sazol wax and paraffin wax, aliphatic solid alcohol and the like can be mentioned.

The preferable range of the molecular weight of these waxes is 5 for the number average molecular weight (Mn, calculated as polyethylene).
00-1200, weight average molecular weight (Mw) is 800-
Those of 3600 are preferably used. If the molecular weight is smaller than the above range, blocking resistance and developability will be poor, and if the molecular weight is larger than the above range, good fixability and offset resistance will be difficult to obtain. The wax used in the present invention preferably has a Mw / Mn of 5.0 or less, more preferably a Mw / Mn of 3.0.
The following should be used. The content of such wax is 0.5 to 1 with respect to 100 parts by weight of the binder resin.
It is effective to use about 0 parts by weight.

[0053] As a colorant, a component of the electrostatic image developing preparative toner of the present invention, for example, carbon black, lamp black, iron black, ultramarine, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6G, chalco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triarylmethane dye,
Examples thereof include monoazo dyes and disazo dyes and pigments. As these dyes, conventionally known dyes and pigments may be used alone or in combination.

In the toner for developing an electrostatic image of the present invention, for example, toner particles having a weight average particle diameter of 3 to 15 μm can be used. In particular, 12 to 60% by number of toner particles having a particle size of 5 μm or less are contained, and
1 to 33% by number of toner particles having a particle size of 12.7 μm are contained, 2.0% by weight or less of toner particles having a particle size of 16 μm or more are contained, and the weight average particle size of the toner is 4 to 10 μm. It is more preferable from the standpoint of development characteristics.

To the toner for developing an electrostatic image of the present invention, in addition to the above-mentioned ones, the following additives may be added as necessary for the purpose of imparting various characteristics. Examples of the additives that can be used in the present invention include the followings. These can be appropriately selected according to the purpose and added to the toner.

1) Abrasives: metal oxides such as strontium titanate, cerium oxide, aluminum oxide, magnesium oxide and chromium oxide, nitrides such as silicon nitride, carbides such as silicon carbide, calcium sulfate, barium sulfate and calcium carbonate. And the like.

2) Lubricants: Fluorine-based resin powders such as vinylidene fluoride and polytetrafluoroethylene, and fatty acid metal salts such as zinc stearate and calcium stearate.

3) Charge controllable particles: metal oxides such as tin oxide, titanium oxide, zinc oxide, silicon oxide and aluminum oxide, carbon black, average particle size 0.05 to 3 μm.
Spherical resin fine particles and the like.

These additives are used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner particles. These additives may be used alone or in combination.

In the production of the toner for developing an electrostatic image of the present invention, the above-mentioned toner constituent materials are thoroughly mixed by a ball mill or other mixer, and then a heat kneader such as a heat roll kneader or an extruder is used. A method of obtaining a toner by mechanically pulverizing and classifying after thoroughly kneading and solidifying by cooling is preferable. Alternatively, a method of obtaining a toner by dispersing constituent materials in a binder resin solution and then spray drying. A polymerization method of producing a toner by mixing a predetermined material with a monomer that constitutes a binder resin to form an emulsion suspension, and a so-called microcapsule including a core material and a shell material In the toner, a method such as a method of incorporating a predetermined material into the core material or the shell material, or both of them can be appropriately applied. Furthermore, the toner of the present invention can be manufactured by sufficiently mixing desired additives with a mixer such as a Henschel mixer, if necessary.

The method of measuring each characteristic value used in the present invention will be described below. First, in the present invention, the size (volume) of the ion B refers to the entire area occupied by the van der Waals radius of the atoms constituting the ion, and can be calculated. For example, the minimum energy structure can be easily calculated by using a commercially available chemical calculation program such as Polygraph (manufactured by MSI).

The molecular weight distribution by GPC of the compound used in the present invention is measured under the following conditions. First, 23
Stabilize the column in a heat chamber at 0 ° C. and allow the solvent to flow through the column at this temperature at a flow rate of 0.5 m / min,
The sample solution is injected by about 300 μm for measurement. In addition, when measuring the molecular weight of the sample,
It was calculated from a calibration curve (relationship between logarithmic value of molecular weight and count number) prepared from several different monodisperse PMMA standard samples. As a standard PMMA sample for preparing a calibration curve, for example, the molecular weight of Tosoh or Showa Denko is 10 ² to
It is suitable to use about 10 ⁷ and use at least about 10 standard PMMA samples. An RI (refractive index) detector is used as the detector. In addition, as a column,
It is preferable to combine a plurality of commercially available polystyrene gel columns, for example, Shodex manufactured by Showa Denko KK
HPIP-80M, GPC KF-801, 802, 8
03, 804, 805, 806, 807, 800P combination, TSKgel G100H made by Tosoh Corporation
(H _XL ), G2000H (H _XL ), G3000H
(H _XL ), G4000H (H _XL ), G5000H
(H _XL ), G6000H (H _XL ), G7000H
(H _XL ), a combination of TSKguardcolumn can be mentioned.

The measurement sample used for measuring the molecular weight distribution is prepared as follows. First, the sample is dissolved in a solvent. The solvent used may be, for example, a mixture of hexafluoroisopropanol and a trace amount of sodium trifluoroacetate. After allowing the solution in which the sample is dissolved to stand for several hours, the sample is shaken sufficiently until there is no union of the samples, and the sample is left standing for 12 hours or more. Then, a sample processing filter having a pore size of about 0.45 to 0.5 μm (for example, Mysholydisk H-13-
5 manufactured by Tosoh Co., Ltd., Excicro Disc 25CR manufactured by Gelman Science Japan Co., Ltd.) can be used as a sample for GPC. The sample concentration is adjusted so that the resin component is 0.3 to 5 mg / ml.

The Tg is measured with a highly accurate differential scanning calorimeter of the internal heat type input correction type. For example, DSC-7 or the like manufactured by Perkin Elmer can be used. The measuring method is performed according to ASTM D3418-82.

The particle size distribution of the toner can be measured by various methods. In the present invention, it is suitable to use a Coulter Multisizer. That is, Coulter Multisizer II (manufactured by Coulter, Inc.) was used as a measuring device, a 100 μm aperture was used as an aperture, and the volume and number of toner were measured to
The volume distribution and number distribution of 40 μm particles were calculated. Then, the weight-based weight average diameter obtained from the volume distribution is obtained, the weight-based coarse amount (16 μm or more) obtained from the volume distribution, and the number-based ratio obtained from the number distribution (for example, 2.0 to 4). 0.0 μm range, 5 μm or less, 8 to 1
The content in the range of 2.7 μm) was determined.

Further, the toner cohesion is measured by using a powder tester (manufactured by Hosokawa Micron Co., Ltd.). First, the sieve is set on the vibrating table in the order of 200 mesh, 100 mesh, and 60 mesh from the bottom. 5 g of toner is gently placed on the stacked sieves, and then vibration is applied for 15 seconds. After that, the mass of the toner remaining on each screen is measured, and the degree of aggregation is determined by the following formula. Aggregation degree (%) = {a / 5 + (b / 5 × 3/5) + (c / 5 × 1/5)} × 100 a: toner mass on 60 mesh (g) b: toner mass on 100 mesh ( g) c: toner mass on 200 mesh (g)

[0067]

EXAMPLES The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention.
All parts in the following formulations are parts by weight unless otherwise specified.

Synthesis of Compound (Synthesis Example 1-1) Vinylbenzyltrimethylammonium chloride was polymerized to obtain polyvinylbenzyltrimethylammonium chloride. This was dissolved in water to obtain a first solution.
Separately, sodium-tetraphenylborate (anion diameter: 0.44 nm ³ ) was dissolved in water, and this was gradually added dropwise to the first solution while stirring. The precipitate was filtered, washed with water, and vacuum dried to obtain the compound. Elemental analysis,
When proton NMR was performed, it was almost in agreement with the structure of the above compound example (1). When the molecular weight distribution of the obtained compound was measured by GPC, the weight average molecular weight (Mw) was 56,000 and Mw / Mn was 2.4. In addition, the content of components having a molecular weight of 3,000 or less in this compound was 5%.

(Synthesis Example 1-2) Methyl chloride quaternary salts of styrene and dimethylaminoethyl methacrylate were charged at a weight ratio of 10:50, and a polymerization initiator was added to carry out solution polymerization of methanol / toluene to obtain a polymer. Obtained. This polymer was dissolved in water to obtain a first solution. Separately, sodium-tetraphenylborate was dissolved in water, and this was gradually added dropwise to the first solution while stirring. The precipitate was filtered, washed with water, and vacuum dried to obtain the compound. When the elemental analysis and the proton NMR were performed, it was almost in agreement with the structure of the above-mentioned compound example (2). When the molecular weight distribution of the obtained compound was measured by GPC, the weight average molecular weight (Mw) was 30,000,
Mw / Mn was 3.6. In addition, 12% of the compound had a molecular weight of 3,000 or less.

(Synthesis Example 1-3) Sodium tetraphenylborate was converted into sodium salt of di- [catechol] borate (anion diameter: 0.26n).
A compound was obtained in the same manner as in Synthesis Example 1-1, except that m ³ ) was used instead. When elemental analysis and proton NMR were performed,
The structure was almost the same as that of the compound example (3) described above. When the molecular weight distribution of the obtained compound was measured by GPC,
Weight average molecular weight (Mw) is 50,000, Mw / Mn
Was 2.5. In addition, the content of components having a molecular weight of 3,000 or less in this compound was 5%.

(Synthesis Example 1-4) A homopolymer of polydiallyldimethylammonium chloride was obtained by subjecting diallyldimethylammonium chloride to a cyclopolymerization reaction. A compound was obtained in the same manner as in Synthesis Example 1-1 except that this was dissolved in water to obtain the first solution. When the molecular weight distribution of the obtained compound was measured by GPC, the weight average molecular weight (Mw) was 71,000 and Mw / Mn was 3.4. In addition, the proportion of the compound having a molecular weight of 3,000 or less was 7%.

(Synthesis Example 1-5) A compound was obtained in the same manner as in Synthesis Example 1-1, except that sodium-tetraphenylborate was replaced with sodium methylsulfate (anion diameter: 0.11 nm ³ ). When the molecular weight distribution of the obtained compound was measured by GPC, the weight average molecular weight (Mw) was 46,000 and Mw / Mn was 2. It was 4 . In addition, the content of components having a molecular weight of 3,000 or less in this compound was 5%.

(Synthesis Example 1-6) Synthesis Example 1 except that 4,4'-diamino-3,3'-diethylphenylmethane was dissolved in dilute hydrochloric acid to prepare a first solution.
A compound was obtained in the same manner as in -1. The molecular weight of the obtained compound was 571.

Synthesis of Binder Resin (Synthesis Example 2-1) -Propoxylated bisphenol 52 mol% -Fumaric acid 40 mol% -Terephthalic acid 5 mol% -Trimellitic anhydride 1 mol% Binder by condensation polymerization using the above components Resin 1 was obtained.

[0075] Polymer A was obtained by suspension polymerization using the above components. -Styrene 83 parts-Butyl acrylate 17 parts-Di-t-butyl peroxide 2.0 parts Using the above components , solution polymerization was carried out using xylene as a solvent to obtain a polymer B. The polymer A: polymer B: polypropylene wax (Mn = 810, Mw = 1330) was mixed in a solution at a weight ratio of 30: 70: 3 to obtain a binder resin 2.

(Synthesis Example 2-3) ・ Propoxylated bisphenol 55 mol% ・ Terephthalic acid 38 mol% ・ Trimellitic anhydride 7 mol% Binder resin 3 was obtained by condensation polymerization using the above components.

Example 1 Binder resin 2 100 parts Magnetite 100 parts Synthetic example 1-1 powder 3 parts After thoroughly mixing the above materials with a blender, kneading with a twin-screw kneading extruder set at 130 ° C. did. The obtained kneaded product was cooled, coarsely pulverized, and finely pulverized using a fine pulverizer using a jet stream. Further, the finely pulverized product thus obtained is subjected to strict classification of ultrafine powder and coarse powder at the same time with a multi-division classifier utilizing the Coanda effect (Elbow Jet classifier manufactured by Nittetsu Mining Co., Ltd.) to give a weight average particle size of 6. A black fine powder of 5 μm was obtained. The saturation magnetization of this fine powder is 38 Am ² / kg, and the acid value is 3 mg.
It was KOH / g. The cohesion degree was 35%.
100 parts of the obtained resin fine powder was mixed with 1.0 part of silica fine powder (particle size 15 nm) treated with hexamethyldisilazane and dimethyl silicone oil and 3.0 parts of strontium titanate (particle size 900 nm). A toner of this example was obtained.

[Evaluation] A commercially available electrophotographic copying machine GP was used for the above magnetic toner.
Using a modified machine of -55 (made by Canon Inc.), 23 ° C, 10
A copy test was performed on 10,000 sheets in an environment of% RH. As a result, a bright black image having an image density of 1.40 was obtained from the initial stage, and thereafter, the level changed to 1.45 ± 0.03. At this time, the charge amount on the sleeve is -10.
1 mC / kg, at the 10,000th sheet -9.8 mC / kg
It was stable. Following that, 30 ℃, 80
When a copy test was performed on 20,000 sheets in a high humidity environment of% RH, the image density was 1.40 ±, except immediately after left for 1 day.
The image remained at the level of 0.05, and an image free from fog was obtained. When the recording was restarted after being left, it was 1.30 at the lowest image density, but reached a stable level after copying about 50 sheets.

Example 2 Binder Resin 1 100 parts Copper phthalocyanine pigment 5 parts Synthetic Example 1-1 powder 3 parts After mixing the above materials well with a blender, put them in a twin-screw kneading extruder set at 110 ° C. After kneading, the resin fine powder having a weight average particle diameter of 7.2 μm was obtained in the same manner as in Example 1.
The acid value of the obtained fine powder was 9 mgKOH / g, and the degree of aggregation was 62%. To 100 parts of the obtained fine powder, 0.8 part of hydrophobized titanium oxide (average particle size 25 nm) was mixed with a Henschel mixer to obtain a toner. Next, a carrier in which ferrite particles having an average particle diameter of 45 μm are coated with a silicone resin is mixed with a toner to form a two-component toner. The mixing ratio was 94 parts of carrier and 6 parts of toner.

[Evaluation] This two-component toner was used as a commercially available color electrophotographic copying machine CLC.
A copying test was performed with -550 (manufactured by Canon Inc.). 23
When copying was performed in an environment of 60 ° C. and RH, a good image with a density of 1.65 was obtained from the beginning. Further, the halftone image was very smooth and the image without fog was obtained. When 10,000 copies were made, a good image with a density of 1.71 was obtained, and at that time, almost no deterioration of image quality was observed with an increase in the number of copies. At this time, 2 on the sleeve
The component toners were sampled and the charge amount was measured. As a result, they were stable at −24.6 mC / kg on the 50th sheet and −23.1 mC / g on the 10,000th sheet.

Further, even under the environmental conditions of low humidity of 23 ° C. and 10% RH, a good image having a density of 1.60 was obtained from the initial stage. After copying 10,000 sheets, no phenomenon of reduction in image density was observed. Further, the deterioration of the image quality such as the smoothness of the halftone image and the sharpness of the image with the increase of the number of copies was not recognized. Next, when a copying test was similarly performed under an environmental condition of high humidity of 30 ° C. and 80% RH, a good image having a density of 1.71 was obtained from the initial stage. Moreover, when 10,000 sheets were copied, no reduction in image density was observed. Furthermore,
The copying test was restarted after leaving it in an environment of high humidity of 30 ° C. and 80% RH for 3 days. As a result, the image density of the first sheet after resumption was 1.80, which was slightly higher than that before leaving, but it was 1.72 after copying 20 sheets, returning to the state before leaving. In addition, no toner scattering was observed in the copying machine.

Example 3 The same as Example 2 except that 3 parts of the compound obtained in Synthesis Example 1-2 was used in place of the compound obtained in Synthesis Example 1-1. To obtain toner.
The weight average particle diameter of the obtained toner was 7.4 μm, and the degree of aggregation of the resin fine powder was 75%.

[Evaluation] Using the obtained two-component toner, a copying test was conducted in the same manner as in Example 2. When copying was performed in an environment of 23 ° C. and 60% RH, a good image with a density of 1.70 was obtained from the initial stage. Further, a very smooth halftone image and a sharp image were obtained. Also, after copying 10,000 sheets,
A good image with a density of 1.75 was obtained, and almost no deterioration of image quality was observed with an increase in the number of copies. At this time, the two-component toner on the sleeve was sampled and the charge amount was measured. As a result, the 50th sheet was −23.8 mC / kg, and the 10,000th sheet was −22.1 mC / kg. Was there.

A good image with a density of 1.70 was obtained from the beginning even under environmental conditions of low humidity of 23 ° C. and 10% RH.
Moreover, when 10,000 sheets were copied, no reduction in image density was observed. No deterioration of the image quality such as the smoothness of the halftone image or the sharpness of the image with the increase in the number of copies was observed. Next, when a copy test was similarly performed under an environmental condition of high humidity of 30 ° C. and 80% RH, the density was 1.7 from the initial stage.
A good image of 5 was obtained. Moreover, when 10,000 sheets were copied, no reduction in image density was observed. Furthermore, 30
The copying test was restarted after leaving it in a high humidity environment of 80 ° C. and 80% RH for 3 days. As a result, the image density of the first sheet after resumption was 1.85, which was slightly higher than that before leaving,
After copying 40 sheets, it returned to the condition before leaving 1.75. In addition, no toner scattering was observed in the copying machine.

Comparative Example 1 Example 2 was repeated except that 3 parts of the compound obtained in Synthesis Example 1-3 was used instead of the compound obtained in Synthesis Example 1-1. to obtain the door toner Te.
This toner had a weight average particle diameter of 7.5 μm, and the degree of aggregation of the resin fine powder was 61%.

[Evaluation] Using the obtained two-component toner, a copying test was conducted in the same manner as in Example 2. When copying was performed in an environment of 23 ° C. and 60% RH, a good image with a density of 1.70 was obtained from the initial stage. Further, a very smooth halftone image and a sharp image were obtained. Also, after copying 10,000 sheets,
A good image with a density of 1.73 was obtained, and almost no deterioration in image quality was observed with an increase in the number of copies. At this time, the two-component toner on the sleeve was sampled to measure the charge amount, which was -22.5 mC / kg on the 50th sheet and -20.2 mC / kg on the 10,000th sheet, which was stable. Was there.

A good image with a density of 1.61 was obtained from the initial stage even under environmental conditions of low humidity of 23 ° C. and 10% RH.
Moreover, when 10,000 sheets were copied, no reduction in image density was observed. No deterioration of the image quality such as the smoothness of the halftone image or the sharpness of the image with the increase in the number of copies was observed. Next, when a copy test was similarly performed under an environmental condition of high humidity of 30 ° C. and 80% RH, the density was 1.7 from the initial stage.
7 good images were obtained. Moreover, when 10,000 sheets were copied, no reduction in image density was observed. Furthermore, 30
The copying test was restarted after leaving it in the environment of 80 ° C. and 80% RH for 3 days. The image density of the first sheet after restarting was 1.90, which was slightly higher than that before leaving, but after copying 40 sheets, it was 1.79, returning to the state before leaving. Further, almost no toner scattering was observed in the copying machine.

Comparative Example 2 Example 2 was repeated except that 3 parts of the compound obtained in Synthetic Example 1-4 was used instead of the compound obtained in Synthetic Example 1-1. To obtain a comparative toner. The weight average particle diameter of the toner was 7.2 μm, and the degree of aggregation of the resin fine powder was as high as 90%.

[Evaluation] A copying test was conducted in the same manner as in Example 2 using the obtained two-component toner. When copying was performed in an environment of 23 ° C. and 60% RH, an image with a density of 1.65 was initially obtained, but the halftone image was inferior in smoothness to Example 2. When 10,000 copies were made, the density was 1.75, which was not so different from the initial density, but deterioration of image quality was observed as the number of copies increased. At this time, when the two-component toner on the sleeve was sampled and the charge amount was measured,
The second sheet is −24.0 mC / kg, and the 10,000th sheet is −22.
The charge amount was 6 mC / kg, and the charge amount was stable.

Comparative Example 3 Example 2 was repeated except that 3 parts of the compound obtained in Synthesis Example 1-5 was used in place of the compound obtained in Synthesis Example 1-1. To obtain a comparative toner. This toner had a weight average particle size of 7.1 μm, and the degree of aggregation of the resin fine powder was 74%.

[Evaluation] The obtained two-component toner was subjected to a copy test in the same manner as in Example 2. When copying was performed in an environment of 23 ° C. and 60% RH, an image with a density of 1.65 was initially obtained, but the halftone image was inferior in smoothness to Example 2.
Further, the density became 1.90 at the time of copying 3,000 sheets. At this time, the two-component toner on the sleeve was sampled to measure the charge amount.
While it was 2 mC / kg, it was -15.
It was as low as mC / kg. Further, the deterioration of image quality and the deterioration of fog with the increase in the number of copies were remarkable, so the durability test was stopped.

Comparative Example 4 Example 2 was repeated except that 3 parts of the compound obtained in Synthesis Example 1-6 was used instead of the compound obtained in Synthesis Example 1-1. To obtain a comparative toner. The weight average particle diameter of this toner is 7.2 μm,
The degree of aggregation of the resin fine powder was 66%.

[Evaluation] Using the obtained two-component toner, a copying test was conducted in the same manner as in Example 2. When the image was copied under the environment of 23 ° C. and 60%, the image density was as high as 1.78 from the initial stage. However, when copying 10,000 sheets, the density became even higher at 1.87, and toner scattering in the copying machine was also recognized. The image quality was also inferior to that of Example 2 as a whole. At this time, when the two-component toner on the sleeve was sampled and the charge amount was measured, the 50th sheet was -19.0 mC / k.
g, which was a low value of -17.6 mC / kg for 10,000 sheets.

Example 4 Binder Resin 3 100 parts Carbon black 5 parts Synthetic Example 1-1 powder 4 parts In the same manner as in Example 1 using the above materials, resin fine powder having a weight average diameter of 9.0 μm. Got the body Obtained resin fine powder 1
Hydrophobized alumina fine powder (average particle size 20n
m) 0.6 part was mixed to obtain a toner. Next, 94 parts of an acrylic-coated ferrite carrier having an average particle diameter of 55 μm and 6 parts of the obtained toner were mixed to obtain a two-component toner.

[Evaluation] With respect to this two-component toner, a copying machine of NP-6060 (manufactured by Canon Inc.) was used to perform a copying test on 50,000 sheets by using a two-component developing device. As a result, a clear image free from fog was obtained at an image density of 1.38 from the initial stage. Again 5
The image after copying 10,000 copies is also clear with a density of 1.42.
No image defect due to toner fusion was observed. No deposit was found on the photosensitive drum.

Example 5 Binder Resin 3 100 parts Copper phthalocyanine pigment 5 parts Synthetic Example 1-1 powder 4 parts A resin having a weight average diameter of 8.6 μm was prepared in the same manner as in Example 1 using the above materials. A fine powder was obtained. Obtained resin fine powder 1
To 100 parts, 1.3 parts of acid value titanium fine powder treated with dimethyl silicone oil (average particle size 30 nm) was mixed to obtain a toner.

[Evaluation] With respect to this magnetic toner, FC-310 was modified for a negative toner, and a copying test of 5,000 sheets was carried out using a modified developing device for a non-magnetic one-component developer. As a result, a clear image free from fog was obtained at an image density of 1.38 from the initial stage. The image after copying 5,000 sheets was also clear with a density of 1.42, and no image defect due to toner fusion was observed. No deposit was found on the photosensitive drum.

[0098]

[0099]

Example 6 As described below, a yellow toner, a magenta toner, and a black toner were obtained in the same manner as in Example 2. or,
The characteristics of each of the obtained toners are as follows. (1) The yellow toner colorant is C.I. I. Pigment Yellow 17 The following yellow toner was prepared in the same manner as in Example 2 except that 3 parts were used.・ Weight average diameter: 7.5 μm ・ Acid value: 9 mg KOH / g ・ Cohesion degree: 66%

(2) The magenta toner colorant is C.I. I. Pigment Red 122 The following magenta toner was prepared in the same manner as in Example 2 except that 5 parts were used. -Weight average diameter: 7.2 μm-Acid value: 9 mg KOH / g-Aggregation degree: 65%

(3) Black Toner The following black toner was prepared in the same manner as in Example 2 except that 5 parts of carbon black (particle size: 30 μm) was used as the colorant. Weight-average diameter: 8.0 .mu.m, acid value: 9 mg KOH / g · cohesion: 59% using these toners were two-component toner by mixing the carrier in the same manner as in Example 2.

[Evaluation] Using these two-component toners and the cyan toner of Example 2, a full color copying test was carried out with CLC-800 (manufactured by Canon Inc.). The obtained image had good color reproduction in the highlight portion and had uniform dots and smooth image quality. When the image densities of the respective colors were evaluated, the cyan toner was 1.62, the yellow toner was 1.66, the magenta toner was 1.59, and the black toner was 1.58. After that, 10,000 copies were made, but the image density variation during that period was small, and the images after 10,000 copies had almost the same image quality as the initial image.

[0104]

As described above, according to the present invention, there is provided an electrostatic charge image developing toner capable of obtaining an image having high image density, no fog, and excellent highlight reproducibility. Further, according to the present invention, there is provided a toner for developing an electrostatic charge image, which has an appropriate amount of charge very quickly and is excellent in stability of the amount of charge in long-term durability. Further according to the invention,
Provided is a toner for developing an electrostatic charge image, which stably produces an image having a high image density when copying is restarted after being left under low humidity or high humidity, and in which toner scattering does not occur. Furthermore, according to the present invention, since the compound having a function as a charge control agent is colorless or light-colored, a color toner for developing an electrostatic charge image having good color reproducibility is provided.

─────────────────────────────────────────────────── --- Continued from the front page (56) References JP-A-4-261549 (JP, A) JP-A-4-215665 (JP, A) JP-A-4-142555 (JP, A) JP-A-62-1 264066 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 9/097

Claims (3)

(57) [Claims] 1. An ion A, which is a polymer having a linear main chain obtained by an acyclic polymerization reaction having a structure containing an ionized element as a repeating unit and having no crosslinked structure , The polarity is opposite to that of the ion A and the volume is 0.4.
A toner for developing an electrostatic charge image, wherein a compound having a molecular weight of 600 or more and an ion B having a size of 0 nm ³ or more is internally added. 2. The toner for developing an electrostatic charge image according to claim 1, which has the same polarity as that of the ion B. 3. The toner for developing an electrostatic charge image according to claim 1, wherein the ion B is an anion.