JP2899038B2 - Toner for developing electrostatic images - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a toner for visualizing a latent electrostatic image in an image forming method such as electrophotography and electrostatic recording.

[Conventional technology]

Conventionally, as electrophotography, U.S. Patent No. 2,297,691,
Various methods are described in JP-B-42-23910 and JP-B-43-24748.

Developing methods applied to the electrophotographic method and the like are roughly classified into a dry developing method and a wet developing method. The former is further classified into a method using a two-component developer and a method using a one-component developer.

Conventional toners applied to these dry development methods include:
Fine powders in which dyes and pigments are dispersed in natural or synthetic resins are used. For example, particles obtained by finely pulverizing a dispersion of a colorant in a binder resin such as polystyrene to about 1 to 30 μm are used as the toner. As the magnetic toner, a toner containing magnetic particles such as magnetite is used. In the case of using a two-component developer, the toner is usually used by mixing with carrier particles such as glass beads and iron powder.

Any toner must have a positive or negative charge, depending on the polarity of the electrostatic latent image to be developed.

In order to cause the toner to retain an electric charge, it is possible to use the frictional charging property of the resin which is a component of the toner.However, in this method, since the charging property of the toner is low, an image obtained by development is easily fogged and unclear. It will be. Therefore,
In order to impart an appropriate triboelectric charging property to a toner, a dye, a pigment, and a charge control agent for imparting charging property are added.

As the charge control agents known in the art today, metal complex salts of monoazo dyes, metal complex salts of salicylic acid, alkyl-substituted salicylic acid, naphthoic acid, dicarboxylic acid, copper phthalocyanine pigment, and the like are known.

[Problems to be solved by the invention]

However, since some of these charge control agents easily contaminate the sleeve or carrier, the amount of triboelectricity of the toner using the same decreases with an increase in the number of copies, resulting in a decrease in image density. In addition, some charge control agents have insufficient triboelectric charge and are susceptible to temperature and humidity, which causes environmental fluctuations in image density. In addition, certain charge control agents have poor storage stability, and their triboelectric charging ability decreases during long-term storage. In addition, since a certain type of charge control agent has poor dispersibility in a resin, a toner using the same has a non-uniform triboelectric charge amount between particles and is easily fogged. Further, certain charge control agents have poor thermal stability and may be decomposed and deteriorated during the heating and kneading process during toner production. A toner manufactured by reusing a part of the toner using such a charge control agent is liable to generate reverse-charging particles and easily cause fogging. Some charge control agents are colored and cannot be used substantially in color toners.

At present, there is a strong demand for the development of charge control agents that satisfy all of these.

[Means and actions for solving the problem]

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the p-phenylcalix [n] arene compound formed of the constituent elements A and B represented by the general formula (I) has a sufficient triboelectric charge. It is colorless or substantially colorless at the same time as having the ability, and when incorporated in a toner, it has been found that this toner has a sufficient amount of triboelectric charge and solves the above problems, and has reached the present invention. Things.

General formula (I) [Where A is the following formula Where B is the following formula Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a halogen, a carboxyl group, a hydroxy group, a cyano group, a nitro group, Methyl halide, trimethylsilyl, ester having 1 to 8 carbons, amide having 1 to 8 carbons, acyl having 1 to 12 carbons, sulfonyl having 1 to 8 carbons, 1 to 8 carbons
Wherein n is an integer of 4 to 8, and m is n
The following integers of 0 to n are shown. However, in the general formula (I), m and n indicate the number of components A and B, and do not define the order in which the components A and B are combined. The present invention relates to a toner containing the p-phenylcalix [n] arene compound as a negatively chargeable charge control agent.

As examples in which a phenol type compound is used as a charge control agent, low molecular weight resins containing an amino group and a phenol group are proposed in JP-A-63-138355 to JP-A-138357. However, these resins are contained in the toner for the purpose of imparting positive chargeability, and have different purposes and performance from the present invention.

JP-A-63-260253 and JP-A-63-266462 propose a phenol compound as a toner composition. However, when we have examined these phenol compounds, these phenol compounds themselves have low negative triboelectric charging properties and are difficult to use as charge control agents.

Further, JP-B-58-9415 and JP-A-63-260253 propose a polycondensate of a phenol compound and an aldehyde or ketone or a phenol resin as a toner composition for controlling a negative charge. . However, when these polycondensates or phenolic resins are included in the toner, they have the following problems although they have negative triboelectric charging properties.

(1) Many of them have insufficient negative triboelectrification, so that they must be added in large amounts to the toner.

(2) The fixing properties of the toner are significantly changed depending on the amount of addition.

(3) Since the toner is decomposed and deteriorated during heating and kneading in the toner production process, the toner characteristics greatly depend on the production conditions.

(4) A toner produced by reusing dust powder produced during production is apt to fog.

The monomer serving as a raw material of the p-phenylcalix [n] arene compound of the present invention, for example, p-phenylphenol, has a low charge-imparting ability by itself. By forming the monomer into a cyclic oligomer, p-phenylcalix [n] arene, instead of a high-molecular-weight chain resin by reaction with formaldehyde, the monomer has high negative triboelectric chargeability and the above problem. Solve.

Since p-phenylcalix [n] arene is a cyclic oligomer having a unique structure, it has a high melting point,
There is a feature in the place where it is hard to change. For this reason, compared to polycondensates and phenolic resins, it does not affect the fixing properties of the toner and does not decompose or change during heating and kneading. An advantage is that fogging does not occur even in a toner manufactured by reuse.

Further, the p-phenylcalix [n] arene compounds of the present invention are characterized by having a phenyl group on the calix [n] arene. In the case of calix [n] arene and alkylcalix [n] arene, p-phenylcalix [n] arene has a high triboelectric charging ability, whereas triboelectricity is insufficient as a charge control agent. . This is considered to be due to the electron withdrawing property of the phenyl group. Furthermore, p-phenylcalix [n] arene having an electron-withdrawing group in the phenyl group tends to have a higher triboelectric charge.

The number of phenylphenols constituting the cyclic structure of the p-phenylcalix [n] arene is preferably from 4 to 8.

Also, because the dispersibility of the binder resin has been improved,
The frictional charging between the toner particles became uniform, the generation of the oppositely charged particles was suppressed, and no fogging occurred. Further, contamination of the toner carrier such as a sleeve and a carrier can be reduced, and an image of good image quality can be obtained even when the toner is stored for a long time under high temperature and high humidity. Further, the dependence of the image on the environment is reduced, and an image having a sufficient density can be obtained under high temperature and high humidity conditions or low temperature and low humidity conditions.

As described above, the p-phenylcarboxylic acid [n] of the present invention is used.
The present inventors have found that a toner containing an arene compound has superior properties as compared with a toner containing a conventional charge control agent, and have reached the present invention.

Further, the p-phenylcalix [n] arene compounds of the present invention have an absorption band in the range of 3150 to 3250 cm ^-1 due to stretching vibration of a hydroxyl group in an IR spectrum. The position of this absorption band indicates that the hydroxyl group forms a strong hydrogen bond. If the absorption band is higher than this, the charge amount tends to be low.

It is appropriate that the IR spectrum is measured by a KBr method using a measuring instrument using a Fourier transform method.

Further, the molecular weight of the p-phenylcalix [n] arene compounds of the present invention is not particularly limited, but is preferably in the range of 500 to 2,000.

In the present invention, the value of the molecular weight is suitably calculated from mass spectrometry, a method using a rise in boiling point, a method using a drop in freezing point, and further, a value measured by gel permeation chromatography.

The gel permeation chromatography was performed under the following conditions: tetrahydrofuran was flowed at a flow rate of 1 ml per minute as a solvent at a temperature of 40 ° C., and 0.5 ml of a tetrahydrofuran sample solution having a sample concentration of 8 mg / ml was injected. I do.
In order to accurately measure the molecular weight region of 10 ² to 10 ⁷ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, Shodex G manufactured by Showa Denko KK
Combination of PC KF-801, 802, 803, 804, 805, 806, P800 and ultra styradiel 500A-THF, 1
A combination of 0 ³ A-THF, 10 ⁴ A-THF, 10 ⁵ A-THF, 10 ⁶ A-THF, or a combination of A-Toluene series can be given. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, manufactured by Pressure Chemical Co., or
Tosoh Corporation has a molecular weight of 6 × 10 ² , 2.1 × 10 ³ , 4 × 1
0 ³ , 1.75 × 10 ³ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 ×
10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶
It is appropriate to use about a few standard polystyrene samples. As the detector, an RI (refractive index) detector or a UV (ultraviolet light) detector is used.

The p-phenylcalix [n] arene compounds of the present invention can be synthesized from the corresponding phenol compound and formaldehyde using a known method.

The p-phenylcalix [n] arene compounds of the present invention can be obtained by heating p-phenylphenols and formaldehyde or paraformaldehyde in an organic solvent to 50 to 200 ° C. using a strong base as a catalyst. Can be. Further, p-phenylphenol and p-formaldehyde obtained from paraformaldehyde according to the above synthesis method
It can also be obtained by introducing a substituent into the -phenylcalix [n] arene.

For example, in the case of p- (4-bromophenyl) calix [n] arene, bromophenylphenol and excess paraformaldehyde are mixed with xylene as a solvent and potassium hydroxide as a catalyst, and the mixture is mixed at 60 ° C. for 6 hours. It can be obtained by heating and stirring, and then heating and stirring at 140 ° C. for 10 hours.

Further, p-phenylphenol and formaldehyde are mixed in a xylene solvent, and potassium hydroxide is used as a catalyst.
The mixture was heated and stirred at 130 ° C. for 10 hours to obtain p-phenylcalix [n] arene, and then reacted with bromine in a tetrahydrofuran solvent to obtain p- (a) with another bromine-substituted product. 4-bromophenyl)
A calixus [n] arene can be obtained.

Further, as described in J. Org. Chem. 1982, 47 , 2708-2712, the p-phenyl phenol [n] arene compounds of the present invention are linear oligomers of p-phenyl phenols. It can also be obtained by synthesizing a compound and further subjecting it to condensed cyclization.

Specific examples of the p-phenylcalix [n] arene compounds that can be used in the present invention are shown below, but these are representative examples in consideration of ease of handling and the like, and do not limit the compounds of the present invention at all. is not.

(10) Compound obtained by reacting compound example (1) with bromine in a dark place.

(11) A compound obtained by reacting compound example (2) with actyl chloride, then with benzo chloride in the presence of aluminum chloride, and then washing with an aqueous solution of potassium hydroxide.

(12) Compound obtained by reacting compound example (1) with concentrated sulfuric acid, then reacting with concentrated nitric acid at a low temperature, and washing with alkaline water.

In the present invention, as a method for incorporating the p-phenylcalix [n] arene compound into the toner, there are a method of adding the compound to the inside of the toner and a method of externally adding the compound. The amounts of these compounds used are determined by the type of the binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and are not specifically limited. However, when internally added, it is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the binder resin. Or, if externally added, use resin
0.01 to 10 parts by weight per 100 parts by weight is preferred.

In the case of external addition, it is particularly preferable to fix or bury the particles near the surface of fine particles made of a binder resin and a colorant by mechanical impact. First, as a pretreatment, while dispersing the charge control agent particles (B), the particles are rubbed with the colored fine particles (A) and adhere to the colored fine particles by electrostatic force and Van der Waals force. Generally, a mixer with a high-speed stirring blade is used, but any mixer having a mixing function and a dispersing function may be used. Further, a pulverizer, a vibration mill or the like may be used with a reduced impact force. In order to make the pretreatment dispersion more uniform, a fluidity-imparting agent, a lubricant, a conductivity-imparting agent, and the like may be added as a dispersing aid, if necessary. For example, fine silica powder, polytetrafluoroethylene powder, polyvinylidene fluoride powder, metal salts of higher fatty acids, carbon black, conductive tin oxide and the like are used, and particularly preferably fine silica powder is used.

The effect is exhibited when the addition amount of the dispersing aid is 5 parts by weight or less, preferably 3 parts by weight or less based on 100 parts by weight of the particles (Y). The ratio of the particles (Y) to (Z) is 0.1 to 20 parts by weight based on 100 parts by weight of the particles (Y).
The pretreatment is preferably performed in the range of 0.5 to 15 parts by weight.

The mixture of the particles (Y) and (Z) obtained in this manner was mixed with the apparatus shown in FIG.
The toner was processed for 3 minutes at / sec, and the toner was observed with an electron microscope. As a result, it was observed that the toner was partially fixed. In addition, the sticking rate was determined to be 96% by the following method.
Met.

The ratio of the particles (Z) fixed to the particles (Y) was determined as follows.

First, the particles (Y), the mixture of the particles (Y) and (Z), and the processed product are each dispersed in the same amount of water containing a surfactant, and further dispersed in an ultrasonic disperser for 5 minutes. Then, suction filtration is immediately performed. At this time, the size of the opening of the filter is slightly larger than the diameter of the particles (Z). Next, the obtained filtrate is further ultrasonically dispersed, and the transmittance T% of the filtrate is measured using a spectrophotometer. At that time, the equipment is adjusted with the filtrate containing only the particles (Y) as 100%. The values measured as described above were determined by defining the sticking rate using the following formula.

Permeability of filtrate of treated product of particles (Y) and (Z) ... T _AB % Permeability of filtrate of mixture of particles (Y) and (Z) ... T _{A + B} % As conditions for the fixing and burying treatment, it is important to control the impact force in a range where the particles (Y) are not pulverized and the temperature control in a range where fusion and aggregation do not occur. As an example of a fixing device for carrying out the present method, a pin mill having a recycle function and having a large number of rotating pins, and applying an impact between a rotating blade or a hammer (rotating piece) and a liner (fixing piece), and A crusher having a recycling mechanism is effective.

The peripheral speed of the tip of the rotary piece in the device is preferably 30 to 150 m / sec. The temperature varies depending on the physical properties of the particles (Y) and the particles (Z), but is preferably 20 to 90 ° C, preferably 30 to 70 ° C, and the residence time of the impact portion is preferably 0.2 to 12 seconds. In the case of a pin mill, it is necessary to increase the powder concentration. In the apparatus of the type shown in FIG. 1, since the powder to be processed by the centrifugal force is collected near the liner 7, the latitude of the powder concentration is wide. The shortest gap between the pin mills or between the blade 4 or the hammer and the liner is preferably about 0.5 to 5 mm, and more preferably 1 to 3 mm gives good results.

Further, the p-phenylcalix [n] arene compounds of the present invention can be used in combination with a conventionally known charge control agent.

In the toner of the present invention, a silica fine powder can be externally added to the toner. As the silica fine powder, silica fine powder produced by a dry method and a wet method can be used.

The dry method referred to here is a method for producing silica fine powder generated by vapor phase oxidation of a silicon halide. For example, in a method utilizing the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen-hydrogen, the basic reaction formula is as follows.

SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl Also, in this production process, for example, by using another metal halide such as aluminum chloride or titanium chloride together with a silicon halide, a fine composite powder of silica and another metal oxide is obtained. It is also possible to obtain and include them.

On the other hand, as a method for producing the silica fine powder used in the present invention by a wet method, various conventionally known methods can be applied. For example, decomposition of sodium silicon with an acid, if represented by a general reaction formula (hereinafter, the reaction formula is abbreviated), Na ₂ O · XSiO ₂ + HCl + H ₂ O → SiO ₂ · nH ₂ O + NaCl, and other ammonium salts or alkali salts of sodium silicate , An alkaline earth metal silicate is produced from sodium silicate, then decomposed with acid to form silicic acid, a sodium silicate solution is converted to silicic acid with ion exchange resin, natural silicic acid or silicic acid There is a method using an acid salt.

Silica such as aluminum silicate, sodium silicate, potassium silicate, magnesium silicate, zinc citrate, etc. can be applied to the silica fine powder here.

Among the above-mentioned silica fine powders, those having a specific surface area of 30 m ² / g or more (particularly 50 to 400 m ² / g) by nitrogen adsorption measured by the BET method are preferable.

Further, the silica fine powder used in the present invention may be treated with a silane coupling agent, if necessary, with a treating agent such as an organosilicon compound for the purpose of hydrophobization, and a known method is also used. Then, it is treated with the treating agent which reacts or physically adsorbs with the silica fine powder. Such treating agents include, for example, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchloro Silane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3
Diphenyltetramethyldisiloxane, and dimethylpolysiloxane having from 2 to 12 siloxane units per molecule and having terminal hydroxyl units each containing one hydroxyl group bonded to Si. These are one or two
Used in mixtures of more than one species.

Finally, the degree of hydrophobicity of the treated silica fine powder was determined as a degree of hydrophobicity measured by a methanol titration test, 30
It is preferred that the developer containing such silica fine powder exhibits a triboelectric charge amount which is sharp and uniform and exhibits a negative chargeability when hydrophobicized so as to show a value within the range of -80. Here, in the methanol titration test, the degree of hydrophobicity of the silica fine powder having a hydrophobicized surface is confirmed.

The "methanol titration test" defined herein for evaluating the degree of hydrophobicity of the treated silica fine powder is performed as follows. 0.2 g of the test silica fine powder is added to 50 ml of water in a 250 ml Erlenmeyer flask. Methanol is titrated from the vial until all of the silica has been wetted.
At this time, the solution in the flask is constantly stirred with a magnetic stirrer. The end point is observed as the entire amount of fine silica powder is suspended in the liquid, and the degree of hydrophobicity is expressed as the percentage of methanol in the liquid mixture of methanol and water when the end point is reached.

Examples of the coloring agent used in the present invention include carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6G, coco oil blue, chrome yellow, quinacridone, Conventionally known dyes and pigments such as benzidine yellow, rose bengal, triarylmethane dyes, monoazo and disazo dyes can be used alone or in combination.

The resin used in the present invention includes, for example, styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyl toluene, and a homopolymer of a substituted product thereof;
p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrenacrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer Copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene- Styrene copolymers such as acrylonitrile-indene copolymer; polyvinyl chloride, phenolic resin, naturally modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyester resin Urethane, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, Kumaroinden resins, and petroleum resins.

Further, a crosslinked styrene copolymer is also a preferable binder resin.

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, and methacrylic acid. Monocarboxylic acid having a double bond such as acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide or a substituted product thereof; for example, maleic acid, butyl maleate Dicarboxylic acids having a double bond, such as methyl, methyl maleate, dimethyl maleate, and the like; and vinyl chloride, vinyl acetate,
Vinyl esters such as vinyl benzoate; ethylene-based olefins such as ethylene, propylene, butylene; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; vinyl methyl ether, vinyl ethyl ether; Vinyl monomers such as vinyl isobutyl ether and the like; vinyl monomers such as alone or two or more are used.

Here, as the cross-linking agent, a compound having two or more polymerizable double bonds is mainly used, and examples thereof include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; for example, ethylene glycol diacrylate and ethylene glycol diacrylate. Carboxylic acid esters having two double bonds such as methacrylate and 1,3-butanediol dimethacrylate; divinyl compounds such as divinylaniline, divinylether, divinylsulfide and divinylsulfone; and three or more vinyl groups Is used alone or as a mixture.

When a pressure fixing method is used, a binder resin for a pressure fixing toner can be used. For example, polyethylene, polypropylene, polymethylene, polyurethane elastomer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer can be used. Coalescent, ionomer resin, styrene-butadiene copolymer, styrene-isoprene copolymer, linear saturated polyester, paraffin and the like.

Further, the toner for electrostatic charge development of the present invention may contain a magnetic material and be used as a magnetic toner. Examples of the magnetic material used include iron oxides such as magnetite, γ-iron monoxide, ferrite, and iron-rich ferrite; metals such as iron, cobalt, and nickel; or these metals and aluminum, cobalt, copper, lead, magnesium, and tin. And alloys with metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof. These magnetic materials preferably have an average particle size of 0.1 to 1 μm, preferably about 0.1 to 0.5 μm, and the amount contained in the magnetic toner is 40 to 150 parts by weight per 100 parts by weight of the binder resin component. Preferably it is 60 to 120 parts by weight.

In the magnetic toner using the charge control agent of the present invention,
A toner having a volume average particle diameter of 3 to 15 μm can be used;
In particular, 12 to 60 magnetic toner particles having a particle size of 5 μm or less
1 to 33% by number of magnetic toner particles having a particle size of 8 to 12.7 μm, 2.0% by volume or less of magnetic toner particles having a particle size of 16 μm or more, and a volume average particle size of the magnetic toner. The diameter is more preferably 4 to 10 μm from the viewpoint of developing characteristics.

Magnetic toner particles having a particle size of 5 μm or less have a total particle number of 12 to
It is preferably 60% by number, more preferably 25 to 50% by number, and even more preferably 30 to 50% by number. When the number of magnetic toner particles having a particle size of 5 μm or less is less than 12% by number, the amount of magnetic toner particles effective for high image quality is small. In particular, as the toner is used by continuing copying or printing out, the effective magnetic toner particles are effective. Ingredients decrease,
As shown in the present invention, the balance of the particle size distribution of the magnetic toner deteriorates, and the image quality gradually decreases. On the other hand, if it exceeds 60% by number, the magnetic toner particles tend to aggregate with each other, resulting in a toner mass larger than the original particle size, resulting in rough image quality, reduced resolution, or a latent image. The density difference between the edge portion and the inside becomes large, and the image tends to be slightly hollow.

The particle size in the range of 8 to 12.7 μm is preferably 1 to 33% by number, and more preferably 8 to 20% by number. If the content is more than 33% by number, the image quality is deteriorated and the development is performed more than necessary, that is, the toner is excessively applied, which leads to an increase in toner consumption. On the other hand, if it is less than 1% by number, it becomes difficult to obtain a high image density. Further, there is a relationship of N / V = -0.04N + k between the number% (N%) and the volume% (V%) of the magnetic toner particle group having a particle diameter of 5 μm or less, and 4.5 ≦ k ≦ 6.5.
Indicates a positive number in the range. Preferably, 4.5 ≦ k ≦ 6.0, more preferably 4.5 ≦ k ≦ 5.5. As shown above, 12 ≦
N ≦ 60, preferably 25 ≦ N ≦ 50, more preferably 30 ≦
N ≦ 50.

When k <4.5, the number of magnetic toner particles having a particle diameter smaller than 5.0 μm is small, and the image density, resolution, and sharpness are poor. The appropriate presence of fine magnetic toner particles, which has conventionally been considered unnecessary, contributes to the closest packing of the toner in development and contributes to the formation of a uniform image without roughness. In particular, by uniformly filling the fine lines and the contours of the image, the sharpness is further enhanced visually.
That is, when k <4.5, these properties are inferior due to the lack of the particle size distribution component.

From another aspect, in production, it is necessary to cut a large amount of fine powder by classification or the like to satisfy the condition of k <4.5, which is disadvantageous in terms of yield and toner cost.
When k> 6.5, the presence of more fine powder than necessary
During repeated copying, the balance of the particle size distribution may be lost, the degree of aggregation of the toner may be increased, or frictional charging may not be performed effectively, resulting in poor cleaning or fogging.

The content of the magnetic toner particles having a particle diameter of 16 μm or more is preferably 2.0% by volume or less, more preferably 1.0% by volume.
Or less, more preferably 0.5% by volume or less.
When the content is more than 2.0% by volume, not only does it hinder the reproduction of fine lines, but also in the transfer, coarse toner particles of 16 μm or more protrude from the thin layer surface of the toner particles developed on the photoreceptor. The delicate state of contact between the photoreceptor and the transfer paper via the layer is made irregular, causing fluctuations in the transfer conditions and causing poor transfer images.

Further, the charge control agent of the present invention cannot sufficiently control the charge of the magnetic toner particles having a size of 16 μm or more, resulting in poor charging and fogging of the background portion and the reversal portion.

A magnetic toner having a volume average diameter of 3 to 15 μm can be preferably used. More preferably, it is 4 to 10 μm, and this value cannot be considered separately from the above-mentioned components. If the volume average particle size is less than 4 μm,
For applications with a high image area ratio, such as graphic images,
The problem that the amount of applied toner on the transfer paper is small and the image density is low tends to occur. This is considered to be due to the same reason as described above in which the density inside the edge portion in the latent image decreases. If the volume average particle size is larger than 15 μm, the resolution is not good, and if the use is continued at the beginning of copying, the image quality is likely to deteriorate.

The particle size distribution of the toner can be measured by various methods, but in the present invention, it is appropriate to use a Coulter counter.

In other words, the Coulter Counter TA is used as a measuring device.
-Using type II (manufactured by Coulter) and connecting an interface (manufactured by Nikkaki) and a CX-1 personal computer (manufactured by Canon) that output the number distribution and volume distribution,
Prepare an approximately 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter Science Japan) can be used. As a measuring method, a surfactant as a dispersant in the aqueous electrolytic solution 100 to 150 ml,
Preferably, 0.1 to 5 ml of an alkylbenzene sulfonate is added, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and the Coulter Counter TA-II was used, and a 100 μm aperture was used as an aperture, and particles having a particle size of 2 to 40 μm were used. Measure and convert the particle size distribution of
Obtain the particle size distribution of the toner.

Further, the toner of the present invention can be used as a two-component toner by mixing with a carrier. As the carrier that can be used in the present invention, known carriers can be used, for example, iron powder, ferrite powder, magnetic powder such as nickel powder, glass beads, and the like, and the surface thereof is treated with a resin or the like. What is done is raised. Examples of the resin for coating the carrier surface include styrene-acrylate copolymer, styrene-methacrylate copolymer, acrylate copolymer, methacrylate copolymer, silicone resin, and fluorine-containing resin. , A polyamide resin, an ionomer resin, a polyphenylene sulfide resin, or a mixture thereof.

The toner of the present invention may optionally contain additives. Examples of the additive include a lubricant such as zinc stearate; an abrasive such as cerium oxide and silicon carbide; a fluidity imparting agent such as aluminum oxide; an anti-caking agent; and a carbon black and tin oxide. There is a conductivity imparting agent.

Further, a fluorine-containing polymer fine powder such as a polyvinylidene fluoride fine powder is also a preferable additive from the viewpoint of fluidity, abrasiveness, charge stability and the like.

In addition, wax-like substances such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, microcrystalline wax, carnauba wax, sasol wax, and paraffin wax are used for the purpose of improving the releasability at the time of hot roll fixing.
Addition of about 5% by weight to the toner is also a preferred embodiment of the present invention.

In producing the toner according to the present invention, the above-mentioned toner constituent materials are sufficiently mixed with a ball mill or other mixer, then kneaded well using a hot kneader of a hot roll kneader or an extruder, and cooled and solidified. Preferred is a method of obtaining a toner by mechanical pulverization and classification. Another method is to obtain a toner by dispersing the constituent materials in a binder resin solution and then spray-drying; or, in a so-called microcapsule toner composed of a core material and a shell material, a core material or a shell material, A method of including a predetermined material in both of them can be applied.

Further, a polymerization toner production method in which a predetermined material is mixed with a monomer to form a binder resin to form an emulsified suspension and then polymerized to obtain a toner can be applied.

The polymerized toner used in the present invention is obtained by the following method. That is, in the polymerizable monomer was added a wax, a colorant, a polymerization initiator and other additives, an ultrasonic disperser,
The monomer system uniformly dissolved or dispersed by a homogenizer or the like is dispersed in an aqueous phase (that is, a continuous phase) containing a suspension stabilizer by an ordinary stirrer, a homomixer, a homogenizer, or the like. Preferably, the stirring speed and time are adjusted so that the monomer droplets have the desired size of the toner particles, generally 30 μm or less, and then the dispersion is stabilized by the action of the dispersion stabilizer. The bond may be made to the extent that settling of the particles is prevented. The polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. After completion of the reaction, the produced toner particles are washed, collected by filtration and dried. In the suspension polymerization method, it is generally preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of a monomer.

Examples of the polymerizable monomer applicable to the toner of the present invention include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-methylstyrene.
Styrene such as ethylstyrene and derivatives thereof; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Methacrylates such as stearyl, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate Acrylates such as, decyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; acrylonitrile, methacrylonitrile Le, and vinyl monomers such as acrylic acid or methacrylic acid derivatives such as acrylamide.

These monomers can be used alone or as a mixture.
Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or as a mixture with other monomers as a polymerizable monomer from the viewpoint of the developing characteristics and durability of the toner.

It is more preferable to add a polymer or a copolymer having a polar group as an additive during the polymerization of the monomer to polymerize the monomer. In the present invention, a polymer having a polar group at the time of polymerization, a polymerizable monomer system to which a copolymerized or cyclic rubber is added is suspended in an aqueous phase in which the polar polymer and a dispersant having an opposite charge are dispersed. It is preferable to conduct turbidity and polymerize. That is, the cationic or anionic polymer contained in the polymerizable monomer system, the copolymerized or cyclic rubber is undergoing polymerization with a reverse-charged anionic or cationic dispersant dispersed in the aqueous phase. Electrostatically meet on the particle surface of the toner, and the dispersant covers the particle surface to prevent coalescence of the particles and stabilize, and the polar polymer added during polymerization gathers on the surface layer of the toner particle Therefore, it becomes a kind of shell-like form, and the obtained particles become pseudo capsules. A relatively high molecular weight polar polymer, copolymer or cyclized rubber is used to impart excellent blocking and developing abrasion resistance to the toner particles, while improving the fixing properties with a relatively low molecular weight inside. By carrying out polymerization so as to contribute, it is possible to obtain a toner which satisfies conflicting requirements of fixing property and blocking property. The polar polymer (including the polar copolymer) and the reverse charge dispersant which can be used in the present invention are exemplified below.

(I) Examples of the cationic polymer include polymerization of a nitrogen-containing monomer such as dimethylaminoethyl methacrylate and diethylaminoethyl acrylate or a copolymer of styrene, an unsaturated carboxylic acid ester and the like with the nitrogen-containing monomer. .

(Ii) Examples of the anionic polymer include nitrile monomers such as acrylonitrile, halogen-containing monomers such as vinyl chloride, unsaturated carboxylic acids such as acrylic acid, unsaturated dibasic acids, and unsaturated dibasic acids. There are polymers of anhydrides and nitro monomers. A cyclized rubber may be used instead of the polar polymer.

(Iii) Aerosil # 200,
There are colloidal silicas such as # 300 and # 380 (manufactured by Nippon Aerosil Co., Ltd.).

(Iv) Examples of the cationic dispersant include fine particles of hydrophilic positively chargeable silica such as aluminum oxide and aminoalkyl-modified colloidal silica.

Such a dispersant is based on 100 parts by weight of the polymerizable monomer.
0.2 to 20 parts by weight is preferred. More preferably, it is 0.3 to 15 parts by weight.

As the polymerization initiator, any suitable polymerization initiator, for example, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'- Azobis (cyclohexane-1-carbonitrile), 2,
2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, other azobisisobutyronitrile (AIBN)
Azo-based or diazo-based polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorylbenzoyl peroxide, and lauroyl peroxide. Initiators. Generally, about 0.5 to 10% of these polymerization initiators by weight of the polymerizable monomer is sufficient.

Further, a fluidity modifier may be mixed (externally added) with small toner particles and used. Colloidal silica as a fluidity modifier,
Examples include fatty acid metal salts and fine powder of Teflon. In addition, fillers such as calcium carbonate and finely powdered silica are used in an amount of 0.
It may be blended in the toner in the range of 5 to 20% by weight.

Further, if necessary, desired additives are sufficiently mixed by a mixer such as a Hensiel mixer, and the toner according to the present invention can be manufactured.

The toner of the present invention can be used for development for suspending an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like by a conventionally known means.

The p-phenylcalix [n] arene compounds of the present invention are colorless or pale and have good triboelectric charging properties.

Therefore, the toner of the present invention hardly causes image quality deterioration due to continuous copying and can provide an image having excellent density uniformity.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. All parts in the following formulations are parts by weight.

Example 1 After the above materials were mixed well in a blender, they were kneaded with a biaxial kneading extruder set at 150 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, and then finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified by a fixed wall type air classifier.

Further, the obtained classified powder was strictly classified and removed simultaneously by a multi-segment classifier using a Coanda effect (an elbow jet classifier manufactured by Nippon Steel Mining Co., Ltd.) to obtain a volume average particle size of 8.3 μm.
m was obtained. What was classified and removed in this process is referred to as fine powder A.

Silica fine powder (BET specific surface area: 300 m ² / g) obtained by hydrophobizing 100 parts of the obtained fine powder A with hexamethyldisilazane
0.6 part was added and mixed with a Hensiel mixer to obtain a toner to which silica fine powder was externally added.

Next, 5 parts of the obtained toner were mixed with 100 parts of an acrylic-coated ferrite carrier having an average particle diameter of 65 μm to prepare a developer.

This developer was subjected to a copy test using a commercially available color electrophotographic copying machine CLC-1 (manufactured by Canon Inc.).

As a result, under an environmental condition of 23 ° C./60%, a bright black image having an image density of 1.46 was obtained from the beginning, and no deterioration was observed after copying 10,000 sheets.

Next, when a copy test was performed under an environment condition of 15 ° C./10%, an image with a high density of 1.41 was obtained from the beginning. In addition, 32
A good image with a density of 1.50 was obtained even under the environmental conditions of ° C / 85%.

Example 2 A fine powder having a volume average particle diameter of 8.2 μm was obtained in the same manner as in Example 1 except that 5 parts of the carbon black in Example 1 was changed to 4 parts of a copper phthalocyanine pigment (CI Pigment Blue 15), and silica was further mixed. To obtain a toner.

Next, the same carrier as in Example 1 was mixed at the same ratio to obtain a developer.

This developer was subjected to a copy test in the same manner as in Example 1. As a result, under the environmental conditions of 23 ° C / 60%,
An excellent fog-free blue image having a density of 1.42 was obtained. 1
No deterioration in image quality was observed even after copying 10,000 sheets.

A copy test was performed under environmental conditions of 35 ° C./85% and 15 ° C./10%, and good results were obtained as in the case of 23 ° C./60%.

Example 3 A fine powder having a volume average particle size of 8.4 μm was obtained in the same manner as in Example 1 except that 5 parts of the carbon black in Example 1 was changed to 4 parts of a quinacridone-diameter pigment (CI pigment red 122). Thus, a toner was obtained.

Next, the same carrier as in Example 1 was mixed at the same ratio to obtain a developer.

This developer was subjected to a copy test in the same manner as in Example 1. As a result, under the environmental conditions of 23 ° C / 60%,
A good magenta image with a fog density of 1.41 was obtained. No deterioration in image quality was observed even after copying 10,000 sheets.

A copy test was performed under environmental conditions of 35 ° C./85% and 15 ° C./10%, and good results were obtained as in the case of 23 ° C./60%.

Example 4 A fine powder having a volume average particle size of 8.4 μm was obtained in the same manner as in Example 1, except that 5 parts of the carbon black in Example 1 was changed to 5 parts of a yellow pigment (CI Pigment Yellow 17). A toner was obtained.

Next, the same carrier as in Example 1 was mixed at a ratio of 6 parts of the toner to 100 parts of the carrier to obtain a developer.

This developer was subjected to a copy test in the same manner as in Example 1. As a result, under the environmental conditions of 23 ° C / 60%,
A good yellow image without fog having a density of 1.45 was obtained. 1
No deterioration in image quality was observed even after copying 10,000 sheets.

A copy test was performed under environmental conditions of 35 ° C./85% and 15 ° C./10%, and good results were obtained as in the case of 23 ° C./60%.

Example 5 Black, cyan, magenta, and black used in Examples 1 to 4
Where a full-color image was obtained using a yellow developer,
A vivid full-color image with excellent color mixing and gradation was obtained.

Comparative Example 1 2 parts of the compound example (1) in Example 1 was replaced with pt-butylcalix [6] arene (manufactured by Tokyo Chemical Industry Co., Ltd.) 3
In the same manner as in Example 1, except that the parts were changed, fine powder having a volume average particle diameter of 8.6 μm was obtained, and the same silica was mixed at the same ratio to obtain a toner. This toner was applied to a commercially available color electrophotographic copying machine CLC-1 (manufactured by Canon Inc.) in the same manner as in Example 1, and a copy test was conducted under an environmental condition of 23 ° C./60%. An image was obtained. However, when a continuous copy test was performed to check the durability performance,
With 2000 sheets, the image density dropped to 1.23, and fog occurred,
The quality was problematic in practice.

Comparative Example 2 2 parts of the compound example (1) in Example 1 was replaced with 3 parts of 5,11-diphenyl-17,23-di-t-butyl-25,26,27,28-tetrahydroxycalix [4] arene. Except for the change, the volume average particle diameter was 8.5 μm in the same manner as in Example 1.
Was obtained, and the same silica was mixed at the same ratio to obtain a toner. This toner was applied to a commercially available color electrophotographic copying machine CLC-1 (manufactured by Canon Inc.) in the same manner as in Example 1, and a copy test was conducted under an environmental condition of 23 ° C./60%. An image was obtained. However, when a continuous copying test was performed to check the durability performance, the image density was 1.000 on 5000 sheets.
It has dropped to 28.

Example 6 The above material was prepared in the same manner as in Example 1 and had a volume average particle size of 8.5 μm.
m, and the same silica was mixed in the same amount to obtain a toner.

Next, similarly, 100 parts of an acrylic coated ferrite carrier having an average particle size of 65 μm was mixed with 5 parts of the obtained toner to prepare a developer, and the same evaluation as in Example 1 was performed.

As a result, a clear and high-density image was obtained from the beginning under each environmental condition, and an image of good image quality was obtained even in a 10,000-sheet copy test.

Comparative Example 3 An oil-soluble p-phenylphenol resin (manufactured by Gunei Chemical Industry Co., Ltd., pp-81)
1) A fine powder having a volume average particle diameter of 8.3 μm was obtained in the same manner as in Example 1 except that the amount was changed to 7 parts, and the same silica was mixed at the same ratio to obtain a toner. What was classified and removed in this process is referred to as fine powder B.

Next, this fine powder powder B was reused as a toner raw material in the same manner as in Example 6, and the compound example (1) 2 in Example 6 was used.
Parts and fine powder A20 parts were changed to oil-soluble p-phenylphenol resin 7 parts and fine powder B20 parts in the same manner as in Example 6 to obtain a fine powder having a volume average particle size of 8.7 μm. The mixture was mixed to obtain a toner.

Next, 5 parts of the obtained toner were mixed with 100 parts of an acrylic-coated ferrite carrier having an average particle diameter of 65 μm to prepare a developer, and the same evaluation as in Example 1 was performed.

As a result, under an environmental condition of 23 ° C./60%, an image having a sufficient image density of 1.40 was initially obtained, but as the copying test was continued, the image became fogged.
After 5,000 copies, the fog became severe and had a quality that would pose a practical problem.

Example 7 After well mixing the above materials with a blender,
And kneaded with a twin-screw kneading extruder. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, and then finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified by a fixed wall type air classifier.

Further, the obtained classified powder was strictly classified and removed simultaneously with a multi-segment classification device (Elbojet classifier manufactured by Nittetsu Mining Co., Ltd.) utilizing the Coanda effect, and the volume average particle diameter was 8.1 μm.
m was obtained.

Silica fine powder (BET specific surface area: 300 m ² / g) obtained by hydrophobizing 100 parts of the obtained fine powder with hexamethyldisilazane
0.7 part was added and mixed with a Hensiel mixer to obtain a toner.

Next, 5 parts of the obtained toner was mixed with 100 parts of a styrene-acryl-coated ferrite carrier having an average particle diameter of 65 μm to prepare a developer.

This developer was subjected to a copy test using a commercially available color electrophotographic copying machine CLC-1 (manufactured by Canon Inc.).

As a result, a clear black image having an image density of 1.43 was obtained from the beginning under an environmental condition of 23 ° C./60%, and an image of good image quality was obtained even after copying 10,000 sheets.

Next, when a copy test was performed under an environment condition of 15 ° C./10%, an image with a high density of 1.41 was obtained from the beginning. In addition, 32
Even under an environmental condition of ° C / 85%, an image of good quality was obtained without fog at a density of 1.47.

Example 8 After the above materials were mixed well in a blender, they were kneaded with a twin screw extruder set at 140 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, and then finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified by a fixed wall type air classifier.

Further, the obtained classified powder is strictly classified and removed simultaneously by a multi-division classifier using a Coanda effect (an elbow jet classifier manufactured by Nippon Steel Mining Co., Ltd.), and the volume average particle size is 8.5 μm.
m was obtained. The particle size distribution of this fine powder is shown in Table 1.

Silica fine powder (BET specific surface area: 300 m ² / g) obtained by hydrophobizing 100 parts of the obtained fine powder with hexamesyldisilazane
0.6 part was added and mixed with a Hensiel mixer to obtain a magnetic toner.

When this toner was applied to a commercially available copying machine (trade name: NP-6650, manufactured by Canon Inc.) and subjected to a copying test at 23 ° C./60% environmental conditions, the image density was 1.36, and there was no fog or dust. A clear image having a resolution of 6.3 lines / mm was obtained. Further, when the durability performance was examined by continuously copying 30,000 sheets, a good image comparable to the initial image was obtained with an image density of 1.33 and a resolution of 6.3 lines / mm. Further, when the triboelectric charge amount of the toner on the developing sleeve was measured, it was -11.3 μc / g at the initial stage, and -10.3 μc / g after 30,000 copies, and almost no sleeve contamination was observed. Then 15 ℃ / 10
%, A high-density image of good image quality was obtained. The results were similarly good in the 30,000-sheet continuous copying test. When the same copy test and continuous copy test were performed under the environmental conditions of 35 ° C./85%, good results were obtained. Further, after the toner was allowed to stand for one month under these environmental conditions, the same copying test and continuous copying test were performed. The results were satisfactory without any problem.

Comparative Example 4 The classified powder obtained in Example 8 was similarly classified to obtain a fine powder having a volume average particle size of 7.7 μm and 63% by number of particles of 5 μm or less.

This fine powder was mixed with silica in the same manner as in Example 8 to obtain a magnetic toner, and the toner was evaluated in the same manner as in Example 8.

When a copy test was performed under an environment condition of 23 ° C./60%, an image having a sufficient density of 1.32 was obtained, but roughness occurred in the image halftone portion. As the number of copies increased, the degree of roughness increased.

Comparative Example 5 The classified powder obtained in Example 8 was similarly classified to obtain a fine powder having a volume average particle size of 8.8 μm and particles having a size of 16 μm or more being 4.0% by volume.

This fine powder was mixed with silica in the same manner as in Example 8 to obtain a magnetic toner, and the toner was evaluated in the same manner as in Example 8.

When a copy test was conducted under an environment condition of 23 ° C./60%, an image having a sufficient density of 1.32 was obtained, but fogging occurred in the image reversal portion.

In a copy test under an environmental condition of 35 ° C./85%, the fogging of the image reversal portion was severe, and had a quality that was problematic in practical use.

Example 9 A fine powder having a volume average particle size of 8.7 μm was obtained in the same manner as in Example 8, except that 2 parts of Compound Example (4) in Example 8 was changed to 3 parts of Compound Example (3).

Silica fine powder (BET specific surface area: 200 m ² / g) treated with hydrophobic treatment with dimethyldichlorosilane was added to 100 parts of this fine powder.
6 parts were added and mixed with a Hensiel mixer to obtain a magnetic toner.

When this toner was applied to a commercial copying machine (trade name: NP-6650, manufactured by Canon Inc.) and subjected to a copying test under an environment of 23 ° C./60%, the image density was as high as 1.33 and the resolution was high. 6.3 /
A clear image with no fog or roughness was obtained. Then, 30,000 copies were continuously copied and the durability performance was examined. As a result, a good image comparable to the initial image was obtained. Also, when the amount of triboelectric charge of the toner on the developing sleeve was measured, the initial value was -10.8 μc / g, and after copying 30,000 sheets,
At -10.1 μc / g, almost no sleeve contamination was observed. Next, when a copy test was conducted under an environmental condition of 15 ° C./10%, an image of high density and good image quality was obtained.
The results were similarly good in the 30,000-sheet continuous copying test.

When the same copy test and continuous copy test were performed under an environmental condition of 35 ° C./85%, good results were obtained. Further, after the toner was allowed to stand for one month under these environmental conditions, the same copying test and continuous copying test were carried out. The results were satisfactory without any problem.

Example 10 After the above materials were mixed well in a blender, they were kneaded with a twin screw extruder set at 140 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, and then finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified by a fixed wall type air classifier.

Furthermore, the obtained fine powder was strictly classified and removed simultaneously by a multi-division classifier utilizing a Coanda effect (an elbow jet classifier manufactured by Nippon Mining Co., Ltd.) to obtain a volume average particle diameter of 10.9 μm.
m was obtained.

Silica fine powder (BET ground surface area: 200 m ² / g) obtained by hydrophobizing 100 parts of the obtained fine powder with dimethyldichlorosilane.
Five parts were added and mixed with a Hensiel mixer to obtain a toner.

Next, 10 parts of the obtained toner were mixed with 100 parts of an acrylic-coated ferrite carrier having an average particle diameter of 65 μm to prepare a developer.

When this developer was applied to a commercial copying machine (trade name: NP-6650, manufactured by Canon Inc.) and subjected to a copying test at 23 ° C./60% environmental conditions, an image with good image quality of 1.29 was obtained. Was done.
Using the above-mentioned developer, continuous printing was performed for 4,000 sheets, and the durability performance was examined. As a result, a good image comparable to the initial image was obtained.

Next, a copy test was performed under environmental conditions of 15 ° C./10% and 35 ° C./83%, and similarly good results were obtained.

Example 11 After the above materials were mixed well in a blender, they were kneaded with a biaxial kneading extruder set at 150 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, and then finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified by a fixed wall type air classifier.

Furthermore, the obtained fine powder was strictly classified and removed simultaneously by a multi-division classifier using a Coanda effect (Nippon Mining Co., Ltd. Elbow Jet Classifier), and the volume average particle size was 8.7μ.
m was obtained.

Silica fine powder (BET specific surface area: 300 m ² / g) obtained by hydrophobizing 100 parts of the obtained fine powder with hexamethyldisilazane.
6 parts were added and mixed with a Hensiel mixer to obtain a toner.

Next, 6 parts of the obtained toner were mixed with 100 parts of an acrylic-coated ferrite carrier having an average particle size of 65 μm to prepare a developer.

This developer was subjected to a copy test using a commercially available color electrophotographic copying machine CLC-1 (manufactured by Canon Inc.).

As a result, under an environmental condition of 23 ° C./60%, a bright black image with an image density of 1.42 was obtained from the beginning, and no deterioration was observed after 10,000 copies.

Next, when a copy test was performed under an environmental condition of 15 ° C./10%, an image with a high density of 1.35 was obtained from the beginning. In addition, 32
A good image with a density of 1.44 was obtained even under the environmental conditions of ° C / 85%.

Example 12 After the above materials were mixed well in a blender, they were kneaded with a biaxial kneading extruder set at 150 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, and then finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified by a fixed wall type air classifier.

Further, the obtained classified powder was strictly classified and removed simultaneously by a multi-division classifier using a Coanda effect (an elbow jet classifier manufactured by Nippon Steel Mining Co., Ltd.), and the volume average particle diameter was 9.1 μm.
m was obtained.

To 100 parts of this fine powder, 1.0 part of Compound Example (6) and 0.3 part of silica fine powder were mixed with a Hensiel mixer to perform pretreatment.

Next, processing was performed using the apparatus shown in FIG. 1 under the conditions of a minimum gap of 1 mm, a peripheral speed of the blade of 60 m / sec, and a processing time of 5 minutes. When the processed product was observed with an electron microscope, it was observed that the processed product was partially fixed and embedded on the toner surface. The fixation ratio was measured to be 94%. This processed material 10
0.5 parts of silica fine powder (BET specific surface area: 300 m ^{2 /} g) hydrophobized with hexamethyldisilazane was added to 0 parts to obtain a toner.

This toner was applied to a commercially available copying machine (trade name: NP-6650, manufactured by Canon Inc.) and subjected to a copying test at 23 ° C./60% under environmental conditions. As a result, the image density was 1.32 and the resolution was 6.3 lines / A clear image with no fog or roughness was obtained. In addition, 2
When the durability performance was examined after continuous copying of 10,000 sheets, the image density was 1.
31 and a good image comparable to the initial image were obtained.

Next, when a copy test was conducted under an environmental condition of 15 ° C./10%, an image of high density and good image quality was obtained. 2
The results were similarly good in the continuous copying test of 10,000 copies.

Further, when the same copy test and continuous copy test were performed under the environmental conditions of 35 ° C./85%, good results were obtained.

Example 13 0.5 g of γ-aminopropyltrimethoxysilane was added to 1200 ml of ion-exchanged water, and 10 g of Aerosil 200 (Nippon Aerosil) was further added. The mixture was heated to 70 ° C., and a TK homomixer M type (manufactured by Tokushu Kika Kogyo Co., Ltd.) ) And dispersed at 10,000 rpm for 15 minutes. Further, 19 g of N / 10HC was added to adjust the pH in the system to 6.

The components of the above formulation were heated to 70 ° C. in a container, and dissolved and dispersed at 10,000 rpm for 5 minutes using a TK homomixer M type to obtain a monomer mixture. While maintaining the temperature at 70 ° C., 10 parts of an initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added and dissolved to prepare a monomer composition.

Into a 2 liter flask containing the dispersion medium obtained above, the monomer composition was charged, and the mixture was stirred at 10,000 rpm for 60 minutes using a TK homomixer at 70 ° C. under a nitrogen atmosphere. The product was granulated. Then, while stirring with a paddle stirring blade, 70
Polymerization was performed at 10 ° C. for 10 hours. After the completion of the polymerization reaction, the reaction product was cooled, NaOH was added to dissolve the dispersant, and the mixture was filtered, washed with water, and dried to obtain a polymerized toner.

When the particle size of the obtained toner was measured by a Coulter counter (aperture system: 100 μm), the volume average diameter was 8.9.
It had a sharp particle size distribution at μm.

When this toner was applied to a commercial copying machine (trade name: NP-6650, manufactured by Canon Inc.) and subjected to a copying test at 23 ° C./60% environmental conditions, the image density was 1.35, and there was no fog or dust. A clear image was obtained. Furthermore, when the durability performance was examined by continuously copying 5,000 sheets, an image density of 1.34 and a good image comparable to the initial image were obtained.

Next, when a copy test was performed under environmental conditions of 15 ° C./10% and 35 ° C./85%, a high-density and good-quality image was similarly obtained. The results were similarly good in the 5,000-sheet continuous copy test.

Example 14 After the above materials were mixed well in a blender, they were kneaded with a twin screw extruder set at 140 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, and then finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified by a fixed wall type air classifier.

Further, the obtained classified powder is strictly classified and removed simultaneously with a multi-division classifier using a Coanda effect (an elbow jet classifier manufactured by Nippon Mining Co., Ltd.), and the volume average particle size is 12.3 μm.
m was obtained.

Silica fine powder (BET specific surface area 200 m ² /
g) 0.4 part was added and mixed with a Hensiel mixer to obtain a magnetic toner.

This toner was applied to a commercial copying machine (trade name: NP-6650, manufactured by Canon Inc.) and subjected to a copying test at 23 ° C./60% under environmental conditions. A clear image without fog of mm was obtained. Furthermore, when the durability performance was examined by continuously copying 20,000 sheets, an image having an image density of 1.30 and a good image comparable to the initial image were obtained.

Next, when a copy test was conducted under an environmental condition of 15 ° C./10%, an image of high density and good image quality was obtained. 2
The results were similarly good in the continuous copying test of 10,000 copies.

When the same copy test and continuous copy test were performed under the environmental conditions of 35 ° C./85%, good results were obtained.

〔The invention's effect〕

As described above, the toner containing the p-phenylcalix [n] arene of the present invention as a charge control agent has a sufficient triboelectric charge amount, has a uniform triboelectric charge amount between toner particles, and has no fog. Gives good images. Further, since the contamination of the toner carrier such as the sleeve and the carrier by the charge control agent is reduced, an image having a sufficient density can be obtained even after a large number of copies, and the density is stable. further,
Since the dependency of image density on temperature and humidity is small, an image of excellent quality can be provided under a wide range of environmental conditions. In addition, since it does not easily change over time, it has excellent quality stability during storage. Further, since the toner is not decomposed and deteriorated at the time of heating and kneading, waste toner generated at the time of toner production can be reused, and resource saving can be achieved.

Further, since the color tone disturbance due to the charge control agent is small, it can be used for a color toner.

[Brief description of the drawings]

FIG. 1 is an explanatory view schematically showing an example of an apparatus for fixing and embedding particles (Z) on particles (Y). DESCRIPTION OF SYMBOLS 1 ... Rotating shaft 2 ... Rotor 3 ... Dispersion blade 4 ... Rotating piece (blade) 5 ... Partition disk 6 ... Casing 7 ... Liner 8 ... Impact part 9 ... Inlet chamber 10 ... Outlet Chamber 11 Return path 12 Product take-out unit 13 Raw material input valve 14 Blower 15 Jacket

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) G03G 9/08 CA (STN)

Claims (1)

(57) [Claims] 1. The compound of the general formula (I) [Where A is the following formula Where B is the following formula Wherein R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen, carbon atom 1
To 6 alkyl groups, halogens, carboxyl groups, hydroxy groups, cyano groups, nitro groups, methyl halide groups,
A trimethylsilyl group, an ester group having 1 to 8 carbon atoms, an amide group having 1 to 8 carbon atoms, an acyl group having 1 to 12 carbon atoms,
It represents a sulfonyl group having 1 to 8 carbon atoms and an ether group having 1 to 8 carbon atoms, n represents an integer of 4 to 8, and m represents an integer of 0 to n of n or less. However, in the general formula (I),
m and n indicate the number of components A and B, and do not define the order in which the components A and B are combined. A toner for developing an electrostatic image, comprising at least one p-phenylcalix (n) arene compound represented by the formula: