JP3211504B2 - Toner for developing electrostatic latent images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel toner for developing an electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing and the like, and more particularly to a toner containing a specific calixarene compound.

[0002]

2. Description of the Related Art In developing an electrostatic latent image, a negatively or positively triboelectrically charged toner is electrostatically applied to an electrostatic latent image having a positive or negative charge formed on a photoreceptor by various methods. Then, the developed image is fixed by transferring and fixing the toner image on the transfer paper.

[0003] Toner used for developing such an electrostatic latent image is first required to have an appropriate charge amount in order to obtain a clear developed image without fog or the like. Further, it is also required that the charge amount does not change with time and that the charge amount does not significantly change or change due to environmental changes, for example, humidity change. This is because if the charge amount attenuates from the initially set value and becomes smaller, toner scattering increases, causing problems such as background fog, toner scattering on blank paper, and toner contamination around the developing device. is there.

[0004] In order to meet the above demand, a charge control agent is usually added during the production of a toner.
A white or pale yellow charge control agent having excellent color reproducibility is required.

[0005] Colorless, white, and pale yellow negative charge control agents for imparting a negative charge are commercially available, but most of them are metal-containing compounds containing heavy metals, such as complexes or salts containing chromium. In particular, from the viewpoint of safety, a metal-free negative charge control agent containing no heavy metal is demanded.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a toner for developing an electrostatic latent image using a negative charge controlling agent containing no heavy metal.

[0007] Another object of the present invention is to increase the charge,
An object of the present invention is to provide an electrostatic latent image developing toner having excellent charge stability, spent resistance, and environmental resistance.

Another object of the present invention is to provide a toner for developing an electrostatic latent image which is excellent in color reproducibility and light transmission.

[0009]

That is, the present invention provides a compound represented by the following general formula [I]:

Embedded image [Wherein, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or — (CH ₂ ) m COOR ₃ (R ₃ represents a hydrogen atom or a lower alkyl group, and m is an integer of 1 to 3. ); N represents an integer of 1 to 7. And a calixarene compound represented by the formula:

In the general formula [I], R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or — (CH ₂ ) mCO
OR ₃ (R ₃ represents a hydrogen atom or a lower alkyl group (preferably methyl or ethyl), and m represents an integer of 1 to 3 (preferably 1)). n represents an integer of 1 to 7.

In the above formula [I], the bonding order of the aryl group to which the t-octyl group is bonded and the aryl group to which the t-butyl group is bonded are not particularly limited.

The calixarene compound of the present invention is useful as a charge control agent for toner, and is particularly used as a negative charge control agent.

Examples of the calixarene compound represented by the general formula [I] of the present invention include the following.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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The above calixarene compounds may be used, for example, by mixing the compounds of Examples 1 to 5. Further, for example, only the compound of Example 1 may be used alone. When used alone, a compound having a specific value of n may be used alone, or a mixture of compounds having various values of n may be used. In this case, n = 0 or n = 8
May be included.

The calixarene compounds of the present invention are described in J.
Am. Chem. Soc. 1033782-3792
(1981), Pure & Appl. Chem. Vo
l. 58. No. 11 1523-1528 (198
5), Tetrahedron LetterS. Vo
l. 26. No. 28 3343-3344 (198
5), which can be easily synthesized according to literatures such as Hyundai Kagaku, 18214-23 (1986). The calixarene compound of the present invention is synthesized in high yield, for example, when phenol and formaldehyde are used as raw materials and a particularly strong alkali is used.

The calixarene compound represented by the general formula [I] is obtained by heating and melting a known toner, for example, a binder resin, a colorant and other components as necessary, cooling, pulverizing and classifying. Pulverized toner,
A core comprising a suspension-polymerized toner, a fixing resin, and a colorant obtained by dispersing at least one or more monomers and a polymerization initiator that is sparingly soluble in water and easily soluble in monomers in water and performs polymerization. Capsule toner in which a substance is coated with an outer shell layer, suspension-granulated toner in which a resin solution in which a binder resin is dissolved in an organic solvent is dispersed in a dispersion medium, and granulation is performed. A non-aqueous dispersion polymerized toner obtained by dispersing a polymerization initiator which is hardly soluble and easily soluble in a monomer in a dispersion medium comprising an organic solvent or a water / organic solvent mixture, and a matrix of a thermoplastic resin. Having a dispersed phase of a thermoplastic resin dispersed in the matrix and being phase-separated from the matrix, a toner in which substantially all of the colorant is filled in the dispersed phase, at least one obtained by suspension polymerization. Resin Toner obtained by crushing after heating and aggregating the particles comprising a colorant and a colorant, a spherical toner obtained by subjecting a toner obtained by subjecting a pulverized toner to a heat treatment, a spherical toner and an irregular toner Can be applied to a toner or the like in which is mixed. The calixarene compound may be contained inside the toner, or may be adhered and fixed on the toner surface.

When it is contained inside, in addition to additives such as a coloring agent, the calixarene compound charge control agent of the present invention is further added, and the pulverized toner, the suspension polymerization toner, the capsule toner and the like are formed by a usual method. It may be prepared. In the case of a capsule toner, it is desirable to prepare the outer shell layer so as to contain the charge control agent.

In the embodiment in which the charge control agent is attached to the surface of the outer shell layer, the charge control agent is attached to the toner surface by the action of van der Waals force, electrostatic force, or the like, and then fixed by mechanical impact force or the like. This treatment can be performed by a wet method or a dry method.

Examples of the dry method apparatus that can be suitably used in such a method include a hybridization system (manufactured by Nara Machinery Co., Ltd.) to which a high-speed air impact method is applied, an ng mill (manufactured by Hosokawa Micron Corporation), and a mechano mill.
(Made by Okada Seiko). However, it is of course not limited to such a method.

The content of the calixarene compound represented by the general formula [I] is appropriately determined according to the type of the toner, the toner additive, the type of the binder resin, and the like, and the developing method (two-component or one-component) of the toner. Is something to choose,
When the toner is contained in the toner by a pulverization method, a suspension method, or the like, 0.1 to 20 parts by weight,
Preferably it is 1 to 10 parts by weight, more preferably 1 to 5 parts by weight. If the amount is less than 0.1 part by weight, a desired charge amount cannot be obtained. If the amount is more than 20 parts by weight, the charge amount becomes unstable, and the fixability decreases.

When the calixarene compound is used by adhering and fixing it on the toner surface, 0.001 to 10 parts by weight, preferably 0.05 to 100 parts by weight of the toner particles is used.
To 2 parts by weight, more preferably 0.1 to 1 part by weight. If the amount is less than 0.001 part by weight, the amount of the charge control agent present on the surface of the toner particles is small, so that the charge amount becomes insufficient,
If the amount is more than 10 parts by weight, the adhesion of the charge control agent to the toner surface becomes insufficient, and peeling of the charge control agent from the toner surface during use becomes a problem. When the charge control agent is adhered and fixed on the toner surface, a stable charge amount can be imparted by using a very small amount as described above, and the calixarene compound of the present invention is also white, It is possible to provide a color toner excellent in charging performance and capable of forming a clear color image.

When the calixarene compound represented by the general formula [I] is contained in the toner, it is used in a particle size of 5 μm or less, preferably 3 μm or less, more preferably 1 μm or less. When used with a particle size larger than 5 μm, the dispersion state becomes non-uniform, and various characteristics of the charge amount become non-uniform. When the calixarene compound is attached to the toner surface, the calixarene compound is used in a particle size of 1 μm or less, more preferably 0.5 μm or less. Use of a particle size larger than 1 μm is disadvantageous in that it is uniformly adhered and fixed to the toner surface.

The charge control agent calixarene compound of the present invention may be used in combination as another negative charge control agent. Also,
In order to stabilize the chargeability, a very small amount of a positive charge control agent may be added. As described above, when the charge control agent of the present invention is used in combination with another charge control agent, the total amount thereof is set to be within the above-mentioned usage range.

Examples of the negative charge control agent include oil black (Color Index 26150) and oil black B
Y (manufactured by Orient Chemical Industries), metal salicylate complex E-
81 (manufactured by Orient Chemical Industries), thioindigo pigment,
Sulfonylamine derivative of copper phthalocyanine, Spiron Black TRH (manufactured by Hodogaya Chemical Industry Co., Ltd.), Bontron S-
34 (manufactured by Orient Chemical Co., Ltd.), Nigrosine SO (manufactured by Orient Chemical Co., Ltd.), Celes Schwarz (R) G (manufactured by Farben Fabriken Bayer), Chromogen Schwarz ETOO (CI No. 14645), Azo oil black (R) (manufactured by National Aniline Co., Ltd.), various boron compounds, calcium compounds and the like.

Examples of the positive charge control agent include Nigrosine Base EX (manufactured by Orient Chemical Industry), quaternary ammonium salt P-51 (manufactured by Orient Chemical Industry), Nigrosine, Bontron N-01 (Orient Chemical Co., Ltd.) Sudan Chief Schwarz BB (Solvent Black 3: Color Index 26150), Fettschwarz HBN (CI No. 26150), Brilliant Spirits Schwarz TN (Vanben, Fabriken
Bayer), Zavonschwarz X (Falberge Hoechst), alkoxylated amines, alkylamides, molybdate chelate pigments, imidazole compounds and the like. Further, a small amount of the calixarene compound of the present invention may be added to a positively charged toner using a positively charged control agent in order to stabilize the chargeability.

As the resin constituting the toner, any resin that is generally used as a binder in a toner can be used.
There is no particular limitation, for example, styrene resin, (meth) acrylic resin, olefin resin, amide resin, carbonate resin, polyether, polysulfone, polyester resin, thermoplastic resin such as epoxy resin Alternatively, a thermosetting resin such as a urea resin, a urethane resin, and an epoxy resin, and a copolymer and a polymer blend thereof are used. As the synthetic resin used in the toner for developing an electrostatic latent image of the present invention, not only those in a perfect polymer state as in a thermoplastic resin, but also oligomers or prepolymers as in a thermosetting resin In addition, those containing a prepolymer, a cross-linking agent and the like partially in the polymer can also be used.

Specific examples of the monomers constituting the resin used in the present invention include the following. That is, as the vinyl monomer, for example, styrene, o-methylstyrene, m-methylstyrene, p-
Methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene,
Styrene such as p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene and 3,4-dichlorostyrene and derivatives thereof are mentioned, and among them, styrene is most preferred.

Other vinyl monomers include, for example, ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene, vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride, and acetic acid. Vinyl esters such as vinyl, vinyl propionate, vinyl benzoate, and vinyl butyrate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-methyl methyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobu methacrylate Le, propyl methacrylate,
Α such as n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc.
-Methylene fatty acid monocarboxylic acid esters, (meth) acrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl methyl ketone, vinyl hexyl ketone And vinyl ketones such as methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; and vinyl naphthalenes.

Caprolactam is used as a monomer to obtain an amide resin, and terephthalic acid, isophthalic acid, adipic acid, maleic acid, succinic acid, sebacic acid, thioglycolic acid and the like are mentioned as dibasic acids. Classes include ethylenediamine, diaminoethyl ether, 1,4-diaminobenzene, and 1,4-diaminobenzene.
Diaminobutane and the like can be mentioned.

Examples of the monomer for obtaining the urethane resin include diisocyanates such as p-phenylene diisocyanate, p-xylene diisocyanate, and 1,4-tetramethylene diisocyanate. Examples of the glycols include ethylene glycol, diethylene glycol, and propylene. Glycol and polyethylene glycol.

As a monomer for obtaining a urea resin, diisocyanates include p-phenylene diisocyanate, p-xylene diisocyanate, and 1,4-tetramethylene diisocyanate. Diamines include ethylene diamine, diaminoethyl ether, Examples thereof include 1,4-diaminobenzene and 1,4-diaminobutane.

Further, as a monomer for obtaining an epoxy resin,
Examples of amines include ethylamine, butylamine, ethylenediamine, 1,4-diaminobenzene, 1,4-diaminobutane, and monoethanolamine. Examples of diepoxy compounds include diglycidyl ether,
Examples thereof include ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, and hydroquinone diglycidyl ether.

As a monomer for obtaining a polyester resin, as a polyol component, ethylene glycol, diethylene glycol, triethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, neo Pentyl glycol, 2-ethyl-1,3-pentanediol, 2,2,4
-Trimethyl-1,3-pentanediol, 1,4-bis
(2-hydroxymethyl) cyclohexane, 2,2-bis
(4-hydroxypropoxyphenyl) propane, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, etc., and as the polybasic acid component, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, Unsaturated carboxylic acids such as glutaconic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, malonic acid,
Sebacic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,5-cyclohexanetricarboxylic acid, 1,2,
4-butanetricarboxylic acid, 1,3-dicarboxy-2
-Methyl-2-methylcarboxypropane, saturated carboxylic acids such as tetra (methylcarboxy) methane and the like, or an acid anhydride and an ester thereof with a lower alcohol may also be used.Specifically, for example, Maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, dimethyl terephthalate, and the like can be given.

The polyester resin used in the present invention is not limited to one obtained by polymerizing a combination of the above-mentioned polyol component and another basic acid component one by one, but may be one obtained by polymerizing a plurality of types. In particular, as the polybasic acid component, a combination of an unsaturated carboxylic acid and a saturated carboxylic acid, or a combination of a polycarboxylic acid and a polycarboxylic anhydride is often performed.

It is desirable to add a low molecular weight polyolefin wax to the thermoplastic resin, and the amount is 1 to 10 parts by weight, preferably 2 to 6 parts by weight, per 100 parts by weight of the thermoplastic resin. The compound represented by the general formula [I] of the present invention exhibits good negative charge controllability with respect to these compositions, and can impart practically sufficient chargeability.

Recently, there has been a demand for a technique capable of copying at a higher speed. For toner used for such high-speed development, the toner can be fixed to transfer paper in a short time, and the toner can be separated from a fixing roller. Need to be improved.

Accordingly, the styrene monomer, (meth) acrylic monomer, (meth)
A homopolymer or a copolymer polymer synthesized from an acrylate resin, or the polyester resin described above, has a number average molecular weight (Mn), a weight average molecular weight (Mw), and a relationship with a Z average molecular weight (Mz) as its molecular weight. 1,000 < Mn < 7,000 40 < Mw / Mn < 70 200 < Mz / Mn < 500, and the number average molecular weight (Mn) is further 2,000.
It is preferable to use those in which < Mn < 7,000.

The resin constituting the toner includes PVC resistance,
Polyester resins have attracted attention from the viewpoint of translucency as a translucent color toner and adhesion to an OHP sheet.
These polyester resins have a glass transition temperature of 55 to 70 ° C. and a softening point of 8 when used for translucent toner.
It is desirable to use a linear polyester at 0 to 150 ° C. When used as an oilless fixing toner, the glass transition temperature is 55 to 80 ° C., and the softening point is 80 to 150.
It is desirable that the composition contains a gelling component at 5 ° C. and 5 to 20 wt%.

When used as a low-temperature fixing toner,
It is desirable to use a toner having a flow starter temperature of 100 ° C. or lower and a softening point of 110 ° C. or lower as a toner constituent resin.

The calixarene compound represented by the general formula [I] of the present invention comprises, as a main component, a linear urethane-modified polyester (C) obtained by reacting a linear polyester resin (A) with a diisocyanate (B). It can also be used for toner composed of resin. The linear urethane-modified polyester referred to here is a linear polyester resin (A) 1 comprising a dicarboxylic acid and a diol, having a number average molecular weight of 1,000 to 20,000, an acid value of 5 or less, and having a substantially terminal hydroxyl group. A linear urethane-modified polyester resin (C) obtained by reacting 0.3 to 0.95 mol of diisocyanate (B) per mol, and having a glass transition temperature of 40 to 80 ° C. The main component is one having a value of 5 or less. As the dicarboxylic acid, diol and diisocyanate, those described above can be used.

The calixarene compound of the present invention is obtained by graft polymerization of a vinyl monomer component containing a vinyl monomer and an amino group-containing vinyl monomer onto an unsaturated polyester component comprising at least an aliphatic unsaturated dibasic acid and a polyhydric alcohol. It can also be used for a toner composed of a vinyl-modified polyester resin obtained by block polymerization.

As the colorant contained in the toner for developing an electrostatic latent image of the present invention, various kinds of organic or inorganic pigments and dyes as shown below can be used.

That is, black pigments include carbon black, copper oxide, manganese dioxide, aniline black,
Activated carbon and the like.

Examples of the yellow pigment include graphite, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navels yellow, naphthol yellow S, banza yellow G, banza yellow 10G, benzidine yellow G, and benzidine. Yellow GR, Quinoline Yellow Lake, Permanent Yellow N
There are CG and tartrazine lake.

Examples of orange pigments include red lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, indaslen brilliant orange RK, benzidine orange G, and indaslen brilliant orange GK.

Red pigments include red iron, cadmium red, lead red, mercury sulfide, cadmium, permanent red 4R, lithol red, pyrazolone red, watching red, calcium salt, lake red D, brilliant carmine 6B, oxi lake, rhodamine lake. B, Alizarin Lake, Brilliant Ant Carmine 3B and the like.

The purple pigment includes manganese purple, fast violet B, methyl violet lake and the like.

As blue pigments, navy blue, cobalt blue, alka blue lake, victoria blue lake,
Phthalocyanine blue, metal-free phthalocyanine blue,
Phthalocyanine blue partially chlorinated product, Fast Sky Blue, Indaslen Blue BC, and the like.

Examples of the green pigment include chrome green, chromium oxide, pigment green B, malachite green lake, final yellow green G, and the like.

As white pigments, zinc white, titanium oxide,
Examples include antimony white and zinc sulfide.

The extender includes baryte powder, barium carbonate, clay, silica, white carbon, talc, alumina white and the like.

Various dyes such as basic, acidic, disperse, and direct dyes include nigrosine, methylene blue, rose bengal, quinoline yellow, and ultramarine blue.

These colorants can be used alone or in combination of two or more. However, the colorants are used in an amount of 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the resin constituting the toner. Is desirable. That is, when the amount is more than 20 parts by weight, the fixing property of the toner is reduced.
If the amount is less than 1 part by weight, a desired image density cannot be obtained.

When used as a translucent color toner, pigments and dyes of various colors and colors as described below can be used as the colorant.

As the yellow pigment, C.I. I. 10316
(Naphthol yellow S), C.I. I. 11710 (Hanza Yellow 10G), C.I. I. 11660 (Hanza Yellow 5G), C.I. I. 11670 (Hanza Yellow 3G),
C. I. 11680 (Hanza Yellow G), C.I. I. 11
730 (Hanza Yellow GR), C.I. I. 11735 (Hanza Yellow A), C.I. I. 11740 (Hanza Yellow RN), C.I. I. 12710 (Hanza Yellow R), C.I.
I. 12720 (Pigment Yellow L), C.I. I. 210
90 (benzidine yellow), C.I. I. 21095 (benzidine yellow G), C.I. I. 21100 (benzidine yellow GR), C.I. I. 20040 (Permanent Yellow NCG), C.I. I. 21220 (Vulcan Fast Yellow 5), C.I. I. 21135 (Vulcan Fast Yellow R).

As red pigments, C.I. I. 12055
(Stalin I), C.I. I. 12075 (permanent orange), C.I. I. 12175 (Resole Fast Orange 3GL), C.I. I. 12305 (Permanent Orange GTR), C.I. I. 11725 (Hanzaa 3R),
C. I. 21165 (Vulcan Fast Orange GG),
C. I. 21110 (benzidine orange G), C.I. I.
12120 (Permanent Red 4R), C.I. I. 127
0 (para red), C.I. I. 12085 (Fire Red), C.I. I. 12315 (Brilliant Fast Scarlet), C.I. I. 12310 (Permanent Red FR
2), C.I. I. 12335 (Permanent Red F4
R), C.I. I. 12440 (Permanent Red FR
L), C.I. I. 12460 (Permanent Red FRL
L), C.I. I. 12420 (permanent ke F4RH),
C. I. 12450 (Light Fast Red Toner B), C.I. I. 12490 (Permanent Carmine F
B), C.I. I. 15850 (Brilliant Carmine 6B)
and so on.

As the blue pigment, C.I. I. 7410
0 (metal-free phthalocyanine blue), C.I. I. 74160
(Phthalocyanine blue), C.I. I. 74180 (First Sky Blue).

These colorants can be used alone or in combination of two or more. However, 1 to 10 parts by weight, more preferably 2 to 5 parts by weight, per 100 parts by weight of the resin contained in the toner particles is used. It is desirable to do. That is, if the amount is more than 10 parts by weight, the fixing property and the light transmitting property of the toner decrease. If the amount is less than 1 part by weight, a desired image density may not be obtained.

When carbon black is used as a colorant in the toner of the present invention, it is desirable to use carbon black having a pH of 7 or less. Carbon black having a pH of 7 or less has good dispersibility in a binder resin due to the influence of a polar group present on the surface thereof, and a remarkable effect is obtained particularly when applied to a small particle size toner having an average particle size of 2 to 9 μm. .

For negatively charged toner, it also contributes to improvement of toner chargeability such as improvement of negative chargeability.

In order to improve the dispersibility in the binder resin, a carbon black graft polymer may be used as a coloring agent.

In order to obtain a carbon black graft polymer, a functional group (for example, -O
H, -COOH,> C = O, etc.). As the polymer that can react with carbon black, any polymer having a reactive group that can easily react with a functional group present on the surface of carbon black can be used without particular limitation. Examples of the reactive group capable of easily reacting with a functional group present on the surface of carbon black include an aziridine group, an oxazoline group, an N-hydroxyalkylamide group, an epoxy group, a thioepoxy group, an isocyanate group,
Examples include a vinyl group, a silicon-based hydrolyzable group, and an amino group. It is at least one group selected from these groups.

Examples of the polymer having reactivity with carbon black as described above include vinyl polymers, polyesters and polyethers having at least one reactive group in the molecule. Although the molecular weight of the polymer having reactivity is not particularly limited, the number average molecular weight is 500 to 100000 in terms of a remarkable treatment effect on carbon black and workability at the time of reaction with carbon black.
It is preferably in the range of 0, more preferably 1000
~ 500,000, most preferably 2000-10000
It is in the range of 0. The reactive group must have at least one reactive group in one molecule on average. However, as the amount of the reactive group increases, the dispersibility of the carbon black polymer in other substances deteriorates. On average, 1 to 5 per molecule
It is more preferable that the number be one or two, and most preferably one.

In order to obtain such a polymer having reactivity with carbon black, for example, the above-mentioned polymerizable monomer having a reactive group in the molecule is optionally known in combination with other polymerizable monomers. And a method of reacting a compound having the reactive group in the molecule with a polymer having a group capable of reacting with the compound, and the like. In the present invention, one or more selected from an aziridine group, an oxazoline group, an N-hydroxyalkylamide group, an epoxy group, a thioepoxy group, and an isocyanate group, particularly in terms of reactivity with a functional group present on the surface of carbon black. It is preferable to use a polymer having two or more reactive groups, more preferably a polymer having one or two or more reactive groups selected from an aziridine group, an oxazoline group, and an epoxy group, and most preferably. Is a polymer having at least one reactive group selected from the group consisting of an aziridine group and an oxazoline group.

In the toner of the present invention, an offset preventing agent may be used in combination for improving the fixing property. As the anti-offset agent, various waxes, particularly natural waxes such as polyolefin waxes such as low molecular weight polypropylene and polyethylene, or oxidized polypropylene and polyethylene, carnauba wax, rice wax and montan wax are preferably used. The addition amount of the offset preventing agent is 1 to 10 parts by weight, preferably 2 to 6 parts by weight based on 100 parts by weight of the binder resin. Further, these waxes preferably have a number average molecular weight (Mn) of 1,000 to 20,000 and a softening point (Tm) of 80 to 150 ° C. Number average molecular weight Mn is 1000 or less, or softening point Tm is 80 ° C.
When the content is below, uniform dispersion with the synthetic resin component in the synthetic resin coating layer cannot be performed, and only the wax is eluted on the toner surface, which may cause undesired results during storage or development of the toner. Photoconductor contamination such as filming may occur. Further, the number average molecular weight exceeds 20,000, or Tm is 150 ° C.
If it exceeds, not only the compatibility with the resin is deteriorated, but also the effect of containing a wax such as high-temperature offset resistance cannot be obtained. When used with a synthetic resin having a polar group from the viewpoint of compatibility, a wax having a polar group is desirable.

The toner of the present invention has
A fluidizing agent may be added and mixed. As the fluidizing agent, various metal oxides such as silica, aluminum oxide, titanium oxide, a mixture of silica and aluminum oxide, a mixture of silica and titanium oxide, and magnesium fluoride can be used. These substances may be added internally.

Examples of the cleaning aid include the above-mentioned inorganic fine particles as a fluidizing agent, metal soaps such as stearates, and the like.
Fluorine, silicon, styrene- (meth) acrylic,
Various synthetic resin fine particles such as benzoguanamine, melamine, and epoxy are used. Examples of the synthetic resin particles include a wet polymerization method such as an emulsion polymerization method, a soap-free emulsion polymerization method, a non-aqueous dispersion polymerization method, and a styrene-based (meth) acrylic-based, olefin-based, and fluorinated-based granulated by a gas phase method. And various organic fine particles such as nitrogen-containing (meth) acrylic, silicon, benzoguanamine, and melamine. As these synthetic resin fine particles, substantially spherical particles having an average particle size of 0.01 to 3 μm, preferably 0.05 to 2 μm, smaller than the average particle size of the toner, are added to the toner in an amount of 0.01 to 0.01 μm.
It is desirable to add 10 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.1 to 2% by weight.

Further, the toner of the present invention may be used as a magnetic toner, and known magnetic fine particles may be dispersed in a binder resin. As the magnetic material, for example, cobalt, iron, nickel and other ferromagnetic metals, cobalt,
Iron, nickel, aluminum, lead, magnesium, zinc, antimony, beryllium, bismuth, cadmium,
Alloys of metals such as calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures of these metals, and known magnetic materials such as oxides and sintered bodies (ferrites) can be used. These magnetic substances may be added in an amount of 1 to 80 parts by weight, preferably 5 to 60 parts by weight, based on 100 parts by weight of the binder resin of the toner.

The toner of the present invention has an average particle diameter of 2 to 20 μm.
m is desirable. In particular, when a high-definition image is reproduced, it is preferable to use a small particle size toner having an average particle size of 2 to 9 μm. In the small particle size toner, the charge control agent contained in the toner also requires uniformity. However, the calixarene compound of the present invention is easily formed into fine particles, and has excellent dispersibility in resin. Can be used.

The toner of the present invention can be applied to both two-component developers and one-component developers (magnetic and non-magnetic). When used as a two-component developer, a known carrier powder such as a ferrite carrier, a coating carrier, an iron powder carrier, a binder-type carrier, and a carrier having a composite charged surface can be used.

Further, the toner of the present invention frictionally charges the toner by passing through a gap between a toner regulating member including a blade, a roller and the like, and forms a thin toner layer on the surface of the toner carrier. It is also suitably used in a developing method having means. The toner carrier may be used as a developing roller or as a toner supply roller for the developing roller.

The calixarene compound of the present invention may be used for a photoconductive toner. The toner produced by the above method can be used for development for visualizing an electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing or the like by a conventionally known means.

[0078]

[Synthesis Example] Synthesis of calixarene compound 1 pt-octylphenol 20.4 g (0.1 mol), pt
15.0 g (0.1 mol) of butylphenol, 4.4 g (0.15 mol) of paraformaldehyde and 0.1 g of a 10N aqueous potassium hydroxide solution were heated and stirred in 800 ml of xylene to distill off water, and 138 to 142 ° C. At reflux for 6 hours. Thereafter, the content was allowed to cool, and suction-filtered. The filtrate was washed with xylene and dried under reduced pressure to obtain a white powder. Yield 2
It was 4.7 g (71.0%).

The chemical structure of the obtained calixarene compound 1 is as follows:

Embedded image The composition in which n was from 0 to 8 had the following ratio (% by volume) as measured by liquid chromatography.

[0080]

Table 1 n Composition ratio (%) 0 0.6 1 1.0 2 9.9 3 25.0 4 31.6 5 22.7 6 8.1 7 0.9 0.98 0.2

Synthesis of Calixarene Compound 2 2 g of Compound 1 was separated by preparative chromatography and purified with methanol to obtain a white powder. The yield was 0.58 g (29.0%). The chemical structure of the obtained calixarene compound 2 is

Embedded image It is.

Synthesized Calixus Allen Compound 3 10 g of Compound 1 was separated by preparative chromatography, and white powder purified with acetone was obtained. The yield was 0.65 g (6.5%). The chemical structure of the obtained calixarene compound 3 is

Embedded image It is.

30 g of Calixarene Compound 4 Synthetic Compound 1 was separated by preparative chromatography and then purified with chloroform to obtain a white powder. The yield was 0.25 g (0.8%). The chemical structure of the obtained calixarene compound 4 is

Embedded image It is.

Synthesis of Calixarene Compound 5 10 g of Compound 1 was dissolved in 800 ml of dimethylformamide, 6 g (0.25 mol) of sodium hydride and 56.8 g (0.4 mol) of methyl iodide were added and reacted at 80 ° C. for 12 hours. After allowing the content to cool, it was dispersed in 1000 ml of water. The dispersion was filtered, washed with water and recrystallized from methanol to obtain a white powder. The yield was 4.2 g (39.0%). The chemical structure of the obtained calixarene compound 5 is

Embedded image The composition in which n was from 0 to 8 had the following ratio (% by volume) as measured by liquid chromatography.

[0085]

Table 2 n Composition ratio (%) 0 0.3 1 1.8 2 11.4 3 26.1 4 30.5 5 19.4 6 8.3 7 1.6 8 0.6 0.6

Synthesis of Calixarene Compound 6 10 g of Compound 1 was dissolved in 600 ml of dimethylformamide, and 6 g (0.25 mol) of sodium hydride and 68.0 g (0.4 mol) of propyl iodide were added thereto.
For 24 hours. After allowing to cool, the mixture was dispersed in 2,000 ml of water, filtered, washed with water, and recrystallized from ethanol to obtain a yellowish white powder.
The yield was 3.7 g (30.3%).

The chemical structure of the obtained calixarene compound 6 is

Embedded image The composition in which n was from 0 to 8 had the following ratio (% by volume) as measured by liquid chromatography.

[0088]

Table 3 n Composition ratio (%) 0 0.2 1 1.6 2 9.3 3 22.4 4 35.1 5 21.5 6 7.0 7 1.9 8 1.0

Synthesis of Calixarene Compound 7 20 g of Compound 4 was dissolved in 700 ml of dimethylformamide, and 12 g (0.5 mol) of sodium hydride and 158.4 g (0.8 mol) of pentyl iodide were added thereto.
Reaction was carried out at 48 ° C for 48 hours. After allowing to cool, the mixture was dispersed in 2,000 ml of water, filtered, washed with water, and recrystallized from ethanol to obtain a yellowish white powder. The yield was 7.6 g (26.9%).

The chemical structure of the obtained calixarene compound 7 is

Embedded image It is.

Synthesis of Calixarene Compound 8 10 g of Compound 1 was added to 20 g of sodium hydroxide (0.5 m
ol) and 86 g (0.6 mol) of monobrominated acetic acid in water 30
The reaction was carried out by heating at 0 ° C. for 48 hours in 0 ml. After cooling, the reaction solution was dried under reduced pressure and recrystallized from ethanol to obtain a white powder. The yield was 10.3 g (72.8%).

The chemical structure of the obtained calixarene compound 8 is

Embedded image It is.

In any of the above compounds 1 to 8, the order of bonding is not specified. The calixarene compounds 1 to 8 were applied to various types of developer toners.

Example 1 Component parts by weight Styrene-n-butyl methacrylate 100 (softening point: 132 ° C, glass transition point: 60 ° C) Carbon black (manufactured by Mitsubishi Kasei; MA # 8) (pH: 3) 8 Calixarene Compound 15

After thoroughly mixing the above materials with a ball mill,
The mixture was kneaded on three rolls heated to 140 ° C. The kneaded material was allowed to cool and then coarsely pulverized using a feather mill.

The coarsely pulverized product was finely pulverized by a jet mill. The finely pulverized product was subjected to air classification to obtain a fine powder having an average particle size of 8 μm.

100 parts by weight of the obtained fine powder was mixed with hydrophobic silica R-974 (manufactured by Nippon Aerosil Co., Ltd .; average particle size: 17).
m.mu.) of 0.1 parts by weight, and the mixture was treated at 1,000 rpm for 1 minute with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain Toner 1-1.

Example 2 Example 1 was repeated except that 30 parts by weight of magnetic powder (manufactured by TDK; MFP-2, fine ferrite particles) were added.
A toner 1-2 having an average particle size of 8 μm was obtained in the same manner as described above.

Example 3 Ingredients: parts by weight Polyester resin (Tuffton NE1110; manufactured by Kao Corporation) 100 Carbon black (Mogal L; manufactured by Cabot Corporation) 8 Calixarene compound 2 3 Decarried fatty acid type carnauba wax (melting point 85 ° C., acid value) 0.5) 1.5

After the above-mentioned materials were sufficiently mixed by a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.), they were kneaded using a twin-screw kneader (manufactured by Ikegai Iron Works). The kneaded material was left to cool, coarsely pulverized using a feather mill, and further finely pulverized by a jet mill. The finely pulverized product was subjected to air classification to obtain a fine powder having an average particle size of 8 μm.

100 parts by weight of the obtained fine powder was added to hydrophobic silica H-2000 (manufactured by Wakka Kabushiki Kaisha; average particle size: 17 mμ).
0.2 part by weight was added, and the mixture was treated with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 1,000 rpm for 1 minute to obtain Toner 1-3.

Example 4 A toner 1-4 having an average particle diameter of 8 μm was prepared in the same manner as in Example 3 except that 5 parts by weight of a red pigment Lake Red C (manufactured by Dainichi Seika) was used instead of carbon black. I got

Example 5 Ingredients: parts by weight Polyester resin (Tufton NE-382; manufactured by Kao Corporation) 100 Phthalocyanine pigment (manufactured by Dainichi Seika Co., Ltd.) 5 Calixarene compound 3 3

After thoroughly mixing the above materials with a ball mill,
The mixture was kneaded on three rolls heated to 140 ° C. The kneaded material was allowed to cool, then coarsely pulverized using a feather mill, and further finely pulverized using a jet mill. The finely pulverized product was subjected to air classification to obtain a fine powder having an average particle size of 7 μm.

0.3 parts by weight of hydrophobic silica (H-2000; manufactured by Wacker Corp.) and hydrophobic alumina (RX-C; manufactured by Nippon Aerosil Co., Ltd.) were added to 100 parts by weight of the obtained fine powder.
5 parts by weight were added, and the mixture was treated with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 1,000 rpm for 1 minute to obtain Toner 1-5.

Comparative Example 1 A toner 1-A having an average particle diameter of 8 μm was obtained in the same manner as in Example 1 except that Calixarene Compound 1 was not added.

Comparative Example 2 A toner having an average particle size of 8 μm was obtained in the same manner as in Example 1 except that p-tert-butylcalix (7) arene having the following structural formula was added in place of the calixarene compound 1. 1-B was obtained.

[0108]

Embedded image

Comparative Example 3 The procedure of Example 3 was repeated, except that 3 parts by weight of a chromium complex type dye (S-34; manufactured by Orient Chemical Industries) was used instead of the calixarene compound 2. A toner 1-C having a particle size of 8 μm was obtained.

Example 6 Components Parts by weight Styrene-n-butyl methacrylate 100 (softening point: 132 ° C., glass transition point: 60 ° C.) Carbon black (manufactured by Mitsubishi Kasei; MA # 8) (pH; 3) 8 Low molecular weight Polypropylene (manufactured by Sanyo Chemical Industries, Ltd .; Viscol 550P) 5 Calixarene compound 45

After sufficiently mixing the above materials with a ball mill,
The mixture was kneaded on three rolls heated to 140 ° C. The kneaded material was allowed to cool, then coarsely pulverized using a feather mill, and further finely pulverized using a jet mill. The finely pulverized product was subjected to air classification to obtain a fine powder having an average particle size of 8 μm.

10 parts by weight of the obtained fine powder was added to hydrophobic silica R-974 (manufactured by Nippon Aerosil Co., Ltd .; average particle size: 17 m).
μ) was added, and the mixture was treated at 1,000 rpm for 1 minute with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain Toner 2-1.

Example 7 Ingredients: parts by weight Polyester resin (Tuffton NE1110; manufactured by Kao Corporation) 100 Carbon black (Mogal L; manufactured by Cabot Corporation) (pH: 3) 8 Oxidized low molecular weight polypropylene 4 (TS-200; Sanyo Chemical Industries, Ltd.) Calixarene compound 53

After the above-mentioned materials were sufficiently mixed by a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.), they were kneaded using a twin-screw kneading apparatus (manufactured by Ikegai Iron Works). The kneaded material was left to cool, coarsely pulverized using a feather mill, and further finely pulverized by a jet mill. The finely pulverized product was subjected to air classification to obtain a fine powder having an average particle size of 8 μm.

With respect to 100 parts by weight of the obtained fine powder, hydrophobic silica H-2000 (manufactured by Wakka Kabushiki Kaisha; average particle size: 17 mμ)
0.2 parts by weight were added, and the mixture was treated at 1,000 rpm for 1 minute using a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain Toner 2-2.

Example 8 Polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane 68 parts by weight, isophthalic acid 16 parts by weight, terephthalic acid 16 parts by weight, maleic anhydride 0.3 part by weight, 0.1 part by weight of dibutyltin oxide was charged into a flask and reacted at 230 ° C. for 24 hours under a nitrogen atmosphere. The reaction product was taken out to obtain a polyester resin containing an unsaturated polyester. The weight average molecular weight of the obtained polyester resin was 9,800.

50 parts by weight of the obtained polyester resin and 50 parts by weight of xylene were charged into a flask and dissolved. The temperature was increased until xylenes refluxed. Under refluxing xylene, a solution prepared by dissolving 0.6 parts by weight of azobisisobutyronitrile in 13 parts by weight of styrene and 2 parts by weight of methyl methacrylate was added dropwise in about 30 minutes under a nitrogen atmosphere. After dropping, the temperature was kept for 3 hours. Xylene was distilled under reduced pressure to remove the resin. A styrene-acryl-modified polyester resin having a weight average molecular weight of 11,700, Mw / Mn of 2.8, a melt viscosity at 100 ° C of 5 × 10 ⁴ poise, and a glass transition temperature of 60 ° C was obtained.

However, the melt viscosity is a value measured using a flow tester CFT-500 manufactured by Shimadzu Corporation under the conditions of a nozzle diameter of 1 mm, a nozzle length of 1 mm, a load of 30 kg and a heating rate of 3 ° C./min.

100 parts by weight of the styrene-acryl-modified polyester resin obtained above 2.5 parts by weight of organic pigment Lionol Yellow FG-1310 2.5 parts by weight of calixarene compound 6

The above materials were sufficiently mixed with a Henschel mixer, kneaded with a twin screw extruder, and cooled. The kneaded material was roughly pulverized by a feather mill and further finely pulverized by a jet pulverizer. The finely pulverized product was subjected to air classification to obtain particles having an average particle size of 8 μm.

To 100 parts by weight of the obtained 8 μm particles, 0.3 parts by weight of hydrophobic silica H-2000 / 4 (manufactured by Wakka) and 0.5 parts by weight of hydrophobic titanium oxide T-805 (manufactured by Degussa) were used. Henschel mixer (Mitsui Miike Kakoki Co., Ltd.)
1 minute at 1500 rpm to remove toner 3
-1 was obtained.

Example 9 A 5-liter four-necked flask was equipped with a reflux condenser, a water separator,
The vessel was equipped with a N ₂ gas introduction pipe, a thermometer, and a stirrer, and was installed in a mantle heater. Bisphenol propylene oxide adduct (1370 parts by weight) and isophthalic acid (443 parts by weight) were charged into the flask so as to have a COOH / OH ratio of 1.5, and N ₂ gas was introduced into the flask at 250 ° C. For dehydration polycondensation. Weight average molecular weight (M
w): 4300, low molecular weight polyester having a glass transition temperature (Tg): 59 ° C.

Apart from this, a reflux condenser, a water separator,
₍₂ ) Bisphenol propylene oxide adduct (1720 parts by weight), isophthalic acid (860 parts by weight), diethylene glycol (12 parts) were placed in a 5-liter four-necked flask equipped with a gas inlet tube, a thermometer, and a stirrer and installed in a mantle heater.
(9 parts by weight) to obtain an OH / COOH ratio of 1.2, and dehydrocondensation was performed at 240 ° C. while introducing N ₂ gas into the flask. Weight average molecular weight (Mw): 7000,
A high molecular weight polyester having a glass transition temperature (Tg) of 61 ° C. was obtained.

The obtained low-molecular-weight polyester (60 parts by weight) and high-molecular-weight polyester (40 parts by weight) were charged into a Henschel mixer (Mitsui Miike Kakoki) and dry-blended until sufficiently uniform.

Subsequently, the blend was charged into a heating kneader, and 100 parts by weight of diphenylmethane-4,4-diisocyanate was charged at a temperature of 130 ° C. so as to have an NCO / OH ratio of 1.0 and reacted for 1 hour. After confirming that the remaining free isocyanate groups have almost disappeared by NCO%, the reaction product is cooled and the urethane-modified polyester resin is cooled.
(Tg: 64 ° C., acid value: 25) was obtained.

-100 parts by weight of the obtained urethane-modified polyester resin-8 parts by weight of carbon black (pH: 3 manufactured by Mogal L Cabot)-3 parts by weight of low molecular weight polypropylene (TS200; manufactured by Sanyo Chemical)-Calixarene compound 7 2 parts by weight

The above-mentioned materials were mixed and dispersed by a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) and then kneaded by a twin-screw extruder. After coarsely pulverizing the kneaded material using a feather mill,
It was pulverized using a jet mill. The finely pulverized product was classified by an air classifier to obtain particles having an average particle size of 8 μm.

To 100 parts by weight of the obtained 8 μm particles, 0.5 parts by weight of hydrophobic silica H-2000 (manufactured by Wakka) was added, and the mixture was treated with a Henschel mixer at 1500 rpm for 1 minute to obtain toner 4-1. Obtained.

Example 10 A flask was charged with 60 parts by weight of 2,2'-bis [P- (2-hydroxy) -phenyl] propane, 20 parts by weight of isophthalic acid, and 0.1 part by weight of dibutyltin oxide, and placed in a nitrogen atmosphere. At 230 ° C. for 24 hours. The reaction product was taken out to obtain a polyester resin having a weight average molecular weight of 7,000.

After 50 parts by weight of the obtained polyester resin and 50 parts by weight of xylene were charged into a flask and dissolved, the temperature was raised until xylene was refluxed. A solution prepared by dissolving 0.4 parts by weight of azobisisobutyronitrile in 13 parts by weight of styrene and 0.3 parts by weight of diethylaminoethyl methacrylate was added dropwise under a nitrogen atmosphere for about 30 minutes while refluxing xylene.
After dropping, the temperature was kept for 3 hours. After xylene was distilled under reduced pressure, the resin was taken out.

The resulting amino-modified polyester resin is
Weight average molecular weight (Mw) is 11,000, Mw / Mn is 3.
0, melt viscosity at 100 ° C is 5 × 10 ⁴ poise, Tg
Was 61 ° C.

Component parts by weight Amino-modified polyester resin 100 Organic pigment Lionol Red 6B FG-4213 2.5 (manufactured by Toyo Ink Co., Ltd.) Calixarene compound 8 2.0

The above materials were mixed and dispersed by a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) and then kneaded by a twin screw extruder. After coarsely pulverizing the kneaded material using a feather mill,
It was pulverized using a jet mill. Next, the finely pulverized product was classified by an air classifier to obtain particles having an average particle size of 8 μm.

To 100 parts by weight of the obtained 8 μm particles, 0.5 parts by weight of hydrophobic silica H-2000 (manufactured by Wacker Inc.) was added, and the mixture was treated with a Henschel mixer at 1500 rpm for 1 minute to obtain toner 5-1. Obtained.

Example 11 160 g of styrene, 90 g of butyl methacrylate, 30 g of isobutyl acrylate, 3 g of α-methylstyrene dimer (Nofmer MSD; manufactured by NOF CORPORATION), 2 g of silane coupling agent (TSL8311; manufactured by Toshiba Corporation), 2 g
2'-azobis (2,4-dimethylvaleronitrile) 6
g was uniformly mixed and dispersed using a homojetter (manufactured by Tokushu Kika Kogyo Co., Ltd.).

Next, as a dispersion stabilizer, a 4% solution of methylcellulose (Methocel K35LV; manufactured by Dow Chemical Company) was used.
0 g, 5 g of a 1% solution of dioctyl sulfosuccinate soda (Nikkor OTP-75; manufactured by Nikko Chemical Co., Ltd.), and 0.3 g of sodium hexametaphosphate (manufactured by Wako Pure Chemical Industries) in 650 g of ion-exchanged water. Was used to suspend the above homogeneous dispersion in water.

The suspension was transferred to a four-necked flask and purged with nitrogen. After polymerization at a temperature of 50 ° C. and a stirring speed of 100 rpm for 24 hours, filtration and washing were repeated, and further dried to obtain suspension polymerized resin particles.

-100 parts by weight of the above-mentioned suspension-polymerized particles-8 parts by weight of carbon black (MA # 8; manufactured by Mitsubishi Kasei Kogyo) (pH: 3)-4 parts by weight of low molecular weight polypropylene (660P; manufactured by Sanyo Kasei Kogyo)・ 2 parts by weight of calixarene compound 3

The above materials were sufficiently mixed with a Henschel mixer, kneaded with a twin screw extruder, and cooled. The kneaded material was roughly pulverized by a feather mill, and then finely pulverized by a jet pulverizer. The finely pulverized product was subjected to air classification to obtain particles having an average particle size of 8 μm.

For 100 parts by weight of the obtained 8 μm particles,
0.5 parts by weight of hydrophobic silica (T-500; manufactured by Tokyo Material Co., Ltd.) was added, and the mixture was added at 1500 rpm with a Henschel mixer.
The toner 6-1 was obtained by treating the toner 6-1 for a minute. Glass transition point (Tg): 56 ° C., softening point (Tm): 87 ° C., outflow starting temperature: 78 ° C. The softening point (Tm) was measured using a perfect oven.

Example 12 Polyester resin Tuffton NE1110 (manufactured by Kao Corporation) 70 parts by weight Tufton NE382 (manufactured by Kao Corporation) 30 parts by weight Carbon black Mogal L (manufactured by Cabot) (pH: 3) 8 parts by weight Oxidizing type low Molecular weight polypropylene TS-200 (manufactured by Sanyo Chemical Industries, Ltd.) 3 parts by weight-Calixarene compound 1 2 parts by weight

A toner 6-2 having an average particle size of 8 μm was obtained from the above-mentioned material in the same manner as in the production method of Example 11. Tg: 6
3 ° C., softening point: 100 ° C., outflow starting temperature: 82 ° C.

Example 13 The graft carbon black used in this example was prepared as follows. -Glycidyl methacrylate 10 parts by weight-Styrene 60 parts by weight-Butyl methacrylate 30 parts by weight-Benzoyl peroxide 5 parts by weight

A stirrer, an inert gas introducing pipe,
The mixture was thoroughly mixed and dispersed together with deionized water containing 0.1% by weight of polyvinyl alcohol in a reaction vessel equipped with a reflux condenser and a thermometer. The dispersion was stirred at high speed to a uniform suspension.

Next, the mixture was heated to 80 ° C. while blowing in nitrogen gas, and stirring was continued at this temperature for 5 hours to carry out a polymerization reaction. Thereafter, water was removed to obtain a polymer having an epoxy group as a reactive group.

After mixing 100 parts by weight of the obtained polymer and 40 parts by weight of carbon black MA-100R (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), the mixture was kneaded and reacted at 160 ° C. using a pressure kneader. The reaction was cooled and ground to obtain a carbon black graft polymer as a colorant. (Core particles) 177 g of styrene, 90 g of butyl methacrylate, 30 g of isobutyl acrylate, 3 g of α-methylstyrene dimer (NOFMER MSD; manufactured by NOF CORPORATION), silane coupling agent (T
SL8311; 2 g of Toshiba Silicone Co., Ltd.), 100 g of grafted carbon black, 1 g of lauryl mercaptan, and 6 g of 2,2'-azobisisobutyronitrile were uniformly mixed and dispersed using a homojetter (manufactured by Tokushu Kika Kogyo Co., Ltd.).

Next, a 4% solution of methylcellulose (Methocel K35LV, manufactured by Dow Chemical Co., Ltd.) 6
0 g, 7 g of a 1% solution of dioctyl sulfosuccinate soda (Nikkor OTP-75; manufactured by Nikko Chemical Co., Ltd.), and 0.5 g of sodium hexametaphosphate (manufactured by Wako Pure Chemical Industries, Ltd.) in 1000 g of ion-exchanged water. The homodispersion was suspended in water by adjusting the rotation speed of a homogetter so that the average particle diameter was 3 to 10 μm.

The suspension was transferred to a four-necked flask and purged with nitrogen. A polymerization reaction was performed at 70 ° C. at a stirring speed of 100 rpm for 24 hours to obtain a dispersion of core particles. The core particle is Tg: 53
° C, softening point: 80 ° C, Mw / Mn: 4.0.

(Subparticles) 0.4 g of ammonium persulfate was dissolved in 800 g of ion-exchanged water and charged in a four-necked flask. After the atmosphere in the flask was replaced with nitrogen, the flask was heated to 75 ° C.
A solution prepared by dissolving 30 g of polypropylene (Viscol 660P; manufactured by Sanyo Chemical Industries, Ltd.) in 200 g of styrene and 4 g of methacrylic acid was added. The polymerization reaction was performed at a stirring speed of 500 rpm for 6 hours to obtain a 0.2 μm uniform particle dispersion (Tg: 65 ° C.).

Separately, calixarene compound 1 and hydrophobic titanium oxide (T-805; manufactured by Nippon Aerosil Co., Ltd.) are sufficiently dispersed in ethanol at a weight ratio of 1: 1.

With respect to 100 parts by weight of the solid content of the core particle dispersion,
5 parts by weight of the secondary particles and 0.5 parts by weight (solid content) of a calixarene compound / hydrophobic titanium oxide mixture are dispersed in ion-exchanged water, heated to 70 ° C. and stirred to form small particles and calixarene on the surface of the core particles. Compound / hydrophobic titanium oxide was treated.

The treated product was repeatedly subjected to filtration / washing with water and dried with a slurry drying device (Dispercoat; manufactured by Nisshin Engineering). The dried product is subjected to air classification, and the average particle size is 6
μm colored particles were obtained.

0.2 parts by weight of hydrophobic silica (H-2000; manufactured by Wacker Inc.) based on 100 parts by weight of the obtained colored particles
Is added and the mixture is treated with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 1,000 rpm for 1 minute to form toner 7
-1 was obtained (Tg: 57 ° C, elution start temperature: 73 ° C, softening point: 82 ° C).

Example 14 The colored resin particles before the post-treatment obtained in Example 13 were combined with a hybridization system (Nara Machinery Works; NHS-1).
(3) at 7,200 rpm for 3 minutes. Further, a toner 7-2 having an average particle diameter of 6 μm was obtained by performing a hydrophobic silica treatment under the same conditions as the toner 7-1 (T
g: 56 ° C., elution start temperature: 73 ° C., softening point: 82
° C).

Example 15 Pressure-fixing component ・ Polyethylene wax High wax 405MP 30 parts by weight (manufactured by Mitsui Petrochemical Co., Ltd.) ・ Paraffin wax Paraffin wax 150 70 parts by weight (manufactured by Nippon Seiwa Co., Ltd.) ・ Carbon black Mogal L (Cabot Corporation) (PH: 3) 8 parts by weight ・ Calyxarene compound 2 3 parts by weight

After mixing and melting and kneading the above substances, the mixture was granulated by a spray drier. The granules were subjected to air classification to obtain spherical particles having an average particle diameter of 8 μm.

To 100 parts by weight of the obtained particles, 0.5 part by weight of hydrophobic silica R-974 (manufactured by Nippon Aerosil Co., Ltd.) is added, and the mixture is treated with a Henschel mixer (manufactured by Mitsui Miike Kakoki) at 1000 rpm for 1 minute. By toner 8
-1 was obtained.

Example 16 Ingredients: parts by weight • polyethylene wax (High Wax 200P; manufactured by Mitsui Petrochemicals) 20 • paraffin wax (155; manufactured by Nippon Seiwa Co., Ltd.) 80 • carbon black (MA # 8: manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) ) (pH: 3) 8 ・ Magnetic magnetite (EPT-1000; manufactured by Toda Kogyo Co., Ltd.) 20

The above materials are uniformly melted and mixed at 120 ° C.
Granulation was performed with a spray dryer to obtain a fine powder having an average particle size of 8 μm.

The MM was added to 100 parts by weight of the obtained fine powder.
A / iBMA (1/9) polymer fine particles MP-4951
(Manufactured by Soken Chemical: average particle size 0.2 μm, glass transition temperature 85 ° C.) 15 parts by weight, 1 part by weight of calixarene compound 1, and 0.5 part by weight of hydrophobic alumina (RX-C; manufactured by Nippon Aerosil Co., Ltd.) Into a Henschel mixer,
The mixture was mixed and stirred at a rotation speed of 500 rpm for 2 minutes.

Next, the mixture was subjected to 7,200 rpm using a hybridization system NHS-1 of Nara Machinery Works.
m for 3 minutes, followed by air classification to obtain capsule particles having an average particle size of 8 μm.

0.1 part by weight of hydrophobic silica (R-974; manufactured by Nippon Aerosil Co., Ltd.) based on 100 parts by weight of the obtained particles
The toner 8-2 was obtained by adding 0.1 part by weight and treating with a Henschel mixer (manufactured by Mitsui Miike Koki Co., Ltd.) at 1,000 rpm for 1 minute.

Example 17 A fine powder having an average particle diameter of 6 μm was obtained by controlling the conditions for pulverization and classification in Example 1. Hydrophobic silica H-2000 (manufactured by Wacker Inc.) is used for 100 parts by weight of this fine powder.
Toner 9-1 was obtained by adding 0.3 parts by weight and 0.3 parts by weight of resin fine particles manufactured by the following method and treating the mixture with a Henschel mixer (manufactured by Mitsui Miike Koki Co., Ltd.) at 1500 rpm for 1 minute. .

(Production of Resin Fine Particles)
8 g was dissolved in 1500 g of ion-exchanged water and charged in a four-necked flask. After replacing the atmosphere in the flask with nitrogen, 75
, And 187 g of methyl methacrylate, 15 g of methacrylic acid and 120 g of styrene were added.
The polymerization reaction treatment was performed at 00 rpm for 6 hours to obtain uniform particles of 0.2 μm.

Example 18 Ingredients: 10 parts by weight of glycidyl methacrylate 60 parts by weight of styrene 30 parts by weight of butyl methacrylate 5 parts by weight of benzoyl peroxide

The above materials were thoroughly mixed and dispersed together with deionized water containing 0.1% by weight of polyvinyl alcohol in a reaction vessel equipped with a stirrer, an inert gas inlet tube, a reflux condenser, and a thermometer. The dispersion was stirred at high speed to form a uniform suspension.

Next, the mixture was heated to 80 ° C. while blowing in nitrogen gas, and the polymerization reaction was carried out by continuing stirring at this temperature for 5 hours. Thereafter, water was removed to obtain a polymer having an epoxy group as a reactive group.

100 parts by weight of the obtained polymer, 40 parts by weight of carbon black MA-100R (pH: 3.5; manufactured by Mitsubishi Kasei Kogyo), 5 parts by weight of low molecular weight polypropylene (Viscol 605P; manufactured by Sanyo Kasei Kogyo) After mixing
The mixture was kneaded and reacted under a condition of 160 ° C. using a pressure kneader. The reaction was cooled and ground to obtain a wax-containing carbon black graft polymer as a colorant.

Next, in the same reaction vessel as above, 80 parts by weight of styrene and 20 parts by weight of n-butyl acrylate which had been previously adjusted in deionized water containing 0.5% by weight of sodium dodecylbenzenesulfonate as an anionic surfactant. Was mixed with 50 parts by weight of the carbon black graft polymer, 3 parts by weight of azobisisobutyronitrile and 3 parts by weight of 2-2 ′ azobis- (2,4-dimethylvaleronitrile). The mixture was charged. K. It was mixed and stirred with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to form a uniform suspension.

Next, the mixture was heated to 65 ° C. while blowing nitrogen gas, and stirred at this temperature for 5 hours to carry out a suspension polymerization reaction, and further heated to 75 ° C. to terminate the polymerization reaction.

Apart from this, hydrophobic silica H-2000
2 parts by weight (manufactured by Wacker), silane coupling agent (T
SL8311; Toshiba Silicone Co., Ltd.) A solution prepared by dispersing 2 parts by weight in methyl alcohol was added to the above suspension, mixed, and heated at 80 ° C. for 1 hour to obtain a block-like product in which particles were fused together. Was. The filtration / washing of the block was repeated. Wash the washed product with a hot air dryer at 60 ° C 80
After leaving for 5 hours under the condition of RH%,
Drying was performed for 5 hours under the condition of H%.

With respect to 100 parts by weight of the obtained suspension polymerization aggregate, 0.5 parts by weight of calixarene compound 1, 0.3 parts by weight of hydrophobic silica H-2000 (manufactured by Wacker Inc.), and tin oxide fine particles T- 1 (Mitsubishi Materials Corporation) 0.5 parts by weight with a Henschel mixer (Mitsui Miike Kakoki) 300
After mixing and stirring at 0 rpm, the mixture was stirred at a setting of an inlet air temperature of 0 ° C. using a Kryptron system (K Kawasaki Heavy Industries K.K.).
(TM-XL type) Crushed at 18,000 rpm to obtain crushed particles having an average particle size of 6.0 μm. The temperature of the discharged air at this time was 28 ° C.

To 100 parts by weight of the obtained crushed particles, 0.2 parts by weight of hydrophobic silica H-2000 (manufactured by Wacker Inc.) is added, and the mixture is mixed with a Henschel mixer (manufactured by Mitsui Miike Kakoki) at 1500 rpm for 1 minute. Processing to make toner 11
-1 was obtained.

Example 19 Ingredients: parts by weight: styrene 70, n-butyl methacrylate 28, methacrylic acid 2,2,2-azobis- (2,4-dimethylvaleronitrile) 0.5 (first grade, manufactured by Wako Pure Chemical Industries, Ltd.)・ Carbon black (MA # 8, pH: 13; manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 10 ・ Low molecular weight polyethylene (High Wax 110P; manufactured by Mitsui Petrochemical Co., Ltd.) 3 ・ Calyxarene compound 13

The above materials were sufficiently mixed with a sand stirrer to prepare a polymerizable composition. This polymer composition was stirred in an aqueous solution of gum arabic at a concentration of 3% by weight with a stirrer T.W. K. The polymerization reaction was carried out at a temperature of 60 ° C. for 6 hours while stirring at a rotation speed of 4,000 rpm by an auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).

After the completion of the polymerization reaction, the reaction system was cooled, washed five times with water, filtered and dried to obtain spherical particles. The obtained spherical particles were further subjected to air classification to obtain black particles having an average particle size of 6 μm.

0.2 parts by weight of hydrophobic silica (H-2000; manufactured by Wacker Inc.) is added to 100 parts by weight of the obtained particles, and the mixture is treated with a Henschel mixer (Mitsui Miike Kakoki) at 1500 rpm for 1 minute. With toner 12
-1 was obtained.

Example 20 100 g of polyester resin (NE-382; manufactured by Kao Corporation)
With a mixed solvent of methylene chloride / toluene (8/2) 400
g of phthalocyanine pigment and 5 g of calixarene compound 2 were placed in a ball mill and mixed for 3 hours to be uniformly dispersed.

Next, a 4% solution of methylcellulose (Methocel K35LV; manufactured by Dow Chemical Company) as a dispersion stabilizer was prepared.
TK autohomogen mixer (0 g), an aqueous solution obtained by dissolving 5 g of a 1% solution of dioctyl sulfosuccinate soda (Nikkor OTP75; manufactured by Nikko Chemical Co., Ltd.) and 0.5 g of sodium hexametaphosphate (manufactured by Wako Pure Chemical Industries, Ltd.) in ion-exchanged water (1000 g). The number of revolutions of the uniform dispersion was adjusted to an average of 3 to 10 μm by using Tokushu Kika Kogyo Co., Ltd., and suspended in water.

Thereafter, filtration / washing was repeated, and the particles were dried by a slurry drying apparatus (Dispercoat; manufactured by Nisshin Engineering Co., Ltd.), followed by air classification to obtain colored particles having an average particle diameter of 6 μm. .

0.3 parts by weight of hydrophobic silica (H-2000 / 4; manufactured by Wacker) and 0.5 parts of hydrophobic titanium oxide (T-805; manufactured by Nippon Aerosil Co.) per 100 parts by weight of the obtained colored particles. The toner 13-1 was obtained by adding 1 part by weight and treating with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 1000 rpm for 1 minute.

Example 21 100 g of a polyester resin (NE-382; manufactured by Kao Corporation)
With a mixed solvent of methylene chloride / toluene (8/2) 400
g.

Next, a 4% solution of methylcellulose (Methocel K35LV; manufactured by Dow Chemical Company) as a dispersion stabilizer was prepared.
0 g, 5 g of a 1% solution of dioctyl sulfosuccinate soda (Nikkor OTP75; manufactured by Nikko Chemical Co., Ltd.), and 0.5 g of sodium hexametaphosphate (manufactured by Wako Pure Chemical Industries, Ltd.) in 1,000 g of ion-exchanged water. Using a mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the number of revolutions of the above uniform solution was adjusted so as to have an average of 3 to 10 μm, and the solution was suspended in water.

In this suspension, 1.0 part by weight of calixarene compound 3 previously dispersed in methanol to give a sufficiently fine particle state, and silica (R-974; manufactured by Nippon Aerosil Co., Ltd.) were added to 100 parts by weight of resin. 1.0 part by weight and 3 parts by weight of a blue vat dye (Nihonless Blue BC; manufactured by Sumitomo Chemical Co., Ltd.) were added and mixed.

The medium was heated to 80 ° C. at a rate of 2 ° C./min while vigorously stirring the mixed dispersion with an ultrasonic vibrator, and kept in this state for 1 hour.

Thereafter, the mixed dispersion was cooled, and the dispersion was repeatedly filtered and washed with water. The obtained particles were dried by a slurry drying apparatus (Dispercoat; manufactured by Nisshin Engineering Co., Ltd.), and further subjected to air classification to obtain an average particle diameter of 6%.
μm colored particles were obtained.

0.3 parts by weight of hydrophobic silica (H-2000; manufactured by Wacker Inc.) based on 100 parts by weight of the obtained colored particles
Further, 0.5 parts by weight of hydrophobic titanium oxide (T-805; manufactured by Nippon Aerosil Co., Ltd.) was added, and the mixture was treated with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 1,000 rpm for 1 minute to prepare toner 13-2. Obtained.

Example 22 (Production of Resin Solution IA Using Hydrophobic Solvent as Medium) Ingredients Parts by weight Polyester resin (manufactured by Kao Corporation; Tufton NE-382) 100 Brilliant Carmine 6B (CI. 15850) 3 Calix Allene compound 31 1 The above material was uniformly dispersed and dissolved in 400 parts by weight of methylene chloride to obtain solution IA (viscosity: 10.2 cp).

(Preparation of Aqueous Solution A) Ingredients: parts by weight • distilled water 100 • polyvinyl alcohol (polymerization degree 500; manufactured by Wako Pure Chemical Industries, Ltd.) 2 • sodium laurate 2 solution A by mixing and uniformly dissolving the above materials (Viscosity 4.1 cp).

The solution A was gradually added to 50 parts by volume of the solution IA which was stirred at 20 ° C. and 40,000 rpm with a TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). When 100 parts by volume of the solution A was added, phase inversion occurred. At that point, the addition of solution A was stopped and stirring continued for another 10 minutes.

After the completion of the stirring, the obtained dispersion was poured into distilled water. Further, in this suspension, 0.5 parts by weight of hydrophobic silica (OX50; manufactured by Nippon Aerosil Co., Ltd.) and 0.5 parts by weight of calixarene compound 1 were dispersed in methanol in advance. The mixture was added, mixed and adhered to the surface of the suspended particles. While maintaining the system at 50 ° C., the mixture was stirred at about 500 rpm to evaporate methylene chloride.

Next, filtration / washing was repeated, and the particles were dried by a slurry drying apparatus (Dispercoat; manufactured by Nisshin Engineering Co., Ltd.), followed by air classification to obtain colored particles having an average particle diameter of 6 μm.

Further, with respect to 100 parts by weight of the obtained colored particles, 0.3 parts by weight of hydrophobic silica (H-2000 / 4;
Wacker) and hydrophobic titanium oxide (T-805;
0.5 parts by weight of Nippon Aerosil Co., Ltd.) and 1,000 rpm with a Henschel mixer (Mitsui Miike Koki Co., Ltd.)
For 1 minute to obtain toner 13-3.

Example 23 Ingredients: 350 g of styrene, 150 g of n-butyl methacrylate, 20 g of methacrylic acid, 1.0 g of t-dodecyl mercaptan, 1.0 g of low molecular weight polypropylene (Biscol 605P; manufactured by Sanyo Chemical Industries) 10 g of the above-mentioned material using a sand stirrer By mixing, a polymerization composition was prepared.

Further, an aqueous dispersion medium prepared by dissolving 1500 g of ion-exchanged water, 5 g of sodium dodecylbenzenesulfonate and 5 g of ammonium persulfate was prepared. The polymerization composition was added to the aqueous solution and dispersed by stirring using a stirrer TK Auto Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotation speed of 4000 rpm.

Next, the homogeneous dispersion was transferred to a four-necked flask and purged with nitrogen.
Polymerized at 5 rpm for 5 hours, glass transition temperature (Tg) 6
An emulsion polymerization liquid having a number average molecular weight (Mn) of 15000 and a weight average molecular weight / number average molecular weight (Mw / Mn) of 14 was obtained at 2 ° C.

1000 ml of the obtained emulsion polymerization liquid (resin component 250 g), 20 g of carbon black (MA # 8; manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) and 5 of calixarene compound 1
g of water 50 wt% slurry dispersion in a beaker,
The mixture was dispersed at 3500 rpm for 5 minutes with a K-auto homomixer to obtain a uniform dispersion mixture.

Separately, a 1.0 wt% magnesium sulfate solution was prepared, and while the system was kept at 40 ° C. with stirring, the dispersion mixture was uniformly dropped into the system to coagulate the particles. Further, the temperature of the entire system was raised to 80 ° C. to improve the coagulation force.
Thereafter, the mixture was cooled to room temperature, filtered / washed repeatedly, dried, crushed, and classified by air to obtain particles having an average particle diameter of 8 μm.

0.2 parts by weight of hydrophobic silica (H-2000; manufactured by Wacker Inc.) based on 100 parts by weight of the obtained crushed particles.
Was added thereto, and the mixture was treated at 1,000 rpm for 1 minute with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain Toner 13-4.

Example 24 In addition to the composition of Example 23, a magnetic magnetite (EPT-
1000; manufactured by Toda Kogyo Co., Ltd.)
A toner 13-5 having an average particle size of 8 μm was obtained in the same manner.

Example 25 400 parts by weight of an ethanol solution and 50 parts by weight of pure water were placed in a 1-liter separable flask equipped with a stirrer, a thermometer, and a condenser.
Ten thousand parts by weight were added little by little while stirring, and the mixture was completely dissolved, followed by heating at 70 ° C.

Separately, 70 parts by weight of styrene, 25 parts by weight of n-butyl methacrylate, 5 parts by weight of methacrylic acid, 2 parts by weight of azobisisobutyronitrile, and 10 parts by weight of the graft carbon black used in Example 13 were sufficiently dissolved. ,
A dispersed solution was prepared. The solution was dropped into the above-mentioned ethanol solution over 1 hour, and then polymerized while maintaining the same temperature for 12 hours to obtain particles having an average particle diameter of 6 μm.

Separately, calixarene compound 1 and hydrophobic titanium oxide (T-805; manufactured by Nippon Aerosil Co., Ltd.) were sufficiently dispersed in ethanol at a weight ratio of 1: 1. The resulting calixarene compound / titanium oxide mixture was added to a particle dispersion cooled to room temperature to 1.5 parts by weight based on 100 parts by weight of the solid content of the particles, and then further stirred, and the calixarene compound / The titanium oxide was treated.

Thereafter, filtration / washing was repeated, and the particles were dried by a slurry drying apparatus (Dispercoat; manufactured by Nisshin Engineering Co., Ltd.), followed by air classification to obtain colored particles having an average particle diameter of 6 μm.

0.2 parts by weight of hydrophobic silica based on 100 parts by weight of the obtained colored particles (H-2000; manufactured by Wacker Inc.)
Was added to the mixture and treated at 1,000 rpm for 1 minute with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain 14-
1 was obtained.

Example 26 A 1-liter separable flask equipped with a stirrer, a thermometer and a condenser was charged with 199 parts by weight of isophthalic acid, 88 parts by weight of adipic acid, 142 parts by weight of 1,6-hexanediol and 81 parts by weight of trimethylolpropane. Parts, versatic acid glycidyl ester (Kajura E10; manufactured by Shell Chemical Co.) 150 parts by weight, and xylene 18 parts by weight,
After the temperature was raised to 180 ° C, the temperature was gradually raised to 220 ° C over 3 hours, and the reaction was carried out at the same temperature. Solid content acid value is 4KO
When H mg / g was reached, the reaction was stopped and the system was cooled.

Separately, a 1-liter separable flask equipped with a stirrer, a thermometer and a condenser is charged with deionized water 62
Then, 0 parts by weight, 8 parts by weight of polyvinyl alcohol having a degree of polymerization of 800 and a degree of polymerization of 98% were added, and the temperature was raised to 80 ° C. This is designated as dispersion medium 1.

36 parts by weight of the polyester resin, 58 parts by weight of styrene, 20 parts by weight of n-butyl acrylate, 0.8 parts by weight of divinylbenzene, 3.4 parts by weight of 2-hydroxyethyl methacrylate, 1.7 parts by weight of methacrylic acid Parts by weight, 5 parts by weight of a phthalocyanine pigment, 3 parts by weight of calixarene compound 1, 4.0 azobisisobutyronitrile
After sufficiently mixing and dispersing the parts by weight, the dispersion was added to the dispersion medium 1 and a polymerization reaction was carried out with stirring at 80 ° C. for 6 hours.

Thereafter, the reaction product was repeatedly filtered / washed with water, and the particles were dried by a slurry drying apparatus (Dispercoat; manufactured by Nisshin Engineering Co., Ltd.), followed by air classification to obtain colored particles having an average particle diameter of 6 μm. .

0.3 parts by weight of hydrophobic silica (H-2000; manufactured by Wacker Inc.) based on 100 parts by weight of the obtained colored particles
In addition, 0.5 parts by weight of hydrophobic titanium oxide (T-805; manufactured by Nippon Aerosil Co., Ltd.) was added, and the mixture was treated with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 1,000 rpm for 1 minute, thereby forming toner 14-2. Obtained.

Example 27 100 parts by weight of styrene (manufactured by Wako Pure Chemical Industries, Ltd .; reagent grade 1), 100 parts by weight of 2-ethylhexyl methacrylate (manufactured by Wako Pure Chemical Industries, grade 1), azobisisobutyronitrile (reagent grade 1) 3.0 parts by weight of an aliphatic hydrocarbon (Isoper H; manufactured by Shell Chemical Co., Ltd.) 30 by Wako Pure Chemical Industries, Ltd .;
The solution was dissolved in 0 parts by weight, and the flask was equipped with a cooling tube and a stirrer, and then charged into a four-necked flask. Nitrogen gas was bubbled for 10 minutes to replace the inside of the flask with nitrogen.

Next, the temperature of the system was raised to 75 ° C., and the polymerization was completed with stirring for 6 hours. The resin obtained is Isopar H
It was a highly viscous liquid dissolved inside. Next, 300 g of this resin was added to dichloromethane / acetone (weight ratio: 3/1).
Was dissolved in 100 g of a mixed solvent. In this solution, a non-magnetic ferrite (CuFe204-CuMn204; manufactured by Dainichi Seika Co., Ltd .: average particle size: 0.1 to 0.2 μm, oil absorption: 35 cc)
/ 100 g), and sufficiently mixed and dispersed by a vibration mill.

To 150 g of the obtained black ink, 10 g of isocyanate (Takenate D-102; manufactured by Takeda Pharmaceutical Co., Ltd.)
Was dissolved in 5 g of ethyl acetate and mixed well.
A black ink-isocyanate solution was prepared.

On the other hand, an aqueous solution of 5% by weight of gum arabic (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared and cooled sufficiently in ice water.
The black ink-isocyanate solution was put into the mixture, and the mixture was added to an auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 7000.
By rotating at 0 rpm, the black ink was turned into fine particles, and stirring was continued for 30 minutes to prepare a toner dispersion system.

Next, 20 g of an aqueous solution of 10 wt% hexanemethylenediamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, the reaction was allowed to proceed for 10 minutes, the temperature was gradually raised, the reaction was maintained at 80 to 90 ° C., and the reaction was continued for 6 hours. .

Separately, calixarene compound 7 and hydrophobic titanium oxide (T-805: manufactured by Nippon Aerosil Co., Ltd.) were previously ground at a weight ratio of 1: 1 in an aqueous medium using a sand mill (paint conditioner: manufactured by Red Devil Co.). .
1.5 parts by weight of the obtained calixarene compound / titanium oxide mixture was added to the toner dispersion system based on 100 parts by weight of the solid content of the toner, and the mixture was further stirred to treat the calixarene compound / titanium oxide on the toner surface. . filtration. After repeated washing with water, dry and classify and average particle size 8μ
m black particles were obtained.

To 100 parts by weight of black particles, 0.2 part by weight of hydrophobic silica (R-972; manufactured by Nippon Aerosil Co., Ltd.) was added, and the mixture was treated at 1,000 rpm for 1 minute with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.). Thus, a non-magnetic capsule toner 15-1 containing an aliphatic hydrocarbon solution was obtained.

Example 28 Ingredients 60 g of styrene 35 g of n-butyl methacrylate 5 g of methacrylic acid 0.5 g of 2,2-azobis- (2,4-dimethylvaleronitrile) 0.5 g Low molecular weight polypropylene (Biscol 605P; Sanyo Chemical Industries, Ltd.) 3 g) The above materials were mixed with a sand stirrer to prepare a polymerization composition.

The polymerization composition was subjected to a polymerization reaction at a temperature of 60 ° C. for 6 hours in an aqueous solution of gum arabic at a concentration of 3% while stirring at 4000 rpm using a stirrer TK Auto Homomimixer (manufactured by Tokushu Kika Kogyo KK). And spherical particles having an average particle diameter of 6 μm.

Separately, 10 g of a black disperse dye (Kayaron Preester Black S-CONC; manufactured by Nippon Kayaku Co., Ltd.) was dispersed in 100 ml of pure water, and this dispersion was added to the aqueous dispersion of the above-mentioned suspended polymer particles. The medium was heated to 75 ° C. at a rate of 2 ° C./min while vigorously stirring the mixed dispersion using an ultrasonic vibrator, and kept in this state for 1 hour. Thereafter, the system was cooled, and filtration / washing was repeatedly performed. The particles were dried by a slurry drying device (Dispercoat; manufactured by Nisshin Engineering Co., Ltd.), and further subjected to air classification to obtain colored particles having an average particle diameter of 6 μm. .

With respect to 100 parts by weight of the obtained colored particles, 1.0 part by weight of calixarene compound 6 and 0.5 part by weight of hydrophobic alumina (RFY-C; manufactured by Nippon Aerosil Co., Ltd.) were blended and thoroughly mixed and stirred. Thereafter, using a hybridization system (manufactured by Nara Machinery Co., Ltd .; NHS-O type), an immobilization treatment was performed at a peripheral speed of 60 m / sec.

To 100 parts by weight of the treated product, hydrophobic silica R-974 (manufactured by Nippon Aerosil Co., Ltd .; average particle size: 17 μm)
m) The toner 16-1 was obtained by adding to 0.1 part by weight and treating with a Henschel mixer (manufactured by Mitsui Miike Koki Co., Ltd.) at 1,000 rpm for 1 minute.

Example 29 100 g of a polyester resin (NE-382; manufactured by Kao Corporation)
With a mixed solvent of methylene chloride / toluene (8/2) 400
g of phthalocyanine pigment was placed in a ball mill and mixed for 3 hours to be uniformly dispersed.

Next, a 4% solution of methyl cellulose (Methocel K35LV; manufactured by Dow Chemical Company) as a dispersion stabilizer was prepared.
TK autohomogen mixer (0 g), an aqueous solution obtained by dissolving 5 g of a 1% solution of dioctyl sulfosuccinate soda (Nikkor OTP75; manufactured by Nikko Chemical Co., Ltd.) and 0.5 g of sodium hexametaphosphate (manufactured by Wako Pure Chemical Industries, Ltd.) in ion-exchanged water (1000 g). The number of revolutions of the uniform dispersion was adjusted to an average of 3 to 10 μm by using Tokushu Kika Kogyo Co., Ltd., and suspended in water.

Thereafter, filtration / washing was repeated, and the particles were dried by a slurry drying apparatus (Dispercoat; manufactured by Nisshin Engineering Co., Ltd.). The dried particles were further subjected to air classification to obtain colored particles having an average particle diameter of 6 μm. Obtained.

To 100 parts by weight of the obtained colored particles, 0.3 part by weight of calixarene compound 1 and hydrophobic silica (H
-2000/4: manufactured by Wacker Co.) was added, and the mixture was mixed with a Henschel mixer at 3000 rpm for 2 minutes, and then mixed with a hybridization system (Nara Machinery Co., Ltd .; NHS-O type). Speed 60m /
The immobilization process was performed in sec.

0.3 parts by weight of hydrophobic silica (H-2000; manufactured by Wacker Inc.) based on 100 parts by weight of the obtained colored particles
Toner 16-2 was obtained by adding 0.5 parts by weight of hydrophobic titanium oxide (T-805: manufactured by Nippon Aerosil Co., Ltd.) and treating with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 1500 rpm for 1 minute. .

Example 30 Monodispersed spherical styrene obtained by the seed polymerization method and n
-Butyl methacrylate copolymer polymer particles (average particle size 5 μm, glass transition temperature 54 ° C., softening point 128 ° C.,
100 parts by weight of a gelling component (containing 15% of a toluene insoluble content) and carbon black (MA # 8, manufactured by Mitsubishi Kasei Kogyo Co., Ltd.)
H: 3) Put 8 parts by weight into a Henschel mixer and 1,500 r
The mixture was mixed and stirred at a rotation speed of pm for 2 minutes to deposit carbon black on the surface of the polymer particles.

Next, the hybridization system NH
6,000 rpm using S-1 type (Nara Machinery Co., Ltd.)
m for 3 minutes to immobilize carbon black on the surface of the polymer particles.

Further, 100 parts by weight of the polymer particles treated with carbon black and MMA / iBMA (1/9)
Particles MP-4951 (manufactured by Soken Chemical Co., Ltd., average particle size 0.2 μm)
m, glass transition temperature 85 ° C.) 20 parts by weight of calixarene compound 1 and 0.5 part by weight of calixarene compound 1 were put into a Henschel mixer, mixed and stirred at 1,500 rpm for 2 minutes, and further subjected to hybridization system NHS-1.
3 minutes by treating with a mold at 7200 rpm for 5 minutes.
Colored particles having an average particle size of 6 μm having a layer structure were obtained.

To 100 parts by weight of the obtained colored particles, 0.2 part by weight of hydrophobic silica R-974 (manufactured by Nippon Aerosil Co., Ltd.) was placed in a Henschel mixer, and mixed and stirred at a rotational speed of 1500 rpm for 1 minute to prepare toner 16-. 3 was obtained.

Example 31 (Method for producing core particles) Styrene 160 was used as the polymer composition.
g, butyl methacrylate 90 g, isobutyl acrylate 3 g, low molecular weight polypropylene (Viscol 605)
P; Sanyo Chemical Industries, Ltd.) 5 g, lauryl mercaptan 2
g, 2 g of a silane coupling agent (TSL8311; manufactured by Toshiba Silicone Co., Ltd.), 10 g of carbon black (# 2300; manufactured by Mitsubishi Chemical Corporation), and magnetic magnetite (EPT-
1000; manufactured by Toda Kogyo KK) and 50 g of azobisisobutyronitrile were uniformly mixed with a sand stirrer to prepare a dispersion.

Next, as a dispersion stabilizer, 4% by weight of methylcellulose (Methocel K35LV; manufactured by Dow Chemical Company) was used.
60 g of solution, 1 wt% of dioctyl sulfosuccinate soda (Nikkor OTP-75; manufactured by Nikko Chemical Co., Ltd.) 5
g, sodium hexametaphosphate (manufactured by Wako Pure Chemical Industries, Ltd.)
Using a homojetter (manufactured by Tokushu Kika Kogyo Co., Ltd.) in an aqueous solution obtained by dissolving 3 g in ion-exchanged water (650 g), the rotation speed of the homojetter was adjusted so that the particle diameter of the uniform dispersion was 3 to 10 μm. Suspended in water.

The resulting suspension was transferred to a four-necked flask,
After the atmosphere in the flask was replaced with nitrogen, the temperature was 60 ° C. and the stirring temperature was 1
After polymerizing at 00 rpm for 24 hours, the glass transition temperature (Tg) was 54 ° C., the softening point (Tm) was 82 ° C., the number average molecular weight (Mn) was 8000, and the weight average molecular weight / number average molecular weight (M
(w / Mn) 24 core particles were obtained.

(Preparation method of fine particles) 0.4 g of ammonium persulfate was dissolved in 800 ml of ion-exchanged water and transferred to a four-necked flask.
The system was warmed to 75 ° C. 200 g of methyl methacrylate
And a mixed solution of 8 g of methacrylic acid, and polymerized at a stirring speed of 400 rpm for 6 hours.
m fine particles were obtained (Tg: 63 ° C.).

Separately, calixarene compound 1 and hydrophobic titanium oxide (T-805: manufactured by Degussa Co., Ltd.) were pulverized in advance in a water medium using a sand mill (paint conditioner: manufactured by Red Devil Co.) at a weight ratio of 1: 1. .

(Production Method of Toner) 28w of the above core particles
800 g of the t% slurry, 90 g of the 20 wt% slurry of the fine particles, and 1 g of the calixarene compound / hydrophobic titanium oxide mixture as solids were dispersed in 1000 ml of ion-exchanged water, and 5 g of ammonium persulfate was added. The dispersion was transferred to a four-necked flask, and the inside of the flask was purged with nitrogen, and reacted at 70 ° C. and a stirring speed of 160 rpm for 5 hours.

The reaction product was filtered, washed with water, and then dried to obtain fine resin particles and fine colored resin particles coated with a calixarene compound / titanium oxide.

After the obtained colored resin fine particles were subjected to air classification, 0.1 part by weight of hydrophobic silica (R-972; manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts by weight of the colored resin fine particles, and a Henschel mixer (Mitsui) was added. The mixture was treated at 1,000 rpm for 1 minute with a Miike Chemical Industry Co., Ltd. to obtain a toner 17-1 having an average particle diameter of 7 μm.

Example 32 In the core particle composition of Example 31, carbon black (#
Glass by the same method except that 10 g of a red pigment (Rake Red C; manufactured by Dainichi Seika) was changed to 10 g of magnetic pigment (EPT-1000; manufactured by Toda Kogyo) and 10 g of magnetic magnetite (EPT-1000; manufactured by Toda Kogyo). Transition temperature (Tg) 5
6 ° C, softening point (Tm) 83 ° C, number average molecular weight (Mn) 1
0000, weight average molecular weight / number average molecular weight (Mw / M
n) 26 core particles were obtained.

In addition, using the microparticles of Example 31 and the calixarene compound 1, a red toner 17-2 having an average particle diameter of 7 μm was obtained in the same manner as in Example 31.

Example 33 The classified colored resin fine particles obtained in Example 31 were treated at 7200 rpm for 3 minutes using a hybridization system NHS-1 (manufactured by Nara Machinery Co., Ltd.) to obtain fine resin particles on the surface. Was formed into a film.

To the obtained colored resin fine particles, 0.1 part by weight of hydrophobic silica (R-972; manufactured by Nippon Aerosil Co., Ltd.) was added, and the mixture was stirred at 1,000 rpm with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.). By processing for 1 minute, a toner 17-3 having an average particle diameter of 7 μm was obtained.

Example 34 (Production of Dispersing Aid) In an autoclave having a content of 10 liters, 4 kg of pure water, 80 g of tricalcium phosphate and 0.12 g of sodium dodecylbenzenesulfonate were added to prepare an aqueous medium.

On the other hand, 8 g of benzoyl peroxide (Niper B; manufactured by NOF Corporation) was mixed with 640 g of styrene and n
A solution dissolved in a mixture of 160 g of -butyl methacrylate was added to the aqueous medium and stirred.

Further, a polyester resin (NE-382;
The autoclave was purged with nitrogen, and the temperature in the system was raised to 60 ° C. The temperature is 3
The monomer containing the polymerization initiator was impregnated into the polyester resin particles while maintaining the time.

Next, t-butyl peroxypivalate
11.4 g (Pervable PV; manufactured by NOF CORPORATION) was added to the suspension. The temperature in the system was raised to 65 ° C. and maintained for 2 hours to initiate polymerization on the surface of the polyester particles. Thereafter, the temperature in the system was raised to 90 ° C. and maintained for 3 hours to complete the polymerization. After cooling, the content was taken out, pickled and washed with water to obtain modified resin particles as a dispersing aid.

(Production of Dispersion Phase Agent) In a 10 liter autoclave, 4 kg of pure water and 80 g of tricalcium phosphate were added.
g, and sodium dodecylbenzenesulfonate 0.12
g was added to obtain an aqueous medium.

In this aqueous medium, 28.6 g of t-butyl peroxypivalate (Pervable PV; manufactured by NOF Corporation) and 20 g of benzoyl peroxide (Niper B; manufactured by NOF Corporation) were mixed with 1400 g of styrene and n-butyl methacrylate. A solution dissolved in a mixed solution of 580 g and 20 g of methacrylic acid was added and stirred.

After the atmosphere in the autoclave was replaced with nitrogen, the temperature in the system was raised to 65 ° C., and the temperature was maintained for 3 hours. Further, the temperature in the system was raised to 75 ° C. and maintained for 3 hours. Thereafter, the temperature in the system was raised to 90 ° C. and maintained for 2 hours to complete the polymerization. After cooling, the content was taken out, pickled, washed with water, and dried to obtain a copolymer resin.

(Production of Domain Phase) 30 parts by weight of the copolymer resin and 5 parts by weight of a phthalocyanine pigment were melt-kneaded at 140 ° C. by a vented twin-screw kneader, then coarsely pulverized by a feather mill to obtain a domain phase. Colored particles were obtained.

(Production of Toner) 35 parts by weight of the above colored particles,
After sufficiently mixing 65 parts by weight of a polyester resin (NE-382; manufactured by Kao Corporation), 3 parts by weight of the calixarene compound 1 and 10 parts by weight of the above-mentioned modified resin particles as a dispersing aid, 140 parts by a vented twin-screw kneader. The mixture was melt-kneaded at ℃.

The kneaded material was roughly pulverized by a feather mill, finely pulverized by a jet pulverizer, and then subjected to air classification to obtain a fine blue powder having an average particle diameter of 8 μm.

0.3 parts by weight of hydrophobic silica (H-2000; manufactured by Wacker Inc.) based on 100 parts by weight of the obtained colored particles
Further, 0.5 parts by weight of hydrophobic titanium oxide (T-805; manufactured by Nippon Aerosil Co., Ltd.) was added, and the mixture was treated with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 1,000 rpm for 1 minute to produce blue toner 18-1. I got

Example 35 Ingredients: parts by weight Polyester resin (manufactured by Kao Corporation; Tufton NE-382) 100 Brilliant carmine 6B (CI15850) (preliminarily crushed product 0.1 μm) 3 Calixarene compound 1 1 After sufficient mixing, the mixture was kneaded on three rolls heated to 140 ° C.

After the kneaded material was left to cool, it was coarsely pulverized using a feather mill. 100 parts by weight of the obtained coarsely pulverized product was dissolved / dispersed in 400 parts by weight of a mixed solvent of methylene chloride / toluene (8/2) to obtain a homogeneous mixed dispersion (dispersed phase) (viscosity: 10.
1 cp: 20 ° C.).

Next, methyl cellulose is used as a dispersion stabilizer.
(Methocel K35LV; Dow Chemical Co.) 4% solution 60
g, dioctyl sulfosuccinate soda (Nikkor OTP75; manufactured by Nikko Chemical Co., Ltd.) (5 g), and sodium hexametaphosphate (Wako Pure Chemical Industries) (0.5 g) dissolved in ion-exchanged water (1000 ml) to prepare an aqueous solution (continuous phase). .

Microporous glass (manufactured by Ise Chemical Co., Ltd.)
(Hole diameter 2.0 μm, thickness 1.0 mm, ε = φ ₁₀ / φ ₉₀ =
1.1, hydrophilicity), and an emulsion solution was prepared by injecting the dispersed phase into the continuous phase (the pressure at this time was three times the critical pressure).

Thereafter, while the solution was stirred in a stirring tank, the temperature of the system was maintained at 50 ° C., and the mixed solvent of methylene chloride / toluene was removed. Further washing and filtration are repeated to wash off the dispersion stabilizer and the like adhering to the surface, and dried,
Thus, toner particles having an average particle diameter of 6.2 μm were obtained.

To 100 parts by weight of the obtained toner particles, 0.5 part by weight of hydrophobic silica R-974 (manufactured by Nippon Aerosil Co., Ltd .: average particle size: 17 μm) was put into a Henschel mixer.
The mixture was stirred at 1,500 rpm for 1 minute,
-1 was obtained.

Example 36 Ingredients: parts by weight: styrene 60, n-butyl methacrylate 35, methacrylic acid 5, 2,2-azobis- (2,4-dimethylvaleronitrile) 0.5, low molecular weight polyethylene (Sunwax 131P; 3) Carbon black (MA # 8) (pH: 3) 10 The above materials were mixed with a sand stirrer to prepare a polymerizable composition.

The polymerization reaction was carried out at a temperature of 60 ° C. for 6 hours while stirring this polymerization composition in an aqueous solution of gum arabic at a concentration of 3% using a stirrer TK Auto-Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 4000 rpm. And average particle size 6 μm
Was obtained.

Separately, calixarene compound 5 and hydrophobic titanium oxide (T-805; manufactured by Nippon Aerosil Co., Ltd.) were
It was pulverized in advance in an aqueous medium at a weight ratio of 1 using a sand mill (Paint Conditioner; manufactured by Red Devil Co., Ltd.).

The resulting calixarene compound / titanium oxide mixture was added to the toner spherical particle dispersion in an amount of 1.5 parts by weight based on 100 parts by weight of the solid content of the spherical particles. The titanium oxide was treated.

Thereafter, filtration / washing was repeated to obtain cake-like particles. The obtained cake-like particles are dried at 80 ° C. for 5 hours using a hot-air drier to aggregate the particles, particularly to fix ultrafine particles of 1 μm or less to the surface of the particles of 3 μm or more and to melt them. Aggregates were obtained.

[0266] The obtained aggregate is subjected to a Kryptron system.
(Kawasaki Heavy Industries; KTM-XL type) 10,000 rpm
To obtain a particle having an average particle diameter of 6 μm.

Further, 0.2 parts by weight of hydrophobic silica (H-2000; manufactured by Wacker Inc.) is used for 100 parts by weight of the obtained particles.
Is added and the mixture is treated with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 1,000 rpm for 1 minute to form toner 2
0-1 was obtained.

Example 37 parts by weight Styrene-n-butyl methacrylate resin (softening point: 132 ° C., glass transition temperature: 60 ° C.) 100 carbon black (MA # 8: manufactured by Mitsubishi Kasei Kogyo) (pH: 3) 8 low Molecular weight polypropylene (Viscol 550P; manufactured by Sanyo Chemical Industries) 3 Nigrosine dye (Bontron N-01; manufactured by Orient Chemical Industries) 5 Calixarene compound 6 1

After thoroughly mixing the above materials with a ball mill,
The mixture was kneaded on three rolls heated to 140 ° C. The kneaded product was allowed to cool, coarsely pulverized, and further finely pulverized by a jet mill. Next, air classification was performed to obtain toner particles having an average particle diameter of 8 μm.

To 100 parts by weight of the toner particles, hydrophobic silica R-974 (0.2 parts by weight) was post-treated with a Henschel mixer to obtain toner 21-1.

Example 38 Toner 4-1 obtained in Example 9 was used as one component.

Example 39 (Production of core particles) Monodisperse spherical styrene-n-butyl methacrylate copolymer polymer particles obtained by a seed polymerization method (average particle size: 8 μm, coefficient of variation: 5%, 100 parts by weight of a charge transport material (A-1) having the following structure and 10 parts by weight of a charge transport material (A-1) having the following structure were put into a 10-liter Henschel mixer, and rotated at 1500 rpm. The mixture was stirred for minutes and the charge transport material (A-1) was adhered to the surface of the polymer particles.

Next, a Nara Machine Hybridization System NHS-1 was used for 3 minutes at 9000 rpm to immobilize the charge transporting substance (A-1) on the surface of the polymer particles to obtain nucleus particles.

Charge transport material (A-1)

Embedded image

(Production of fine particles) ・ Styrene monomer (manufactured by Wako Pure Chemical Industries) 70 parts by weight ・ n-butyl methacrylate (manufactured by Wako Pure Chemical Industries) 30 parts by weight ・ 2,2′-azobis (2,4- Dimethylwareronitrile) (v-65) (manufactured by Wako Pure Chemical Industries, Ltd.) 1.5 parts by weight-10 parts by weight of the above charge transporting substance (A-1)-30 parts by weight of the following photoconductive substance (B-1)・ 2 parts by weight of calixarene compound 5 ・ 100 parts by weight of acetone

[0276]

Embedded image

The above materials were placed in a ball mill and mixed for 3 hours to prepare a dispersion. As a dispersion medium, distilled water 100
A solution obtained by adding an appropriate amount of 2% of completely saponified polyvinyl alcohol (polymerization degree: about 1000) and 1% of sodium dodecylbenzenesulfonate to 0 ml was used.

The above dispersion was treated with T.I. Using a K homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the turbine was mixed and dispersed at 10,000 rpm while gradually increasing the rotation speed from 1500 rpm. The dispersion mixture was heated at 80 ° C. for 5 hours while stirring at the final number of revolutions to carry out polymerization.

After the completion of the polymerization, the polymer was filtered with a centrifugal dehydrator and washed with pure water 7 to 8 times. The washed material was vacuum-dried and pulverized to obtain styrene-acryl fine particles having an average particle size of 0.5 μm. The fine particles had a number average molecular weight (Mn) of 8000, a molecular weight distribution (Mw / Mn) of 24, a glass transition point of 60 ° C, and a softening point of 120 ° C. 100 parts by weight of core particles and 10 parts by weight of fine particles were placed in a 10-liter Henschel mixer and mixed and stirred at a rotation speed of 1500 rpm for 2 minutes to cause the fine particles to adhere to the surfaces of the core particles. Next, treatment was performed at 9000 rpm for 3 minutes using a Nara Machine Hybridization System to form fine particles on the surface of the core particles.
A coating layer was formed to obtain a monodispersed photoconductive toner 22-1 having an average particle size of 9 μm.

Production of Carriers As carriers to be mixed with the electrostatic latent image developing toner obtained in the above Examples and Comparative Examples, four types of carriers A to D produced as described below were used. .

(Carrier A) 100 parts by weight of polyester resin (manufactured by Kao Corporation; NE-1110), inorganic magnetic powder (TDK)
600 parts by weight of MFP-2) and 2 parts by weight of carbon black (MA # 8; manufactured by Mitsubishi Kasei) were thoroughly mixed and ground using a Henschel mixer.

Next, the pulverized product was melt-kneaded using an extruder kneader set at a cylinder portion of 180 ° C. and a cylinder head portion of 170 ° C.

The obtained kneaded material was cooled and coarsely pulverized.
The mixture was finely pulverized with a jet mill and further classified using an air classifier to obtain a binder type carrier A having an average particle size of 55 μm.

(Carrier B) Ferrite carrier core
(Powdertech; F-300) Rolled surface
A carrier C having an average particle size of 50 μm was obtained by coating with a thermosetting silicone resin using a (Spirac coater manufactured by Okada Seiko Co., Ltd.).

(Carrier C) Ferrite carrier core
(Powdertech; F-300) was coated with polyethylene by the surface polymerization coating method, and the average particle size was 51 μm.
Was obtained.

(Carrier D) Using the same core material as Carrier B, coating was performed by a dipping method using a thermosetting acrylic-modified silicone resin to obtain Carrier D having an average particle size of 50 μm.

Evaluation (Measurement of Particle Size) The particle sizes of the toner and the carrier were measured as follows.

(1) Toner Particle Size The average toner particle size was measured using a Coulter Counter TA-II.
Using a mold (manufactured by Coulter Counter Co., Ltd.), the relative weight distribution by particle size was measured with a 100 μm aperture tube.

(2) Carrier Particle Size The carrier particle size was measured using SALD 1100 (manufactured by Shimadzu Corporation), and the average particle size was determined.

Measurement of Charge Amount and Low Chargeable Toner Amount The charge amount and low charge toner amount were measured using an apparatus having the structure shown in FIG. The measurement was performed under the following conditions.

1) Measurement of Charge Amount The rotation speed of the magnet roll (3) was set to 1000 rpm, and a developer after stirring the carrier for 30 minutes was used.
1 g of this developer is weighed with a precision balance, and the conductive sleeve
(2) Put it evenly on the entire surface.

Next, a bias voltage of 3 KV was applied from the bias power supply (4) to the same polarity as the charged potential of the toner, and the magnet roll (3) was rotated for 30 seconds.
(3) Read the capacitor potential Vm at the time of stop. At this time, the weight (Mi) of the separated toner (7) attached to the cylindrical electrode (1) is measured by a precision balance, and the average toner charge amount is determined.

A developer having a toner mixing ratio of 5 wt% was prepared and exposed for 24 hours under an environment of measurement environment of 23 ° C. and a relative humidity of 55%, and then mixed and stirred for 30 minutes on a rotating base to evaluate.

2) Measurement of Low Charged Toner Amount In the measurement of the amount of charge, the same measurement was carried out with the conductive sleeve (2) dropped to the ground without applying a bias voltage. How much cylindrical electrode (1)
The amount of low charge toner was determined by measuring whether the toner was blown off. The total amount of toner in the developer was ranked as follows.

×: Greater than 2 wt% Δ: 1-2 wt% Δ: Less than 1 wt%

Environmental stability of charge amount (Q / M) Charge amount (Q _{L / L} ) after exposing the above-mentioned developer at 5 ° C. and relative humidity of 15% (L / L) for 24 hours, Charge amount after exposure for 24 hours at 35 ° C and 85% relative humidity (H / H)
(Q _{H / H} ) and the charge amount (Q _{N / N} ) after exposure to 23 ° C. and a relative humidity of 55% (N / N) for 24 hours.

The following formula

(Equation 1)

(Equation 2) The values A and B were calculated according to the following and ranked as follows.

:: A and B are both 15% or less Δ: Either A or B is 15% or more ×: A and B are both 15% or more

[0299] The predetermined toner and the carrier shown in image formation evaluation in Table 4 and Table 5 were mixed at a ratio of toner / carrier = 5/95, was prepared a two-component type developer. Using this developer, evaluation was performed using the models shown in the table.

(1) Fogging on Image As described above, image formation was performed using the above-described copying machine with various combinations of toner and carrier. Regarding the fog on the image, the toner fog on the white background image was evaluated and ranked. Although it can be practically used at the rank of Δ or higher, it is preferable that the rank is at least ○.

(2) Printing durability test Using a chart having a B / W ratio of 6%, a printing durability test of 10,000 sheets was performed to evaluate images and fog. The results are shown in Tables 4 and 5. In the table, ○ means a practically usable area, and × means a practically problematic area.

(3) Translucency Examples 5, 8, 10, 20, 21, 22, 26, 29,
At 34 and 35, a light transmission test was also performed. The translucency was visually evaluated for the color vividness of the projected image when the fixed image on the OHP sheet was projected by the OHP projector. The results are shown in Tables 4 and 5. In the table, ○ means a practically usable area in terms of color reproduction.

The above results are shown in Tables 4 and 5.

[0304]

[Table 4]

[0305]

[Table 5]

The evaluation machines in the table are copying machines EP-57
0Z, copier EP-350, digital full-color copier CF-70, printer SP-500, printer SP-1
01, the copying machine EP-50, the copying machine EP-350Z, and the copying machine EP-410 are manufactured by Minolta Camera Co., Ltd., and the copying machine PC-30 is manufactured by Canon Inc.

The developing units shown in FIG. 2 in Table 5 were mounted on a copying machine (EP350) (manufactured by Minolta Camera Co.) and used. The developing device shown in FIG. 2 will be briefly described below.

FIG. 2 shows an example of a two-component developing device. The two-component developing device (61) has a photosensitive drum (100) and a casing (64) that are driven to rotate in the direction of the arrow (a). At the front of the casing (64), the photosensitive drum (10
0) is accommodated in the developing sleeve (66).
The developing sleeve (66) is a cylindrical body made of a nonmagnetic conductive material, to which a developing bias (Vb) is applied, and which can be rotationally driven in a direction indicated by an arrow by a driving source (not shown).

A magnetic roller is provided inside the developing sleeve (66).
On the magnetic roller (67), a plurality of magnets having magnetic poles extending in the axial direction are arranged on the outer peripheral portion so that N and S stations are alternately positioned.

A spike height regulating member (68) is provided obliquely rearward and downward of the developing sleeve (66), and its tip end faces the outer peripheral surface of the developing sleeve (66) with a predetermined spike height regulating gap. A developer pool is formed on the upstream side in the direction.

A toner supply roller (toner carrier) (70) is arranged behind the developing sleeve (66) with a predetermined supply gap facing the developing sleeve (66).

The toner supply roller (70) is made of a non-magnetic conductive material similarly to the developing sleeve (66), and a fine concave portion is formed on the outer peripheral portion by blasting, etching, or the like. It can be driven to rotate in the direction of the arrow.

[0313] The toner supply roller (70) has a minus side of a direct current (Vss) provided with a blast side and an alternating current (Vrms).
s) is applied as a recovery bias (Vs),
In particular, the DC (Vss) output is variable.

Further, the tip of a toner regulating blade (toner regulating member) (71) attached to the casing (64) is pressed against the outer peripheral surface of the upper portion of the toner supply roller (70).

Toner supply roller (70), regulating blade
A toner hopper is formed at a rear portion of the casing (64) partitioned by (71), and transport blades (76) and (78) are rotatably arranged.

The developing device (61) having the above-described configuration is such that a toner hopper is loaded with toner, a developing sleeve (66), and a starter in which toner and carrier are mixed at a fixed ratio in a developer reservoir.

The photoconductive toner 22 obtained in Example 39
A two-component developer was prepared using 20 g of -1 and 380 g of carrier A. In the evaluation measuring device shown in FIG. 3, image development evaluation was performed using a developing device for a copying machine EP-360 (manufactured by Minolta Camera Co., Ltd.) as a developing device (12).
A thin layer of photoconductive toner is formed on the conductive substrate (11) by the developing device, and a corona discharge machine (13) is formed thereon in a dark place.
To perform a corona charging of -5 KV, and then perform exposure with a halogen lamp (14) through a document slide (15) to form an electrostatic latent image, and then place a plain paper (16) thereon.
And +5 KV from the paper side with a corona discharger (17)
Charge the photoconductive toner in the latent image area on plain paper
(16) The image was transferred onto the substrate and further fixed using heat fixing (not shown) to obtain a clear blue-violet positive image.

[0318]

According to the present invention, there is provided a negatively chargeable toner for developing electrostatic latent images using a novel charge control agent calixarene compound containing no heavy metal. The toner of the present invention is excellent in charge rising, charge stability, spent resistance, and environmental resistance. According to the present invention, a toner excellent in color reproducibility and translucency can be provided.

[Brief description of the drawings]

FIG. 1 shows an apparatus for measuring the amount of charge and the amount of low-charge toner.

FIG. 2 is a schematic configuration diagram of a developing device.

FIG. 3 is a schematic configuration diagram of an evaluation measuring device.

[Explanation of symbols]

1: cylindrical electrode, 2: conductive sleeve, 3: magnet roll, 4:
Bias power supply, 11: conductive substrate, 12: developing device, 1
3: Corona discharger, 14: Halogen lamp, 15: Slide, 16: Plain paper, 17: Corona discharger, 61: Two-component developing device, 64: Casing, 66: Sleeve, 67:
Magnet roller, 68: Hotaka regulating member, 70: supply roller,
71: toner regulating member, 76: transport blade, 78: transport blade, 100: photosensitive drum

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-201378 (JP, A) JP-A-5-127426 (JP, A) JP-A-4-295862 (JP, A) JP-A-5-29586 119535 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03G 9/08

Claims (2)

(57) [Claims] 1. A compound represented by the following general formula [I]: [Wherein, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or — (CH ₂ ) m COOR ₃ (R ₃ represents a hydrogen atom or a lower alkyl group, and m is an integer of 1 to 3. ); N represents an integer of 1 to 7. A toner for developing an electrostatic latent image, comprising a calixarene compound represented by the formula: 2. The following general formula [I]: [Wherein, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or — (CH ₂ ) mCOOR ₃ (R ₃ represents a hydrogen atom or a lower alkyl group, and m is an integer of 1 to 3. Represents an integer from 0 to 8. ] A first potash <br/> Kkusuaren compounds represented by, n in the above general formula [I] is 1
~ 7 and n is different from the first calixarene compound
A toner for developing an electrostatic latent image , comprising a mixture with a second calixarene compound .