JPH06138696A - Positively chargeable toner - Google Patents

Abstract

PURPOSE:To provide a positively chargeable toner which is not excessively charged even in an environment at low humidity and does not cause ununiformity in a toner coat layer on a developing sleeve in a one-component developing system or the lowering of image density, fog, etc., in a two- component developing system. CONSTITUTION:This positively chargeable toner contains a compd. having a substituent represented by formula I or II in one molecule or a compd. having a substituent represented by the formula I or II and an amino group in the same molecule. In the formulae I, II, each of R1 and R2 is H, alkyl or aryl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used as a developer for electrophotography, electrostatic printing and the like.

[0002]

[Prior art]

(First and Second Inventions) Conventionally, as an electrophotographic method, US Pat. No. 2,297,691 and JP-B-42-2
3910 (US Pat. No. 3,666,363) and JP-B-43-24748 (US Pat.
No. 071,361), a photoconductive material is generally used to form an electric latent image on a photoreceptor by various means, and then the latent image is formed. After developing with developing powder (hereinafter referred to as toner), and transferring the toner image to a transfer material such as paper as necessary, heating, pressure,
A copy is obtained by fixing with a pressure heat fixing roller or solvent vapor. In addition, when there is a step of transferring a toner image, a step for removing the residual toner on the photoconductor is usually provided. Examples of a developing method for visualizing an electric latent image with toner include magnetic brush method described in US Pat. No. 2,874,063 and US Pat. No. 2,618,552. The described cascade development method and US Pat. No. 2,22.
The powder cloud method described in US Pat. No. 1,776, the method using a conductive magnetic toner described in US Pat. No. 3,909,258, and the like are known.

As a toner applied to these developing methods, a fine powder in which a dye or a pigment is dispersed in a natural or synthetic resin has been conventionally used. For example, 1 to 30 μm of a colorant dispersed in a binder resin such as polystyrene
The finely pulverized particles are used as a toner. Further, as the magnetic toner, those containing magnetic particles such as magnetite are used, and in the case of a system using a so-called two-component developer, the toner is usually composed of glass beads and carrier particles such as iron powder. Used as a mixture.

Examples of positive charge control agents used in such dry developing toners are generally quaternary ammonium compounds and organic dyes, particularly basic dyes and salts thereof, and nigrosine base and nigrosine are often positive. Used as a charge control agent. These are usually added to a thermoplastic resin, heated, melted and dispersed, finely pulverized, and adjusted to an appropriate particle size as needed, and used. However, these charge control agents tend to cause a phenomenon in which the charge controllability is deteriorated due to mechanical shock, friction, changes in temperature and humidity conditions, and the like. Therefore, when a toner containing these as a charge control agent is developed using a copying machine, as the number of copying increases,
It may cause deterioration of the toner during running. Further, since it is extremely difficult to uniformly disperse these charge control agents in the thermoplastic resin, there is a problem in that there is a difference in the triboelectric charge amount between the toner particles obtained by pulverization. There is.

Therefore, various methods have been conventionally used for more uniform dispersion. For example, when a basic nigrosine dye is used, in order to improve the compatibility with the thermoplastic resin, it is salted with a higher fatty acid and used, but the unreacted fatty acid or a dispersion component of the salt is often used. It is exposed on the surface of the toner and contaminates the carrier or the toner carrier, which causes deterioration of the fluidity of the toner, fog, and deterioration of the image density. Alternatively, in order to improve the dispersibility of these charge control agents in the resin, a method of mechanically pulverizing and mixing the charge control agent powder and the resin powder in advance and then hot-melt kneading has been used. In reality, it is impossible to avoid the original dispersion failure, and practically sufficient charging uniformity has not been obtained yet. Further, by copolymerizing or graft-polymerizing a positively chargeable monomer such as dimethylaminoethyl methacrylate into the binder resin, the binder resin itself is made positively chargeable by introducing an amino group. Attempts have also been made to give a uniform charge to the toner.

However, the positive chargeability of the binder resin as described above is not constant, and the magnitude of the frictional force received between the toner particles, between the toner and the carrier, or between the toner and the toner carrier such as the sleeve, and It may vary greatly depending on the friction probability, and it may be difficult to always give a constant and stable positive charge to the toner. Therefore, the positive chargeability of the toner when the proper friction cannot be obtained is very unstable, and the copy image obtained by the toner becomes an image with a lot of fog and scattering. On the other hand, when excessive friction is applied, the amount of positively charged charges on the toner surface becomes too large, and only an image with a lot of roughness and a low density can be obtained.

As a method for obtaining a developer having a positive charge controllability, there is a proposal in Japanese Patent Publication No. 53-22447. This is a method in which a metal oxide powder treated with aminosilane is contained as a component of the developer. However, when this method was examined in detail, for example, colloidal silica, alumina, titanium dioxide, zinc oxide, iron oxide, γ
-When a developer is obtained by treating ferrite and magnesium oxide with various aminosilane compounds and obtaining a developer according to the examples described in the specification, a developer showing practically sufficient properties in any combination is used. Not obtained,
It became clear that there were some problems. That is,
Many developers are unable to retain the properties that are desirable for faithfully reproducing latent images for long periods of time. Initially, even if the desired performance is exhibited, the initial characteristics cannot be retained in a continuous use for a long period of time, which makes the product unusable. That is, fogging occurs, toner scatters around edges in copying line images, and image density also decreases. Further, as another problem, when the development and transfer are performed, the image density is reduced, line images are scattered, white spots, fog, and the like occur when the environmental conditions of high temperature and high humidity are reduced.

As another method for obtaining a developer having a positive charge controllability, there is a method described in JP-A-59-201063. This is a method in which, instead of the metal fine powder treated with aminosilane described above, a silicic acid fine powder treated with silicone oil containing an amine in a side chain is contained as a constituent component of a developer. By this method, the above-mentioned problems of the developer containing the fine metal powder treated with aminosilane can be compensated, and a developer having substantially sufficient characteristics can be obtained.

[0009]

However, as copiers and printers using the electrophotographic process have become popular year by year, they have been used in more severe environments. Above all, in a low humidity environment, the toner is excessively charged and various problems occur. In the one-component developing method using magnetic toner or the like, for example, a phenomenon occurs in which the toner coating layer on the developing sleeve becomes non-uniform. On the other hand, in the two-component developing method, phenomena such as image density and fog occur. Therefore, the object of the present invention is to prevent excessive charging even in a low humidity environment, and to prevent unevenness of the toner coat layer on the developing sleeve in the one-component developing system, image density in the two-component developing system, fog, etc. It is to provide a positively chargeable toner that does not generate.

[0010]

[Means for Solving the Problems]

(First and Second Inventions) The above objects can be achieved by the present invention described below. That is, the first invention of the present invention is a positively chargeable toner characterized by containing a compound having a substituent of the following structure (1) or (2) in the molecule.

[Chemical 9]

[Chemical 10] (R ₁ , R ₂ : hydrogen, alkyl group or aryl group)

A second aspect of the present invention is a positively chargeable toner characterized by containing a compound having a substituent of the above structure (1) or (2) and an amino group in the same molecule. Is. As a form in which each of the above compounds is contained in the toner, a form in which particles treated with the above compound are mixed with the toner and contained is preferable.

[0012]

[Action]

(First and Second Inventions) The present inventors have found that when a fine powder of silicic acid treated with a silicone oil containing an amine in a side chain is contained as a component of a developer, the toner is As a result of intensive research to solve the problems of the prior art that excessive charging causes various problems, as a result, when a compound having a substituent having a specific structure is contained in the toner, or when a compound having a specific structure is substituted, The present invention has been completed by discovering that if a compound having a group and an amino group is contained in the toner, the toner will not be excessively charged even in a low humidity environment due to the action due to the structure of the specific substituent. did.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to preferred embodiments of the present invention. (First Invention) The first invention of the present invention is characterized in that the toner contains a compound having a substituent having the following structure (1) or (2) in the molecule.

[0014]

[Chemical 11]

[Chemical 12] (R ₁ and R ₂ : hydrogen, alkyl group or aryl group)

Examples of the substituent of the above structure (1) include:
The following are listed.

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

[Chemical 19]

[Chemical 20]

Examples of the substituent of the above structure (2) include:
The following are listed.

[Chemical 21]

As the compound for treating the particles used in the positively chargeable toner of the present invention, any compound having a substituent of the above structure (1) or (2) in the molecule can be used. However, a compound having a substituent of structure (1) on the side chain of a polymer (or oligomer) or a compound having a substituent of structure (1) or (2) on the coupling agent molecule is preferable. The polymer / oligomer having the substituent of the structure (1) in the side chain is not particularly limited, but among them, a silicon-based polymer / oligomer such as silicon varnish or silicon oil is preferable. Silicon-based Polymer Having Substituent of Structure (1) in Side Chain /
As the oligomer, those having a structure generally represented by the formula (3) can be used.

[0018]

[Chemical formula 22] (Here, R ₁ and R ₃ represent hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₂ represents an alkylene group or a phenylene group, R ₄ and R ₅ represent hydrogen,
Represents an alkyl group or an aryl group. Also, R ₂ may be omitted. However, the above alkyl group, aryl group, alkylene group and phenylene group may contain an amine,
Further, it may have a substituent such as halogen within a range not impairing the charging property. R ₆ is a substituent of structure (1) or structure (2), m is a number of 1 or more, and l (el)
Is a positive number including 0. )

As the derivatives, all known compounds such as vinyl group, mercapto group, methacryl group, glycid group and ureido group can be derived as long as they do not interfere with the charge controllability of the above compounds, and their derivatives. Can be used. The nitrogen atom equivalent of the silicone oil used in the present invention is preferably 10,000 or less, and 300 to 2
000 is preferable. The nitrogen atom equivalent here is a value obtained by dividing the molecular weight by the equivalent per nitrogen atom (g / eqio) by the number of nitrogen atoms per molecule. These are 1
You may use it by 1 type or a mixed system of 2 or more types.

As the coupling agent having the substituent of the structure (1) or the structure (2), a silane coupling agent or a titanium coupling agent is preferable. As the silane coupling agent having a substituent of the structure (1) or (2) or the titanium coupling agent, generally,
Each has a structure represented by the following formulas (4) and (5). _{R m Si-Y n ··· (} 4) R m Ti-Y n ··· (5) wherein, R represents an alkoxy group or a halogen atom,
Y is a group having a substituent of the structure (1) or (2), m and n are integers of 1 to 3, and m + n = 4.

As the particles used when the compound having a substituent of the structure (1) or (2) mentioned above is contained in the particles and mixed with the toner, the following inorganic fine particles and resin particles can be mentioned. . As inorganic fine particles, N
a, Mg, Al, Si, K, Ca, Sc, Ti, V, C
r, Mn, Fe, Co, Ni, Cu, Zn, Ga, G
e, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh,
Examples thereof include metals such as Pd, Ag, Cd, In, Sn, Ba, Ce and Pb, particles of oxides, sulfides, complex oxides and salts of these metals, and carbon black. Among these, oxides or complex oxides of Al, Si and Ti are particularly preferable.

Examples of the organic fine particles include styrene resin, acrylic resin, polyester resin, butanediene resin,
Examples thereof include fine particles of resins such as polyurethane resin, polyamide resin, epoxy resin, silicone resin, polyethylene, polypropylene and polyvinylidene fluoride, and fine particles of fatty acids, fatty acid metal salts and fatty acid esters. The specific surface area of these particles is 0.1 to 500.
m ² / g is preferable, and more preferably 0.5 to 450 m ^2.
/ G, more preferably 1 to 400 m ² / g. Further, the treatment amount for the particles is preferably 0.1 to 70 parts by weight with respect to 100 parts by weight of the particles. The particles containing the compound having the substituent of the structure (1) or (2) exert an effect when the amount of toner is 0.01 to 20% by weight, particularly preferably 0.02 to 10% by weight,
More preferably, the effect is obtained when 0.03 to 5% by weight is added.

(Second Invention) In the second invention of the present invention, the toner contains a compound having a substituent of the following structure (1) or (2) and an amino group in the same molecule. It is characterized by

[0024]

[Chemical formula 23]

[Chemical formula 24] (R ₁ and R ₂ : hydrogen, alkyl group or aryl group)

Examples of the substituent of the above structure (1) include:
The following are listed.

[Chemical 25]

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

[Chemical 30]

[Chemical 31]

[Chemical 32]

Examples of the substituent of the above structure (2) include:
The following are listed.

[Chemical 33]

The amino group may be any of primary amine, secondary amine, tertiary amine and quaternary amine. For example, the followings are listed.

[0028] _{-NH 2 -NH-CH 3, -NH} -C 2 H 5, -NH-C 3 H 7 -N (CH 3) 2, -N (C 2 H 5) 2, -N-C 2 _{H 4 -NH 2 -N (C 3} H 6) 2, -N-C 2 H 4 -N (CH 3) 2 -N (C 4 H 9) 2 -N (CH 3) 3 + Cl -, - N (CH ₃ ) ₃ ⁺・ HCO
^{_{3 - -N (C 2 H 5}} ) 3 + Cl -, -N (C 2 H 5) 3 + · HC
^{_{O 3 - -N (C 3 H}} 7) 3 + Cl - -N (C 4 H 9) 3 + Cl -

[Chemical 34]

As the compound for treating the particles used in the positively chargeable toner of the present invention, any compound having the substituent of the above structure (1) or (2) and an amino group in the same molecule can be used. Although all can be used, compounds having a substituent of structure (1) in the polymer (or oligomer) side chain or a compound having a substituent of structure (1) or (2) on the coupling agent molecule can be used. preferable. At this time,
A substituent of structure (1) or (2) and an amino group may be present in the same side chain, or a substituent of structure (1) or (2) and an amino group may be present in another side chain. Each may exist.

The polymer / oligomer having the substituent of the structure (1) in the side chain is not particularly limited, but among them, a silicon-based polymer / oligomer such as silicon varnish or silicon oil is preferable. As the silicon-based polymer / oligomer having the substituent of the structure (1) in the side chain, those having a structure generally represented by the formula (3), (4 ′) or (5 ′) can be used. .

[0031]

[Chemical 35]

[0032]

[Chemical 36]

[0033]

[Chemical 37] (Here, R ₁ and R ₃ represent hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₂ represents an alkylene group or a phenylene group, R ₄ and R ₅ represent hydrogen,
Represents an alkyl group or an aryl group. Also, R ₂ may be omitted. However, the above alkyl group, aryl group, alkylene group and phenylene group may contain an amine,
Further, it may have a substituent such as halogen within a range not impairing the charging property. R ₆ is a substituent of structure (1) or structure (2), and R ₇ is a substituent having an amino group.
Further, m is a number of 1 or more, and l (ell) is a positive number including 0. )

As the derivatives, all known ones such as vinyl group, mercapto group, methacryl group, glycid group and ureido group can be derived as long as they do not interfere with the charge controllability of the above compound group, and their derivatives. Can be used. The nitrogen atom equivalent of the silicone oil used in the present invention is preferably 10,000 or less, and 300 to 2
000 is preferable. The nitrogen atom equivalent here is a value obtained by dividing the molecular weight by the equivalent per nitrogen atom (g / eqio) by the number of nitrogen atoms per molecule. These are 1
You may use it by 1 type or a mixed system of 2 or more types.

As the coupling agent having the substituent of the structure (1) or the structure (2), a silane coupling agent or a titanium coupling agent is preferable. As the silane coupling agent having a substituent of the structure (1) or (2) or the titanium coupling agent, generally,
Each has a structure represented by the following formulas (4) and (5). _{R m Si-Y n ··· (} 4) R m Ti-Y n ··· (5) wherein, R represents an alkoxy group or a halogen atom,
Y is a group having a substituent of the structure (1) or (2), m and n are integers of 1 to 3, and m + n = 4.

The following inorganic fine particles and resin particles are used as the particles used when the compound having the substituent of the structure (1) or (2) and the amino group mentioned above is contained in the particles and mixed with the toner. I can name it. As the inorganic fine particles, Na, Mg, Al, Si, K, Ca, Sc, T
i, V, Cr, Mn, Fe, Co, Ni, Cu, Zn,
Ga, Ge, Sr, Y, Zr, Nb, Mo, Tc, R
u, Rh, Pd, Ag, Cd, In, Sn, Ba, Ce
And metal such as Pb, particles of oxides, sulfides, complex oxides and salts of these metals, and carbon black. Among these, oxides or complex oxides of Al, Si and Ti are particularly preferable.

The organic fine particles include styrene resin, acrylic resin, polyester resin, butanediene resin,
Examples thereof include fine particles of resins such as polyurethane resin, polyamide resin, epoxy resin, silicone resin, polyethylene, polypropylene and polyvinylidene fluoride, and fine particles of fatty acids, fatty acid metal salts and fatty acid esters. The specific surface area of these particles is 0.1 to 500.
m ² / g is preferable, and more preferably 0.5 to 450 m.
² / g, more preferably 1 to 400 m ² / g. Further, the treatment amount for the particles is preferably 0.1 to 70 parts by weight with respect to 100 parts by weight of the particles. When the amount of the particles containing the compound having the substituent of the structure (1) or (2) and the amino group is 0.01 to 20% by weight with respect to the toner, the effect is exhibited, and particularly preferably, 0.02 to 10% by weight, more preferably 0.0
It is effective when added in an amount of 3 to 5% by weight.

(First and Second Inventions)

Further, the positively chargeable toner of the present invention is particularly effective in the case where a developing sleeve for toner coating has a plurality of spherical imprints on the surface of the sleeve. As a method of obtaining the surface condition,
A blasting method with regular particles can be used. As the regular particles used at this time, for example, various hard spheres having a specific particle diameter and made of metal such as stainless steel, aluminum, steel, nickel and brass, or various hard spheres such as ceramic, plastic and glass beads are used. You can do it. Further, the developing sleeve used in the present invention can also be obtained by further blasting with fixed particles on the surface having random irregularities formed by blasting with irregular particles of various hard spheres as described above. You can Further, a blast treatment method in which irregular particles and regular particles are used at the same time is also possible. Arbitrary abrasive grains can be used as the amorphous particles. It is also possible to form a plurality of spherical trace depressions having substantially the same diameter R by blasting the surface of the sleeve by using the regular particles having a specific particle diameter.

In the present invention, the diameter R of the plurality of spherical dents formed on the surface of the sleeve is preferably 20 to 250 μm, and if the diameter R is less than 20 μm, contamination with components in the magnetic toner increases, which is not preferable. . On the other hand, if the diameter R exceeds 250 μm, the uniformity of the toner coat on the sleeve is deteriorated, which is not preferable. The regular particles have a substantially curved surface and have a diameter / minor axis ratio of 1 to 2 (preferably 1 to 1.5, more preferably 1 to 1.5).
Spherical or spheroidal particles of 1.2) are preferred. Therefore, it is preferable that the regular particles used for the blast treatment of the sleeve surface have a diameter (or major axis) of 20 to 250 μm.

For the pitch P and the surface roughness d of the unevenness of the sleeve surface which has been subjected to the blast treatment with the regular particles, the surface of the sleeve is measured by using a fine surface roughness meter (sales agency, Taylor Hobson Co., Kosaka Laboratory, etc.). Surface roughness d is
10-point average roughness (RZ) "JIS B 0601". A straight line that is parallel to the average line of the reference length L extracted from the cross-section curve and that passes through the third peak from the highest and a straight line that passes through the third trough from the deep
The distance between two straight lines is represented by a micrometer (μm). Here, the reference length is L = 0.25 mm.

The pitch P is 0.
Those having a height of 1 μm or more are counted as one mountain, and are obtained as follows by the number of mountains in the reference length of 0.25 mm. [250 (μm)] / [Number of peaks (μm) included in 250 (μm)] In the present invention, the pitch P of the unevenness on the sleeve surface that has been blasted with the fixed particles is preferably 2 μm or more, and P is If it is less than 2 μm, sleeve contamination by components in the magnetic toner increases, which is not preferable. Further, the surface roughness d of the irregularities on the sleeve surface is preferably 5 μm or less. When d exceeds 5 μm, an alternating voltage is applied between the sleeve and the latent image holding member so that the magnetic field is transferred from the sleeve side to the latent image surface. The method of developing by flying the toner is not preferable because the electric field tends to concentrate on the concave and convex portions to disturb the image.

As the binder resin used in the toner of the present invention, monomers of styrene such as polystyrene, poly-P-chlorostyrene, polyvinyltoluene and the like, and their substitution products; styrene-P-chlorostyrene copolymer, styrene-propylene. Copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer,
Styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-acryl-aminoacrylic copolymer,
Styrene-amino acrylic copolymer, styrene-amino methacrylic copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl Ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butanediene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrenic copolymers such as copolymers; polymethylmethacrylate,
Polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, terpene resin,
Phenolic resin, aliphatic or cycloaliphatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like can be used alone or in combination of two or more as required.

Further, as the binder resin particularly suitable for pressure fixing, the following ones may be used alone or in combination. For example, polyolefin (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, poly-4-fluoroethylene, etc.), epoxy resin,
Polyester resin, styrene-butanediene copolymer (monomer ratio 5 to 30:95 to 70), olefin copolymer (ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer Polymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ionomer resin), polyvinylpyrrolidone,
Mention may be made of methyl vinyl ether-maleic anhydride copolymers, maleic acid modified phenolic resins and phenol modified terpene resins.

When the toner of the present invention is used as a two-component developer, it is used as a mixture with carrier powder.
As the carrier that can be used in the present invention, all known carriers can be used, for example, magnetic powder such as iron powder, ferrite powder and nickel powder, glass beads and the like, and the surface thereof is treated with resin or the like. The ones that have been made are listed. The mixing ratio of toner and carrier is usually 0.1 to 60:
It is 99.9-40. The toner of the present invention can be used as a magnetic toner by further containing a magnetic material. Examples of the magnetic material contained in the magnetic toner of the present invention include iron oxides such as magnetite, maghematite, and ferrite; iron,
Metals such as cobalt and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin,
Examples thereof include alloys with metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof. These ferromagnetic materials preferably have an average particle size of 0.1 to 2 μm, more preferably 0.1 to 1 μm, and the amount contained in the toner is 100 parts by weight of the resin component. About 20 to 200 parts by weight, particularly preferably 40 to 15 parts by weight per 100 parts by weight of the resin component.
0 parts by weight.

Further, as long as it does not adversely affect the toner of the present invention, it can be used in combination with a conventionally known charge control agent. Examples of the charge control agent include nigrosine dye, quaternary ammonium salt, and triphenylmethane compound. Of these, triphenylmethane compounds are particularly preferable. In addition, for the purpose of improving releasability at the time of heat roll fixing, polyalkylene wax such as low molecular weight polyethylene and low molecular weight polypropylene, or a wax thereof such as copolymer wax, microcrystalline wax, carnauba wax and sazol wax, etc. The substances may be added individually or in a combination of about 0.5 to 5% by weight.

Further, the toner of the present invention gives better results when an additive is mixed if necessary. Examples of the additive include a lubricant such as Teflon and zinc stearate, an abrasive such as cerium oxide and silicon carbide, or a fluidity-imparting agent such as aluminum oxide, an anti-caking agent, or carbon black. And a conductivity-imparting agent such as tin oxide or a fixing aid such as low molecular weight polyethylene. Further, white fine particles of opposite polarity can be used as a developing property improver.

To prepare the positively charged toner according to the present invention, a charge control agent as described above is used as a vinyl type or non-vinyl type thermoplastic resin, and a pigment or dye as a colorant, and if necessary, a magnetic material, After thoroughly mixing the additives and the like with a ball mill or other mixer, using a heat kneader such as a heating roll, kneader, or extruder, melting, kneading, and kneading meat to make the resins compatible with each other. It is possible to disperse or dissolve the content or dye, cool and solidify, and then pulverize and classify to obtain a toner having an average particle size of 1 to 20 μm. Alternatively, a method in which a material is dispersed in a binder resin solution and then spray-dried, or a predetermined material is mixed with a monomer that constitutes the binder resin to form an emulsion suspension and then polymerized A method such as a polymerization method toner for obtaining a toner or a capsule toner including a core and a line can be applied.

[0049]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples of the present invention and Comparative Examples, but the present invention is not limited thereto. All parts in the following formulations are parts by weight.

[0050] (first invention) silicone oil <Example 1> side chain is _{-CH 2 CH 2 CH = N-} H (A) ( nitrogen atoms equivalent: 800,25
10 parts by weight of a viscosity at 80 ° C.) diluted 4 times with n-hexane were sprayed with stirring 100 parts by weight of silica (specific surface area: 130 m ² / g) synthesized by a dry method at a temperature of 250. The temperature was raised to 0 ° C. for treatment.

Next, the following materials were well mixed with a blender and then kneaded with a two-roll mill heated to 150 ° C. After allowing the kneaded product to cool naturally, it is roughly crushed with a cutter mill, then crushed with a fine crusher using a jet stream, and further classified with a wind force classifier to obtain a positive charge with a weight average particle size of 8.5 μm. A fine black powder having a small particle size (hereinafter, referred to as black toner) was obtained. -Styrene-butyl acrylate copolymer (80:20) 100 parts-Magnetite 80 parts-Low molecular weight polypropylene wax 4 parts-Charge control agent 2 parts with the following structure

[0052]

[Chemical 38]

Black toner 100 obtained as described above
0.6 part by weight of the above-mentioned treated silica was added to parts by weight and mixed by a Henschel mixer to obtain a toner of the present invention. The toner thus obtained is used in the copying machine NP-2.
020 (manufactured by Canon) under low temperature and low humidity environment (15
℃ / 10%) and normal temperature and low humidity environment (20 ℃ / 5
%), And an image output test of 2,000 sheets was performed. Further, an image output test of 2,000 sheets was performed under a high temperature and high humidity environment (32.5 ° C./85%). The results are shown in Table 1.

Example 2 A toner of the present invention was obtained in the same manner as in Example 1 except that the charge control agent used in Example 1 was replaced by a charge control agent having the following structure. Using this, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[0055]

[Chemical Formula 39]

<Example 3 and Example 4> A toner of the present invention was obtained in the same manner as in Example 1 except that the amounts of silicone oil used in Example 1 were changed as shown in Table 1. . Using this, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 5 The procedure of Example 1 was repeated, except that the silica particles used in Example 1 were replaced by alumina particles synthesized by a dry method (specific surface area: 150 m ² / g). An inventive toner was obtained. Example 1 using this
It evaluated by the method similar to. The results are shown in Table 1.

Example 6 Instead of the silica particles of Example 1, TiO ₂ particles synthesized by a dry method (specific surface area: 1
The toner of the present invention was obtained in the same manner as in Example 1 except that the amount of 00 m ² / g) was used. Using this, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 7 Instead of the silica particles of Example 1, carbon black particles (specific surface area: 200 m ² /
A toner of the present invention was obtained in the same manner as in Example 1 except that g) was used. Using this, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[0060] Instead of silicone oil used in the particles A <Example 8> Example _{1, (CH 3 O) 3} Si-CH 2 CH
₂ A toner of the present invention was obtained in the same manner as in Example 1 except that 10 parts by weight of a silane coupling agent having a structure of 2CH = N-H (C) was used. Using this, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 9 Silicone oil (D) whose side chain has the following structure instead of the silicone oil used in the particles A of Example 1 (nitrogen valence: 850, viscosity at 25 ° C .: 90 cps) And a toner of the present invention was obtained in the same manner as in Example 1 except that 2 parts by weight of the nigrosine dye was used instead of the charge control agent used in the toner of Example 1. Using this, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[0062]

[Chemical 40]

<Example 10> The following materials were well mixed in a blender and then kneaded with a two-roll mill heated to 150 ° C.
After allowing the kneaded product to cool naturally, it is roughly crushed with a cutter mill, then crushed with a fine crusher using a jet stream, and further classified with a wind force classifier to give a positive chargeability of a weight average particle diameter of 12 μm. A red fine powder having a small particle size (hereinafter referred to as red toner) was obtained. -Styrene-butyl acrylate-dimethylaminoethyl acrylate copolymer (80: 17: 3) 70 parts-Styrene-butadiene copolymer (80:20) 30 parts-Red azo pigment 4 parts-Low molecular weight polypropylene 4 parts This red color Toner was treated with the treated silica used in Example 1.
0 part by weight and 0.5 part by weight of polyvinylidene fluoride particles were added to 100 parts by weight of the red toner and mixed with a Henschel mixer to obtain a toner of the present invention.

-Styrene-2-hydroxyethyl methacrylate-methyl methacrylate copolymer (monomer composition weight ratio = 35: 8: 57) 50% -Vinylidene fluoride-tetrafluoroethylene copolymer (monomer composition weight ratio = 75:25) 50% 100 parts by weight of a ferrite carrier (average particle size: 65 μm) coated with the above resin and 8 parts by weight of the red toner are mixed to obtain a color developing machine of a copying machine NP-4835 (manufactured by Canon Inc.). Applied to low humidity environment (15 ℃ / 10%, 2
0 ℃ / 5%) and high temperature and high humidity environment (32.5 ℃ / 85%)
Then, 2,000 sheets were copied and evaluated. The results are shown in Table 2.

Comparative Example 1 Instead of the silicone oil of Example 1, a silicone oil (B) having a group of —CH ₂ CH ₂ CH ₂ —NH ₂ in the side chain (nitrogen atom equivalent: 800, 2
A comparative toner was obtained in the same manner as in Example 1 except that the viscosity at 5 ° C. was 80 cps. Using this, the same image drawing test was carried out, and evaluation was carried out in the same manner as in the examples. The results are shown in Table 1.

Comparative Example 2 A comparative toner was obtained in the same manner as in Example 10 except that the treated silica used in Comparative Example 1 was used instead of the treated silica used in Example 10. It evaluated similarly. The results are shown in Table 1.

[0067]

[Table 1] Table 1

[0068]

[Table 2] Continuation of Table 1

[0069]

[Table 3] Continuation of Table 1

Evaluation of Toner Coat Uniformity A: No problem at all. Δ: Some unevenness of coat occurs on the sleeve, but there is no abnormality on the image. X: Non-uniform coating occurs on the sleeve, and white background is stained on the image.

(Second Invention) <Example 11> The side chain is CH ₂ CH ₂ —NH—CH ₂ CH ₂
10 parts by weight of silicon oil (a) with CH = NH (nitrogen atom equivalent: 600, viscosity 90 cps at 25 [deg.] C.) was diluted 4 times with n-hexane to obtain silica synthesized by a dry method (ratio Surface area: 130 m ² / g) 100
Part by weight was sprayed with stirring, and the temperature was raised to 250 ° C. for treatment.

Next, the following materials were well mixed with a blender and then kneaded with a two-roll mill heated to 150 ° C. After allowing the kneaded product to cool naturally, it is roughly crushed with a cutter mill, then crushed with a fine crusher using a jet stream, and further classified with a wind force classifier to obtain a positive charge with a weight average particle size of 8.5 μm. A fine black powder having a small particle size (hereinafter, referred to as black toner) was obtained. -Styrene-butyl acrylate copolymer (80:20) 100 parts-Magnetite 80 parts-Low molecular weight polypropylene wax 4 parts-Charge control agent 2 parts with the following structure

[0041]

[Chemical 28]

Black toner 100 obtained as described above
0.6 part by weight of the above-mentioned treated silica was added to parts by weight and mixed by a Henschel mixer to obtain a toner of the present invention. The toner thus obtained is used in the copying machine NP-2.
020 (manufactured by Canon) under low temperature and low humidity environment (15
℃ / 10%) and normal temperature and low humidity environment (20 ℃ / 5%),
An image output test of 2,000 sheets was performed. Further, an image output test of 2,000 sheets was performed under a high temperature and high humidity environment (32.5 ° C./85%). The results are shown in Table 2. Furthermore, after that,
A sufficient density was also exhibited when images were printed after being left for one week in a high temperature and high humidity environment.

<Example 12> In place of the charge control agent of Example 11, a charge control agent having the following structure is used, except that
A toner of the present invention was obtained in the same manner as in Example 11. Using this, evaluation was performed in the same manner as in Example 11. The results are shown in Table 2.

[0076]

[Chemical 42]

<Embodiments 13 and 14> Embodiment 11
A toner of the present invention was obtained in the same manner as in Example 11 except that the amount of silicone oil used in Step 1 was changed to Table 1. Using this, evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 15 Example 11 is repeated except that alumina particles (specific surface area: 150 m ² / g) synthesized by a dry method are used in place of the silica particles used in Example 1.
A toner of the present invention was obtained in the same manner as in. Using this, evaluation was performed in the same manner as in Example 11. The results are shown in Table 2.

Example 16 The present invention was carried out in the same manner as in Example 11 except that the TiO ₂ particles (specific surface area: 100 m ² / g) synthesized by the dry method were used instead of the silica particles of Example 11. Toner was obtained. Example 1 using this
Evaluation was performed in the same manner as in 1. The results are shown in Table 2.

Example 17 Carbon black particles (specific surface area: 200 m ²⁾ were used instead of the silica particles of Example 11.
/ G) was used to obtain a toner of the present invention in the same manner as in Example 11. Using this, evaluation was performed in the same manner as in Example 11. The results are shown in Table 2.

Example 18 Instead of the silicone oil (a) used in Example 11, a side chain of —CH ₂ C was used.
Other than using silicone oil (c) having H ₂ CH = N—H and —CH ₂ CH ₂ CH ₂ —NH ₂ in a ratio of 1: 1 (nitrogen valence: 850, viscosity at 25 ° C .: 80 cps), A toner of the present invention was obtained in the same manner as in Example 11. Using this, evaluation was performed in the same manner as in Example 11.
The results are shown in Table 2.

Example 19 Instead of the silicone oil (a) used in Example 1, (CH ₃ O) ₃ Si—CH ₂ CH
A toner of the present invention was obtained in the same manner as in Example 11 except that 10 parts by weight of a silane coupling agent having a structure of ₂ NH-CH ₂ CH ₂ CH = N-H (d) was used. Using this, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 20 The side chain instead of the silicone oil of Example 11 has the following structure and —CH ₂ CH ₂ CH ₂
Silicone oil (e) with a 1: 1 ratio of NH ₂
(Nitrogen valence: 750, viscosity at 25 ° C .: 70 cp
A toner of the present invention was obtained in the same manner as in Example 11, except that s) was used and 2 parts by weight of the nigrosine dye was used instead of the charge control agent used in the toner of Example 11. Using this, evaluation was performed in the same manner as in Example 11. The results are shown in Table 2.

[0084]

[Chemical 43]

Example 21 The following materials were well mixed with a blender and then kneaded with a two-roll mill heated to 150 ° C.
After allowing the kneaded product to cool naturally, it is roughly crushed with a cutter mill, then crushed with a fine crusher using a jet stream, and further classified with a wind force classifier to give a positive chargeability of a weight average particle diameter of 12 μm. A red fine powder having a small particle size (hereinafter referred to as red toner) was obtained. -Styrene-butyl acrylate-dimethylaminoethyl acrylate copolymer (80: 17: 3) 70 parts by weight-Styrene-butadiene copolymer (80:20) 30 parts by weight-Red azo pigment 4 parts by weight-Low molecular weight polypropylene 4 Parts by weight Treated silica used in Example 11 for this red toner
0 part by weight and 0.5 part by weight of polyvinylidene fluoride particles were added to 100 parts by weight of the red toner and mixed with a Henschel mixer to obtain a toner of the present invention.

-Styrene-2-hydroxyethyl methacrylate-methyl methacrylate copolymer (monomer composition weight ratio = 35: 8: 57) 50% -Vinylidene fluoride-tetrafluoroethylene copolymer (monomer composition weight ratio = 75:25) 50% 100 parts by weight of a ferrite carrier (average particle size: 65 μm) coated with the above resin and 8 parts by weight of the red toner are mixed to obtain a color developing device for a copying machine NP-4835 (manufactured by Canon Inc.). Applied to low humidity environment (15 ℃ / 10%, 2
0 ° C / 5%), high temperature and high humidity environment (32.5 ° C / 85%)
Then, 2,000 sheets were copied and evaluated. The results are shown in Table 2.

Comparative Example 3 Silicon oil (b) having a side chain of —CH ₂ CH ₂ CH ₂ —NH ₂ instead of the silicone oil of Example 11 (nitrogen atom equivalent: 800, 25 ° C.)
Example 11 except that a viscosity of 80 cps) is used.
A toner was obtained in the same manner as in, and evaluated in the same manner. The results are shown in Table 2.
Shown in.

Comparative Example 4 A comparative toner was obtained in the same manner as in Example 21 except that the treated silica used in Comparative Example 3 was used instead of the treated silica used in Example 21. It evaluated similarly. The results are shown in Table 2.

[0089]

[Table 4] Table 2

[0090]

[Table 5] Continuation of Table-1

[0091]

[Table 6] Continuation of Table-2-2

Evaluation of uniformity of toner coat O: No problem at all. Δ: Some unevenness of coat occurs on the sleeve, but there is no abnormality on the image. X: Non-uniform coating occurs on the sleeve, and white background is stained on the image.

[0086]

As described above, the positively chargeable toner of the present invention is
Although the developer contains particles treated with silicone oil containing amine in the side chain as a constituent component, the toner is not excessively charged in a low humidity environment. Therefore, in the one-component developing method using magnetic toner or the like, the toner coating layer on the developing sleeve does not become non-uniform. Further, the positively chargeable toner of the present invention does not cause a phenomenon such as image density blur or fog in the two-component developing system.

Claims (4)

[Claims] 1. A positively chargeable toner comprising a compound having a substituent represented by the following structure (1) or (2) in the molecule. [Chemical 1] [Chemical 2] (R ₁ , R ₂ : hydrogen, alkyl group or aryl group) 2. The positively chargeable toner according to claim 1, which contains particles treated with a compound having a substituent having the following structure (1) or (2) in the molecule. [Chemical 3] [Chemical 4] (R ₁ , R ₂ : hydrogen, an alkyl group or an aryl group) 3. A positively chargeable toner containing a compound having a substituent of the following structure (1) or (2) and an amino group in the same molecule. [Chemical 5] [Chemical 6] (R ₁ , R ₂ : hydrogen, alkyl group or aryl group) 4. The positively chargeable toner according to claim 3, which contains particles treated with a compound having a substituent having the following structure (1) or (2) and an amino group in the same molecule. [Chemical 7] [Chemical 8] (R ₁ , R ₂ : hydrogen, alkyl group or aryl group)