JPH05127416A - Electrostatic latent image developing toner - Google Patents

Abstract

PURPOSE:To provide an electrostatic latent image developing toner not showing a wide dispersion in its components or its properties, excellent in charge controlling ability and stable in charge by immobilizing and/or film-forming a salicylic acid metal complex at a uniformly dispersed state on a surface of core particles when the salicylic acid metal complex is immobilized and/or film-formed on the surface of the core particles essentially consisting of a thermoplastic resin. CONSTITUTION:At least a salicylic acid metal complex and an inorg. fine particulate treated by coating the surface with alkyl polysiloxane having active hydrogen are immobilized and/or film-formed on the surface of core particles essentially consisting of thermoplastic resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic latent image developing toner used for developing an electrostatic latent image in an image forming apparatus such as a copying machine or a printer, and particularly to a thermoplastic resin. The present invention relates to a toner for electrostatic latent image development in which a charge control agent or the like is fixed and / or film-formed on the surface of core particles as a component.

[0002]

2. Description of the Related Art Conventionally, in image forming apparatuses such as copying machines and printers, various electrostatic latent image developing toners have been used as developers for developing electrostatic latent images formed on photoconductors. It had been.

In recent years, in the above-mentioned image forming apparatus, there is a demand for higher quality of images to be formed, and accordingly, the particle size of the electrostatic latent image developing toner used for development is reduced. Came to be actively considered.

Here, when manufacturing a toner for developing an electrostatic latent image having such a small particle size, it is difficult to uniformly disperse additives such as a charge control agent in the toner particles. Since the toner particles are contained in the toner particles in a deviated state, the resulting electrostatic latent image developing toner has poor charging stability and the like, resulting in fogging of the formed image or image formation. When performing the above, there is a problem that toner is scattered and the inside of the image forming apparatus is contaminated with the toner as described above.

For this reason, in recent years, Japanese Patent Laid-Open No. 63-
As disclosed in Japanese Patent No. 85756 and Japanese Patent Laid-Open No. 63-244056, fine particles for surface treatment such as a coloring agent and a charge control agent are mainly applied to the surface of core particles containing a thermoplastic resin as a main component. The toner for electrostatic latent image development has been manufactured by fixing or forming a film by the mechanical and thermal energy.

Here, when fine particles for surface treatment such as a charge control agent are fixed or formed into a film on the surface of the core particles containing a thermoplastic resin as a main component as described above, depending on the type of the charge control agent. It has been found that there are particles of the above-mentioned core particles that are not fixed in a sufficiently homogeneous state.

For example, when an attempt is made to immobilize or form a film of a salicylic acid metal complex on the surface of core particles as shown in Japanese Patent Publication No. 55-42752, the metal salicylic acid complex is well dispersed on the surface of the core particles. In this state, the metal salicylate complex is attached to the surface of the core particles in a solidified state, and the metal salicylate complex is detached from the surface of the core particles and aggregates to form an aggregate of the metal salicylate. Existed in the state of.

Therefore, in the conventional electrostatic latent image developing toner in which the charge control agent composed of the salicylic acid metal complex as described above is fixed or formed into a film on the surface of the core particle, its composition and characteristics are shown. Occurs, and in particular, the variation in charge controllability becomes large, stable toner charging is not performed, and when an image is formed using this electrostatic latent image developing toner, the image formed is There still existed problems such as fogging on the surface of the image forming apparatus, deterioration of image quality, and toner scattering to stain the inside of the image forming apparatus with the toner.

[0009]

SUMMARY OF THE INVENTION The present invention is directed to a copying machine,
In an image forming apparatus such as a printer, it is an object to solve the above problems in the toner for developing electrostatic latent image used for developing the electrostatic latent image.

That is, according to the present invention, when a charge control agent comprising a salicylic acid metal complex is immobilized and / or formed into a film on the surface of core particles containing a thermoplastic resin as a main component,
This salicylic acid metal complex is fixed and / or formed into a film in a state in which it is uniformly dispersed on the surface of the core particle,
It does not cause a large variation in its composition and characteristics, it has excellent charge controllability, stable toner charging is performed, and when an image is formed, fogging occurs in the formed image, An object of the present invention is to provide an electrostatic latent image developing toner that can stably form a good image without causing toner to scatter and stain the inside of the image forming apparatus.

[0011]

In the toner for developing an electrostatic latent image according to the present invention, in order to solve the above problems, at least a metal salicylate is formed on the surface of core particles containing a thermoplastic resin as a main component. The complex and the inorganic fine particles whose surface is coated with an alkylpolysiloxane having active hydrogen are immobilized and / or formed into a film.

Here, in the toner for developing an electrostatic latent image according to the present invention, the surface of core particles containing a thermoplastic resin as a main component is coated with a metal salicylate complex and an alkyl polysiloxane having active hydrogen. The immobilization of the inorganic fine particles is a known surface treatment device of the above salicylic acid metal complex and the inorganic fine particles, for example, mechanically on the surface of the core particles by a hybridization system (manufactured by Nara Machinery Co., Ltd.), It means that the particles are thermally immobilized, or one or more kinds of particles that are not softened by the immobilization treatment are added to the salicylic acid metal complex and the inorganic fine particles to immobilize them on the surface of the core particles. Examples of the particles that are not softened here include thermoplastic resin, various metal particles, and ceramic particles.

In the electrostatic latent image developing toner according to the present invention, forming the above-mentioned metal salicylate complex and inorganic fine particles into a film on the surface of core particles containing a thermoplastic resin as a main component means Of the salicylic acid metal complex and inorganic fine particles so as to cover the surface of the core particles, or in addition to these salicylic acid metal complex and inorganic fine particles, one or more kinds of particles that are softened by the film-forming treatment, This means that the particles are attached to and immobilized on the surface of the core particles in advance, and the softening particles are then subjected to a softening treatment so as to cover the surfaces of the core particles. In addition,
When the softening treatment is performed as described above, the film is formed in a form in which the metal salicylate complex and the inorganic fine particles are dispersed in the film forming layer formed by the softening particles.

As the softening particles used in this film-forming treatment, particles made of various thermoplastic resins can be used. For example, styrene resin, (meth)
Acrylic resin, olefin resin, polyester resin, amide resin, carbonate resin, polyether,
Particles composed of a thermoplastic resin such as polysulfone and the like, and copolymers and polymer blends thereof and the like can be used.

Here, the resin constituting the particles used for forming the film-forming layer as described above may be the same as or different from the resin constituting the core particles. However, the glass transition temperature thereof is preferably 50 ° C. in order to achieve higher heat resistance than the core particles.
The glass transition temperature is higher than that of the resin constituting the core particles.

The amount of the above-mentioned thermoplastic resin particles forming the film-forming layer is 50 parts by weight at the maximum, preferably 5 to 30 parts by weight, per 100 parts by weight of the core particles. Is desirable. That is, if the amount of the resin particles forming the film forming layer is less than 5 parts by weight, it becomes difficult to form a uniform film on the surface of the core particles, and stable and uniform charging properties may be hindered. On the other hand, when the amount of the resin particles exceeds 50 parts by weight, it may not be possible to form a stable film formation layer.

In the toner for developing an electrostatic latent image according to the present invention, the core particles as described above are generally used in the production of toners such as a kneading-grinding method, a spray dry method and a wet granulation method. Although it is possible to use those produced by various known methods such as a method, especially core particles obtained by a wet granulation method, which is advantageous for the production of small particle diameter particles, but whose charge control is difficult, are used. It is effective in some cases, and is more effective when using core particles having a small particle size of 10 μm or less, particularly 8 μm or less, which makes it difficult to uniformly apply the salicylic acid metal complex.

The core particles obtained by the wet granulation method may be obtained by any known method,
For example, suspension polymerization method, emulsion polymerization method, soap-free emulsion polymerization method, microcapsule method (interfacial polymerization method, in-situ polymerization method)
u polymerization method, etc.), a non-aqueous dispersion polymerization method, or the like, or a granulation method without a polymerization process, such as a suspension method.

Here, the resin used to form the core particles may be any resin as long as it is generally used as a binder resin in the production of toner, for example, Thermoplastic resins such as polystyrene resin, poly (meth) acrylic resin, polyolefin resin, polyamide resin, polycarbonate resin, polyether resin, polysulfone resin, polyester resin, epoxy resin, butadiene resin, etc. Alternatively, a thermosetting resin such as a urea resin, a urethane resin, a urea resin, an epoxy resin, a copolymer thereof, a block polymer, a graft polymer, a polymer blend, or the like can be used. The above-mentioned resin is not limited to a resin in a complete polymer state such as a thermoplastic resin, and it is possible to use a resin containing an oligomer or a prepolymer such as a thermosetting resin and a crosslinking agent. It is possible.

When the toner for developing an electrostatic charge image used in the high speed system of the present invention is manufactured, it is necessary to fix the toner on a transfer paper or the like in a short time or to improve the separability from the fixing roller. Therefore, it is preferable to use a homopolymer or copolymer polymer synthesized from a styrene monomer, a (meth) acrylic monomer, a (meth) acrylate monomer, or a polyester resin as the resin constituting the core particles.

In such a resin, the number average molecular weight Mn and the weight average molecular weight Mw are 1000 ≦.
Mn ≦ 10000, 20 ≦ Mw / Mn ≦ 70, and regarding the number average molecular weight Mn, 2,000 ≦ Mn ≦
It is desirable to use that which is 7,000.

When this toner for developing an electrostatic image is used as a toner for oilless fixing, the resin constituting the core particles has a glass transition point of 55 to 80 ° C. and a softening point of 80.
It is desirable to use the one containing a gelling component of 5 to 20% by weight at a temperature of 150 ° C.

Further, in the case of producing a full-color translucent color toner in the present invention, it is preferable to use a polyester resin as the resin constituting the core particles.

Here, the polyester resin constituting the core particles in the translucent color toner has a glass transition temperature of 55 to 70 ° C., a softening point of 80 to 150 ° C., and a number average molecular weight Mn of 2000 to 15,000. It is desirable to use a linear polyester having a molecular weight distribution (Mw / Mn) of 3 or less.

Further, linear urethane-modified polyester obtained by reacting the above linear polyester resin with diisocyanate can also be used.

Here, the linear urethane-modified polyester is a linear polyester resin 1 composed of a dicarboxylic acid and a diol, having a number average molecular weight Mn of 2000 to 15,000, an oxidation of 5 or less, and a terminal group substantially having a hydroxyl group.
A linear urethane-modified polyester resin obtained by reacting 0.3 to 0.95 mol of diisocyanate with respect to mol, and having a glass transition temperature of 40 to 80.
A material whose main component is one whose oxidation is 5 ° C. or less is used.

Further, the above linear polyester is modified with a styrene-based, acrylic-based, aminoacrylic-based monomer or the like by a method such as grafting or block polymerization to obtain a glass transition temperature, a softening point, and a glass transition temperature similar to those of the linear urethane-modified polyester. Those having a molecular weight characteristic can also be preferably used.

In addition to the resin as described above, a colorant, a charge control agent, an offset preventive agent, etc. may be added to the core particles.

Here, as the colorant to be contained in the above core particles, various organic or inorganic compounds as shown below,
A pigment or dye of each color can be used.

First, as the black pigment, carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, non-magnetic ferrite, magnetic ferrite, magnetite and the like can be used.

The yellow pigments include yellow lead, zinc yellow,
Cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navels yellow, naphthol yellow S, bunzer yellow G, bunzer yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow rake, permanent yellow NCG, tartrazine rake. Etc. can be used.

As the orange pigment, red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, induslen brilliant orange RK, benzidine orange G, induslen brilliant orange GK and the like can be used.

The red pigments include red iron oxide, cadmium red, red lead, mercury sulfide, cadmium, permanent red 4R, resole red, pyrazolone red,
Watching red, calcium salt, lake red C,
Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B and the like can be used.

Further, as the purple pigment, manganese purple, fast violet B, netyl violet lake, etc. can be used.

As the blue pigment, navy blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated compound, fast sky blue, induslen blue BC, etc. may be used. You can

As the green pigment, chrome green, chrome oxide, pigment green B, malachite green lake, final yellow green G and the like can be used.

As the white pigment, zinc white, titanium oxide, antimony white, zinc sulfide and the like can be used.

As the extender pigment, barite powder, barium carbonate, clay, silica, white carbon, talc, alumina white and the like can be used.

Further, various dyes such as basic, acidic, disperse and direct dyes include nigrosine, methylene blue,
Rose bengal, quinoline yellow, ultramarine blue, etc. can be used.

When the core particles are made to contain these colorants, these colorants may be used alone or in combination.

Regarding the amount of the colorant contained in the core particles, if the amount of the colorant is too large, the fixability of the toner is lowered, while if the amount of the colorant is too small, a desired image is obtained. Since the concentration cannot be obtained, the amount of these colorants is set to the above-mentioned resin 100 in the core particles.
The amount is 1 to 20 parts by weight, preferably 2 to 10 parts by weight with respect to parts by weight.

When the above-mentioned translucent color toner is obtained as the toner for developing an electrostatic latent image according to the present invention, various color and various pigments and dyes as shown below are used as the colorant. Can be used.

Here, as the yellow pigment used for the translucent color toner, C.I. I. 10316 (Naphthol Yellow S), C.I. I. 11710 (Hansa Yellow 10
G), C.I. I. 11660 (Hansa Yellow 5G),
C. I. 11670 (Hansa Yellow 3G), C.I. I.
11680 (Hansa Yellow G), C.I. I. 11730
(Hansa Yellow GR), C.I. I. 11735 (Hansa Yellow A), C.I. I. 11740 (Hansa Yellow R
N), C.I. I. 12710 (Hansa Yellow R), C.I.
I. 12720 (Pigment Yellow L), C.I. I. Two
1090 (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) or the like can be used.

As the red pigment for the translucent color toner, C.I. I. 12055 (Stalin I), C.I.
I. 12075 (permanent orange), C.I. I. 1
2175 (Resor Fast Orange 3GL), C.I.
I. 12305 (Permanent Orange GTR), C.I.
I. 11725 (Hansa Yellow 3R), C.I. I. 21
165 (Vulcan Fast Orange GG), C.I. I. Two
1110 (benzidine orange G), C.I. I. 1212
0 (Permanent Red 4R), C.I. I. 1270 (Para Red), C.I. I. 12085 (Fire Red), C.I. I. 12315 (Brilliant Fast Scarlet), C.I. I. 12310 (Permanent Red F2R), C.I. I. 12335 (Permanent Red F
4R), C.I. I. 12440 (Permanent Red FR
L), C.I. I. 12460 (Permanent Red FRL
L), C.I. I. 12420 (Permanent Red F4R
H), C.I. I. 12450 (Light Fast Red Toner B), C.I. I. 12490 (Permanent Carmine FB), C.I. I. 15850 (Brilliant Carmine 6
B) and the like can be used.

As the blue pigment for the translucent color toner, C.I. I. 74100 (metal-free phthalocyanine blue), C.I. I. 74160 (phthalocyanine blue), C.I. I. 74180 (Fast Sky Blue) or the like can be used.

The colorants for these translucent color toners can be used alone or in combination as in the case of the above-mentioned ordinary colorants, and the colorants can be used as core particles. Regarding the amount to be contained in, when the amount of these colorants is too large, the fixing property and translucency of the toner are deteriorated, while when the amount of the colorant is too small, the desired image density cannot be obtained. The amount of these colorants is set to 1 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the resin as described above in the core particles.

When an offset preventing agent is contained in the above core particles, various waxes, particularly low molecular weight polypropylene, polyethylene, or oxidized polypropylene are used as the offset preventing agent.
Polyolefin wax such as polyethylene is preferably used.

Such a wax has a number average molecular weight Mn of 1,000 to 20,000 and a softening point T.
It is preferable to use one having m of 80 to 150 ° C. That is, in the case of a wax having a number average molecular weight Mn of 1000 or less or a softening point Tm of 80 ° C. or less, the wax is not uniformly dispersed in the resin forming the core particles, and only the wax is eluted on the surface of the core particles. However, not only may there be unfavorable results during toner storage or development, but it may also cause photoreceptor contamination such as filming, while the number average molecular weight Mn exceeds 20,000 and the softening point Tm is 150 ° C. This is because in the case of a wax exceeding the above range, not only the compatibility with the above-mentioned resin constituting the core particles is deteriorated, but also effects such as high temperature offset resistance cannot be obtained.

When the above-mentioned resin constituting the core particles has a polar group, it is desirable to use a wax having a polar group from the viewpoint of compatibility.

When the above core particles contain a charge control agent, examples of the positive charge control agent include azine compound nigrosine base EX and Bontron N.
-01, 02, 04, 05, 07, 09, 10, 13
(Manufactured by Orient Chemical Industry Co., Ltd.), quaternary ammonium salt P
-51 and an imidazole compound can be used. On the other hand, as the negative charge control agent, for example, chromium complex salt type azo dyes S-32, 33, 34, 35, 37, 38,
40,44 (manufactured by Orient Chemical Industry Co., Ltd.), Eisenspiron Black TRH, BHH (manufactured by Hodogaya Chemical Co., Ltd.), Kayaset Black T-22,004 (manufactured by Nippon Kayaku Co., Ltd.),
Aluminum complex salt E-86 (manufactured by Orient Chemical Industry Co., Ltd.), salicylic acid metal complex E-81 (manufactured by Orient Chemical Industry Co., Ltd.), calixarene compound and the like can be used.

Here, in incorporating these charge control agents into the core particles, the amount of the salicylic acid metal complex to be immobilized and / or formed into a film on the surface of the core particles, the type of resin used for the core particles, the core Types of additives to be included in the particles,
Further, the addition amount of these charge control agents should be appropriately selected and determined according to the developing system (two-component system or one-component system) using the toner for developing the electrostatic latent image.

When the charge control agent is contained in the core particles as described above, if the amount of the charge control agent is too large, the charge amount of the toner becomes unstable and the fixability of the toner deteriorates.
Therefore, it is desirable that the charge control agent is 10 parts by weight or less, preferably 5 parts by weight or less, and more preferably 3 parts by weight or less with respect to 100 parts by weight of the resin in the core particles.

Further, since the electrostatic latent image developing toner according to the present invention is used as a magnetic toner, fine particles made of a known magnetic material can be used in incorporating magnetic fine particles into the above core particles. When obtaining a black toner, it is possible to use magnetite (ferric tetroxide), which itself has a black color and also has a function as a colorant, and when obtaining a color toner, a metallic iron is used. Try to use one with less blackness.

Typical examples of such a magnetic material include, for example, metals exhibiting ferromagnetism such as cobalt, iron and nickel, aluminum, cobalt, iron, lead, magnesium, nickel, zinc, antimony and beryllium. ，
Fine particles of a known magnetic material such as an alloy of a metal such as bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, a mixture thereof, an oxide, a fired body (ferrite), and the like can be included.

On the other hand, in the electrostatic latent image developing toner according to the present invention, the salicylic acid metal complex to be fixed and / or formed into a film on the surface of the core particles as described above is represented by the following general formula (Formula 1) ) Can be used.

[0056]

[Chemical 1]

In the general formula (Formula 1), X,
X'represents carboxylate or ether, and both may be the same or different.

The representatives of the above general formula (Formula 1) include those represented by the following general formulas (Formula 2) to (Formula 4).

[0059]

[Chemical 2]

[0060]

[Chemical 3]

[0061]

[Chemical 4]

In the above general formulas (Formula 2) to (Formula 4), Me represents a metal selected from iron, nickel, zinc, chromium, aluminum, cobalt and titanium.
It is effective when Me is composed of zinc.
A and A ′ in the formula are aromatic dicarboxylic acid, aromatic oxycarboxylic acid selected from the group consisting of (a), (b) and (c) shown in the following general formula (Formula 5),
Derivatives of these carboxylic acids or residues of inorganic substances are shown,
Further, in the formula, M is hydrogen, alkali metal, NH
Either ₄ or the ammonium ammonium is shown.

[0063]

[Chemical 5]

In the general formula (Formula 5), r represents an alkyl group having 1 to 9 carbon atoms or a halogen atom, and n represents 0 or an integer of 1 to 4.

When fixing such a metal salicylate complex on the surface of the core particles and / or forming a film as described above, if the amount of the metal salicylate complex to be added is too small, the toner is sufficiently charged. On the other hand, when the amount is too large, the amount of the salicylic acid metal complex liberated without being immobilized and / or formed into a film on the surface of the core particles is increased, and spent is usually formed. Is added to such a salicylic acid metal complex in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight, and more preferably 0.1 to 1 part by weight, relative to 100 parts by weight of the core particles. To

Further, in immobilizing and / or forming a film of such a salicylic acid metal complex on the surface of the core particle,
The larger the particle size of the metal salicylate complex, and the smaller the specific surface area of the metal salicylate complex, the more difficult the metal salicylate complex is uniformly attached to the surface of the core particles.
The particle size is 0.01 to 1 μm, and the BET specific surface area is 15
It is preferable to use a metal salicylate complex of m ² / g or more.

On the other hand, examples of the inorganic fine particles to be fixed and / or formed into a film on the surface of the core particles together with the above salicylic acid metal complex include, for example, silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, carbonization. Various carbides such as vanadium, tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide and diamond carbon random; various nitrides such as boron nitride, titanium nitride and zirconium nitride; boron such as zirconium boride Compounds; various oxides such as iron oxide, chromium oxide, titanium oxide, calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, silica, colloidal silica, and hydrophobic silica; sulfides such as molybdenum disulfide; Fluorides such as magnesium fluoride and fluorocarbon; Aluminum phosphate, calcium stearate, zinc stearate, various metal soaps such as magnesium stearate: talc, those produced by a dry method or a wet method various nonmagnetic inorganic fine particles of bentonite can be used.

When the surface of such inorganic fine particles is coated with an alkylpolysiloxane having active hydrogen, the alkylpolysiloxane is prepared by repeating the constitutional unit represented by the following general formula (Formula 6). It is possible to use a compound having no characteristic group that reacts with the —OH group at both ends.

[0069]

[Chemical 6]

In the above general formula (Formula 6), R
Represents an alkyl group which may be branched, and the hydrogen atom bonded to the silicon atom in the formula acts as active hydrogen.

When the surface of the inorganic fine particles as described above is coated with such an alkyl polysiloxane having active hydrogen, the above-mentioned general formula (Formula 3)
The alkyl polysiloxane itself shown in 1 or a coating solution obtained by dissolving the alkyl polysiloxane in an appropriate solvent (for example, xylene, trichloroethylene, perchloroethylene, methylene chloride, etc.) is used, and the coating solution is sprayed, dipping or the like. The surface of the above-mentioned inorganic fine particles is applied by a suitable method and dried.

Here, when the above-mentioned alkylpolysiloxane is applied to the surface of the inorganic fine particles, the amount of the alkylpolysiloxane used is 1 to the inorganic fine particles.
It should be 15% by weight, preferably 2 to 10% by weight. This is because when the amount of the alkyl polysiloxane is less than 1% by weight, the inorganic fine particles are not sufficiently hydrophobized, the charge level is low even when added to the toner, and background fogging occurs. This is because when the amount of polysiloxane exceeds 15% by weight, the adhesion of the inorganic fine particles to each other becomes a problem due to the subsequent heat treatment, and further it does not contribute to the stability of charging.

Then, after the alkyl polysiloxane is applied to the surface of the inorganic fine particles and dried as described above, this is subjected to heat treatment. When the heat treatment is performed in this manner, the alkyl polysiloxane coated on the surface of the inorganic fine particles is bound two-dimensionally or three-dimensionally, and the two-dimensional or three-dimensional polymer film of the alkyl polysiloxane is formed into the inorganic fine particles. Is formed on the surface of the inorganic fine particles, and the surface of the inorganic fine particles becomes hydrophobic.

In the above general formula (Formula 6),
The hydrogen atom bonded to the silicon atom acts as active hydrogen, and by being heated as described above, the hydrogen atom reacts with oxygen in the air, and the following reaction formula (Formula 7)
This is because the alkylpolysiloxanes are bonded to each other to form a polysiloxane polymerized film on the surface of the inorganic fine particles as shown in FIG.

[0075]

[Chemical 7]

Therefore, the alkyl groups R ₁ and R ₂ in the above reaction formula (Formula 7) may be such that they do not cause steric hindrance when the alkylpolysiloxanes bond with each other. Further, the above heat treatment is carried out in an air atmosphere at a temperature of usually 120 to 180 ° C, preferably 130 to 160 ° C.

Then, the inorganic fine particles whose surfaces are coated with the alkylpolysiloxane as described above are immobilized on the surface of the core particles together with the above-mentioned salicylic acid metal complex and / or
Alternatively, in forming a film, if the particle size of the inorganic fine particles is large, it becomes difficult to uniformly disperse the metal salicylate complex on the surface of the core particles to fix and / or form a film. The average particle size is usually 0.001 to 1 μm, preferably 0.02 to 0.5 μm.
Try to use m.

If the specific surface area of the inorganic fine particles is too small, the dispersibility is deteriorated. On the other hand, if the specific surface area is too large, it becomes difficult to uniformly attach these particles to the core particles. It is preferable that the BET specific surface area is 10 to 100 m ² / g.

When such inorganic fine particles are fixed on the surface of the core particles and / or formed into a film together with the salicylic acid metal complex, if the amount of the inorganic fine particles is small, the effect of dispersing the salicylic acid metal complex is lost. On the other hand, if the amount is too large, the fixing property of the toner may be deteriorated or the photoconductor may be damaged. Therefore, 0.01 to 10 parts by weight of the above inorganic fine particles is usually added to 100 parts by weight of the core particles. , Preferably 0.1 to 2 parts by weight, more preferably 0.1.
5 to 1 part by weight is added.

Further, in the case where the inorganic fine particles and the salicylic acid metal complex as described above are fixed and / or formed into a film on the surface of the core particles, the ratio of the both is not good when the amount of the salicylic acid metal complex is small. On the other hand, when the amount of the salicylic acid metal complex is too large, while the charging performance of is poor, the salicylic acid metal complex is not uniformly fixed and / or formed into a film on the surface of the core particles, so that the charging characteristics vary. Usually, the weight ratio of salicylic acid metal complex / inorganic fine particles is set to 1/4 to 4, preferably 1/2 to 3/2.

In order to immobilize and / or form a film of the above-mentioned metal salicylate complex and the inorganic fine particles whose surface is coated with alkylpolysiloxane on the surface of the core particle, the above-mentioned metal salicylate complex and Since the inorganic fine particles are often aggregated, it is preferable that the fine particles be subjected to a fine particle treatment in advance so as to be crushed into primary particles.

Here, in the fine particle treatment of the salicylic acid metal complex and the inorganic fine particles, known dry and wet methods can be used. Specifically, various dry jet pulverizers and A wet crusher such as a sand mill can be preferably used.

When the metal salicylate complex and the inorganic fine particles are crushed under a wet condition and dried to be used as a powder, an instant drying device (Krax system, manufactured by Hosokawa Micron Co.) is preferably used. Can be used.

In order to fix and / or form a film of the metal salicylate complex and the inorganic fine particles whose surfaces are coated with alkylpolysiloxane on the surface of the core particles, for example, a high-speed air current impact method is applied. Hybridization system (made by Nara Machinery Co., Ltd.),
Cosmos system (made by Kawasaki Heavy Industries, Ltd.), PJM (made by Nippon Pneumatic Industries Co., Ltd.), kryptron system (made by Kawasaki Heavy Industries, Ltd.), mechanofusion system (made by Hosokawa Micron) applying dry mechanochemical method, mechanomill (Okada Seiko Co., Ltd.) Manufactured by Nihon Pneumatic Industry Co., Ltd., a wet coating method applied by Dispercoat (manufactured by Nisshin Seifun Co., Ltd.), Coatmizer (manufactured by Freund Sangyo), etc. The devices can be preferably used, but the devices are not limited to these devices.

In the toner for developing an electrostatic latent image according to the present invention thus obtained, a fluidizing agent can be added in order to enhance its fluidity. For example, silica, aluminum oxide, titanium oxide, magnesium fluoride, etc. can be used alone or in combination.

Further, in the electrostatic latent image developing toner according to the present invention, in order to improve the fluidity and cleaning property thereof, organic fine particles are adhered or fixed to the surface of the electrostatic latent image developing toner. Examples of such organic fine particles include styrene (meth) granulated by a wet polymerization method such as an emulsion polymerization method or a non-aqueous dispersion polymerization method, or a gas phase method.
Various organic fine particles such as acrylic, benzoguanamine, melamine, Teflon, silicon, polyethylene, polypropylene, acryl fluoride and vinylidene fluoride may be used alone or in combination.

The electrostatic latent image developing toner according to the present invention can be mixed with a magnetic carrier and used as a two-component developer.

Here, as the magnetic carrier to be mixed with the toner for developing an electrostatic latent image according to the present invention, a known magnetic carrier generally used in the past can be used. For example, iron, nickel, etc. , Metals such as cobalt, zinc, antimony, aluminum, lead, tin, bismuth, beryllium, manganese, selenium, tungsten,
Alloys or mixtures with metals such as zirconium and vanadium, oxides, metal oxides such as titanium oxide and magnesium oxide, chromium nitride, vanadium nitride and the like, silicon carbide,
It is possible to use a mixture with a carbide such as tungsten carbide, a ferromagnetic ferrite, and iron, a ferrite carrier, and the like made of materials such as a mixture thereof.

Further, as the above-mentioned magnetic carrier, it is possible to use a core material of iron or ferrite carrier, the surface of which is coated with various synthetic resins or ceramic layers. Here, as the above-mentioned synthetic resin for coating the core material, for example, polystyrene resin, poly (meth) acrylic resin, polyolefin resin, polyamide resin,
Various thermoplastics such as polycarbonate resin, polyether resin, polysulfinic acid resin, polyester resin, epoxy resin, polybutyral resin, urea resin, urethane / urea resin, silicone resin, polyethylene resin, Teflon resin, etc. Resins and thermosetting resins and mixtures thereof, copolymers of these resins, block polymers,
Graft polymers and polymer blends can be used, and in addition, resins having various polar groups may be used in order to improve the chargeability thereof. On the other hand, when coating the surface of the core material with the ceramic layer, various ceramic materials are coated on the surface of the core material by a method such as a thermal spraying method, various plasma methods, and a sol-gel method. Further, a carrier coated with polyethylene by the surface polymerization method described in JP-A-60-106808 can also be preferably used.

Further, as the magnetic carrier, the above-mentioned various synthetic resins used for coating are used as a binder resin, and the above-mentioned various magnetic materials and, if necessary, various organic and / or inorganic materials are added, It is also possible to mix, knead, and grind, and use a binder-type carrier whose particle size is adjusted as necessary.

Incidentally, in each of the above magnetic carriers used in the present invention, if the particle size is smaller than 20 μm, there is a problem that the magnetic carrier itself is generally adhered to the photosensitive member and developed. , The particle size is 2
If it is larger than 00 μm, there is a problem that the texture of an image to be formed is generally rough. Therefore, normally, an average particle size of 20 to 200 μm, preferably 30 to 100 μm is used, and a developing method or the like is used. Therefore, a magnetic carrier having an appropriate particle size is appropriately selected and used.

[0092]

In the toner for developing an electrostatic latent image according to the present invention, when the charge control agent comprising the salicylic acid metal complex is fixed and / or formed into a film on the surface of the core particle containing the thermoplastic resin as a main component, Since the inorganic fine particles whose surface is coated with an alkylpolysiloxane having active hydrogen together with the salicylic acid metal complex are immobilized and / or formed into a film on the surface of the core particle, the salicylic acid metal complex is The inorganic fine particles are uniformly dispersed and are uniformly immobilized and / or formed into a film on the surface of the core particle. In particular, it is difficult to fix and / or form a film of a metal salicylate complex in a wet process. Even for small-sized core particles obtained by the particle method, the metal salicylate complex and the inorganic fine particles are immobilized and / or formed into a film in a state in which they are uniformly dispersed. To become.

Therefore, in the toner for developing an electrostatic latent image according to the present invention, there is no great variation in its composition and characteristics, the charge controllability is excellent, and stable charging is performed. When an image is formed using this toner for developing an electrostatic latent image, there is no possibility that the formed image will be fogged or that this toner will scatter and the inside of the device will become dirty.

[0094]

EXAMPLES The electrostatic latent image developing toner according to the examples of the present invention will be specifically described below, and the electrostatic latent image developing toners of the examples will be compared with those of comparative examples which do not satisfy the conditions of the present invention. It is clarified that the electrostatic latent image developing toner according to the embodiment of the present invention is superior to the electrostatic latent image developing toner.

Example 1 In this example, 100 parts by weight of styrene-n-butyl methacrylate (softening point 132 ° C., glass transition point 60 ° C.) and carbon black (MA # 8 manufactured by Mitsubishi Kasei Co.) were used. Parts by weight and low molecular weight polypropylene (manufactured by Sanyo Chemical Industry Co., Ltd., Viscole 550
After thoroughly mixing 5 parts by weight of P) with a ball mill, these were kneaded on a three-roll roller heated to 140 ° C., and the kneaded material was allowed to cool and then coarsely pulverized with a feather mill. Further, finely pulverized with a jet mill and subjected to air classification to obtain core particles having an average particle size of 6 μm.

As the salicylic acid metal complex to be immobilized and / or formed into a film on the surface of the core particles, a salicyl zinc metal complex represented by the following chemical formula (Formula 8) is pulverized by a jet pulverizer. I did it.

[0097]

[Chemical 8]

The zinc salicylate metal complex thus pulverized had a BET specific surface area of 48 m ² / g and a particle size of 0.4 μm.

The inorganic fine particles to be fixed and / or formed into a film on the surface of the core particles together with the salicylzinc metal complex are 100 parts by weight of hydrophilic titanium oxide (P-25, manufactured by Nippon Aerosil Co., Ltd.). On the other hand, a solution prepared by diluting 5 parts by weight of alkylpolysiloxane represented by the following structural formula (Formula 9) with 50 parts by weight of xylene is spray-coated,
After drying this, the titanium dioxide obtained was dried at 150 ° C.
Was used for 2 hours, and the titanium dioxide fine particles coated with alkylpolysiloxane were used.

[0100]

[Chemical 9]

The BET specific surface area of the inorganic fine particles made of titanium dioxide fine particles is 43 m ²
/ G and its particle size was 0.025 μm.

In order to immobilize and / or form a film of the above-mentioned metal salicylate complex and inorganic fine particles on the surface of the above core particles, first, the above metal salicylate complex is added to 100 parts by weight of the above core particles. 1.0 part by weight and 0.5 part by weight of inorganic fine particles were added, and these were mixed and stirred by the surface treatment apparatus shown in FIG.

Here, in the surface treatment apparatus shown in FIG. 1, the lower portion of the processing chamber 10 for mixing and stirring the above-mentioned particles is formed in a hemispherical shape, while the upper portion thereof is formed in a cylindrical shape, and the processing chamber 10 is formed. A plurality of stirring blades 22 are attached to a rotating shaft 21 as a stirring means 20 for mixing and stirring the above-mentioned respective particles inside.
Is provided with the rotary shaft 21 and the processing chamber 10
Processing chamber 1 by inclining the required angle from the hemispherical bottom
The stirring blade 22 provided on the rotary shaft 21 is inclined at a required angle in the processing chamber 10.

Then, the rotating shaft 21 is rotated by the motor 23 via the belt 24 and the pulley 25, whereby the stirring blade 22 is rotated in the processing chamber 10 in a state of being inclined at a required angle, and thus rotated. The above-mentioned particles were mixed and stirred in the processing chamber 10 by the stirring blade 22.

Further, in this surface treatment apparatus, as the adhesion suppressing means 30 for suppressing the adhesion of these particles to the inner wall 11 of the processing chamber 10, a cylinder through which the rotary shaft 21 of the stirring means 20 is inserted. A first scraping member 31 having an arc shape corresponding to the internal shape of the lower portion of the processing chamber 10 is attached to the rotating shaft 31a, and the first scraping member 31 is attached to the inner wall 11 of the lower portion of the processing chamber 10. The second scraping member 32 having a groove shape corresponding to the internal shape of the upper part of the processing chamber 10 is attached to the rotating shaft 32a which is closely contacted and extends into the processing chamber 10 from the upper part of the processing chamber 10.
And the second scraping member 32 is attached to the processing chamber 1
The inner wall 11 at the upper part of 0 is closely contacted.

Then, the rotating shaft 31a to which the first scraping member 31 is attached is rotated by the motor 31b via the belt 31c and the pulley 31d, and the first scraping member 31 is moved to the inner wall 11 below the processing chamber 10. The second scraping member 32 is rotated in close contact with the second scraping member 32.
Is rotated by a motor 32b via a belt 32c and a pulley 32d, the second scraping member 32 is rotated in close contact with the inner wall 11 of the upper part of the processing chamber 10, and the lower part of the processing chamber 10 and Upper inner wall 11
Particles adhering to the inner wall 11 of the processing chamber 10 are scraped off by the first and second scraping members 31 and 32.

When the above-mentioned particles are mixed and stirred by this mixing device, the peripheral speed of the tip of the stirring blade 22 having the longest blade length is 60 m / sec. Thus, the rotary shaft 21
While rotating each stirring blade 22, the first and second scraping members 31, 32 are moved by the stirring blade 2.
The scraping members 31 and 32 are rotated at proper rotation speeds such that the normal rotation and the reverse rotation are performed every 10 seconds with respect to the rotation direction of 2, so that the above-mentioned particles are deposited on the inner wall of the processing chamber 20. The above-mentioned particles were mixed and stirred for 2 minutes by each stirring blade 22 while preventing the particles from adhering and aggregating.

When the above particles are mixed and stirred in this manner, the particles do not adhere to the inner wall 11 of the processing chamber 10 and harden, and the metal salicylate complex and the inorganic fine particles become primary particles. Crushed and mixed with the core particles in a state where these particles are sufficiently dispersed, and the metal salicylate complex and the inorganic fine particles are uniformly dispersed and adhered to the surface of the core particles in the state of primary particles. It was way.

Further, in this mixing apparatus, the stirring blade 22 is rotated in the processing chamber 10 in a state inclined at the required angle as described above.
The stress applied to each of these particles when mixing and stirring each of these particles by 2 was also reduced.

After the core particles, the metal salicylate complex and the inorganic fine particles were mixed in this manner, the mixture was mixed with a hybridization system (Nara Machinery Co., Ltd., NHS-0 type) at a peripheral speed of 60 m. / Sec for immobilization, and the above-mentioned metal salicylate complex and the inorganic fine particles were immobilized on the surface of the core particles.

Then, the treated product 10 in which the metal salicylate complex and the inorganic fine particles are immobilized on the surfaces of the core particles in this manner
0.1 part by weight of hydrophobic silica (R-974 manufactured by Nippon Aerosil Co., Ltd.) having an average particle diameter of 0.017 μm was added to 0 part by weight, and these were mixed by a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.). A toner for developing an electrostatic latent image was manufactured by processing at 1000 rpm for 1 minute.

Comparative Example 1 In this comparative example, the inorganic fine particles used in the production of the electrostatic latent image developing toner of Example 1 were treated with dimethyldichlorosilane to give a hydrophobic silica ( A toner for developing an electrostatic latent image was manufactured in the same manner as in Example 1 except that it was changed to R-972, manufactured by Nippon Aerosil Co., Ltd.

Example 2 In this example, the salicylic acid metal complex and the inorganic fine particles used in the production of the electrostatic latent image developing toner of Example 1 were changed.

In this example, as the salicylic acid metal complex, an aluminum salicylate metal complex represented by the following chemical formula (Formula 10) was pulverized by a jet pulverizer.

[0115]

[Chemical 10]

The salicylic acid metal complex thus obtained had a BET specific surface area of 28 m ² / g and a particle size of 0.6 μm.

As the inorganic fine particles, 5 parts by weight of an alkyl polysiloxane represented by the following structural formula (Formula 11) was added to xylene with respect to 100 parts by weight of hydrophilic silica fine particles (OX-50 manufactured by Nippon Aerosil Co., Ltd.). After spray coating a solution diluted with 50 parts by weight and drying it, 15
Heat treatment was carried out at 0 ° C. for 2 hours, and silica fine particles coated with an alkylpolysiloxane were used.

[0118]

[Chemical 11]

The inorganic fine particles made of the above silica fine particles thus obtained have a BET specific surface area of 42.
m ² / g and the particle size was 0.05 μm.

Then, an electrostatic latent image developing toner was produced in the same manner as in Example 1 except that these salicylic acid metal complex and inorganic fine particles were used.

Comparative Example 2 In this comparative example, the hydrophilic silica fine particles used in Example 2 above (OX-50, manufactured by Nippon Aerosil Co., Ltd.) were used as the inorganic fine particles.
Was treated with octyltrimethoxysilane, and otherwise the electrostatic latent image developing toner was manufactured in the same manner as in Example 2.

(Example 3) In this example, 100 parts by weight of styrene, 35 parts by weight of n-butyl methacrylate, 5 parts by weight of methacrylic acid and 2,2-azobis- (2,4-dimethylvalero) were used. 0.5 parts by weight of nitrile), 3 parts by weight of low molecular weight polypropylene (manufactured by Sanyo Chemical Industry Co., Ltd., Viscole 605P), and 8 parts by weight of carbon black (MA # 8 manufactured by Mitsubishi Kasei Industry Co., Ltd.) were mixed with a sand stirrer. To prepare a polymerization composition.

Then, this polymerization composition was put into an aqueous solution of gum arabic having a concentration of 3%, and this was rotated by a stirrer (TK Auto Homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotation speed of 400.
Polymerization reaction was carried out at a temperature of 60 ° C. for 6 hours while stirring at 0 rpm to obtain spherical core particles having an average particle size of 6 μm.

On the other hand, as the salicylic acid metal complex and the inorganic fine particles, the same salicylic acid metal complex and inorganic fine particles as those used in the above-mentioned Example 1 were used, and these were 1: 1.
Water and methanol were added to a medium having a weight ratio of 80:20 at a weight ratio of 1, and these were pulverized in advance in this medium by using a sand mill (Paint Conditioner, manufactured by Red Devil Co.).

Then, the mixture of the salicylic acid metal complex and the inorganic fine particles thus pulverized was added to the above dispersion system of the core particles in an amount of 3 with respect to 100 parts by weight of the solid content of the core particles.
After adding in a proportion of parts by weight, these were continuously stirred to immobilize the metal salicylate complex and the inorganic fine particles on the surface of the core particles.

Thereafter, this treated product was repeatedly filtered and washed with water, and the cake-like particles obtained were dried at 80 ° C. for 5 hours using a hot air dryer to coagulate the particles with each other. Ultrafine particles of 1 μm or less were adhered to the surface of particles of 3 μm or more and melted to form particles of about 50 μm to 1 mm to obtain an aggregate having an average particle size of about 100 μm to 2 mm.

Next, the agglomerates thus obtained were treated with the Klyptron System (KTM-X manufactured by Kawasaki Heavy Industries, Ltd.).
Type) and crushed at 10000 rpm and subjected to surface modification treatment.

The particles 100 thus crushed
Hydrophobic silica (manufactured by Wacker Co., H-2
000) 0.2 part by weight was added, and these were mixed at 1 to 1000 rpm with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.).
The toner for developing an electrostatic latent image was manufactured by processing for 1 minute.

(Comparative Example 3) In this comparative example, only the above metal salicylate complex was pulverized in advance by a sand mill in the same manner as in Example 3 without using the inorganic fine particles used in Example 3 above. The salicylic acid metal complex pulverized in this way is added to the dispersion system of the core particles at a ratio of 3 parts by weight with respect to 100 parts by weight of the solid content of the core particles. ,
A toner for developing an electrostatic latent image was manufactured in the same manner as in Example 3 above.

Example 4 In this example, the salicylic acid metal complex and the inorganic fine particles used in the production of the electrostatic latent image developing toner of Example 3 were changed.

In this example, as the salicylic acid metal complex, a salicylic acid chromium metal complex represented by the following chemical formula (Formula 12) was pulverized by a jet pulverizer.

[0132]

[Chemical 12]

In this salicylic acid metal complex, its BET specific surface area was 33 m ² / g and its particle size was 0.7 μm.

As the inorganic fine particles, the inorganic fine particles used in Example 2 were used.

Other than the above, a toner for developing an electrostatic latent image was manufactured in the same manner as in Example 3 above.

(Comparative Example 4) In this comparative example, as the inorganic fine particles, the hydrophilic silica fine particles used in the above-mentioned Example 2 (OX-5, manufactured by Nippon Aerosil Co., Ltd.) were used.
0) was used as it was without treatment.

Except for this, the toner for developing an electrostatic latent image was manufactured in the same manner as in Example 4.

(Example 5) In this example, a polyester resin (NE-382 manufactured by Kao Corporation) 10 was used.
0 g was dissolved in 400 g of a mixed solvent of methylene chloride / toluene (8/2), and phthalocyanine pigment 5 was added to this solution.
g was added, and the mixture was placed in a ball mill and mixed for 3 hours for dispersion to obtain a uniform mixed dispersion.

Next, as a dispersion stabilizer, 60 g of a 4% solution of methylcellulose (manufactured by Dow Chemical Co., Methocel K35LV) and 5 g of a 1% solution of dioctyl sulfosuccinate soda (Nikko Chemical Co., Nikkor OTP75).
And sodium hexametaphosphate (Wako Pure Chemical Industries, Ltd.) 0.5g
And 1000 g of ion-exchanged water are dissolved, and the dispersion liquid uniformly mixed as described above is added to this aqueous solution, and the rotation speed is adjusted by TK Auto Homo Mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). The dispersion was suspended in water so that the average size of the dispersion was 3 to 10 μm.

Then, the stirring speed was reduced and the mixture was further stirred, and the mixed solvent of methylene chloride / toluene was removed at a temperature of 60 ° C. for 5 hours to obtain spherical core particles having an average particle size of 6 μm.

On the other hand, the same metal salicylate complex as in Example 1 was used, and as the inorganic fine particles, 100 parts by weight of hydrophilic aluminum oxide (Aluminum Oxide C, manufactured by Nippon Aerosil Co., Ltd.) was used. A solution prepared by diluting 2 parts by weight of the alkylpolysiloxane represented by the above structural formula (Formula 9) with 20 parts by weight of xylene was spray-coated, dried, and then heat-treated at 150 ° C. for 2 hours to obtain an alkylpolysiloxane. The coated aluminum oxide fine particles were used.

The inorganic fine particles made of the aluminum oxide fine particles thus obtained had a BET specific surface area of 82 m ² / g and a particle diameter of 0.02 μm.

Then, the salicylic acid metal complex and the inorganic fine particles were mixed at a weight ratio of 1: 1 with water and methanol at 80: 2.
In a medium having a weight ratio of 0, these were pulverized in advance in this medium using a sand mill (Paint Conditioner, manufactured by Red Devil Co.).

Then, the mixture of the salicylic acid metal complex and the inorganic fine particles thus pulverized was added to the above dispersion system of the core particles in an amount of 3 with respect to 100 parts by weight of the solid content of the core particles.
After adding in a proportion of parts by weight, these were continuously stirred to immobilize the metal salicylate complex and the inorganic fine particles on the surface of the core particles.

Thereafter, this dispersion was dried using a slurry dryer Dispercoat, and at the same time, the above metal salicylate complex and the inorganic fine particles were fixed on the surface of the core particles to give cyan having an average particle diameter of 5.5 μm. Colored particles were obtained.

Next, with respect to 100 parts by weight of the cyan color particles thus obtained, hydrophobic silica (manufactured by Wacker,
H-2000) 0.2 part by weight was added, and these were mixed with a Henschel mixer (Mitsui Miike Kakoki Co., Ltd.) at 1000 r.
A toner for developing an electrostatic latent image was produced by treating with pm for 1 minute.

Comparative Example 5 In this Comparative Example, the inorganic fine particles used in Example 5 were not used, and only the salicylic acid metal complex was pulverized in advance by a sand mill in the same manner as in Example 5. The salicylic acid metal complex thus pulverized was added to the dispersion system of the core particles in an amount of 3 parts with respect to 100 parts by weight of the solid content of the core particles.
It was made to add in the ratio of a weight part. A toner for developing an electrostatic latent image was manufactured in the same manner as in Example 5 except the above.

(Example 6) In this example, as a particle to be treated on the surface of the core particle in the above-mentioned Example 1, the zinc salicylate metal complex represented by the above chemical formula (Formula 8) was jet milled. MMA / iBMA (1/9) polymer particles MP in addition to the pulverized particles and the inorganic particles composed of titanium dioxide surface-coated with the alkylpolysiloxane represented by the above structural formula (Formula 9)
-4915 (manufactured by Soken Chemical Industry Co., Ltd., average particle diameter 0.2 μm, glass transition temperature 85 ° C.) was used.

With respect to 100 parts by weight of the core particles, 1.0 part by weight of the pulverized product of the zinc salicylate metal complex, 1.0 part by weight of the inorganic fine particles, and 15.0 parts of the polymer fine particles were used. The mixture was added at a ratio of parts by weight, and these mixtures were treated at a peripheral speed of 90 m / sec using a hybridization system (Nara Machinery Co., Ltd., NHS-O type), otherwise, the same as in Example 1 above. A toner for developing an electrostatic latent image was manufactured by the same method as in the case.

Next, Example 1 manufactured as described above.
6 to 6 and the toners for developing electrostatic latent images of Comparative Examples 1 to 5, their charge amount [μC / g] and low chargeable toner amount [wt%] are obtained, and the above electrostatic latent image developing is performed. The image quality is evaluated when the image is formed using the toner for use.

Here, in carrying out these evaluations, as the carrier to be mixed with these electrostatic latent image developing toners, three types of carrier C produced as described below are used.
1 to C3 were used.

Here, as the carrier C1, 100 parts by weight of a polyester resin (NE-1110, manufactured by Kao Corporation), 600 parts by weight of inorganic magnetic powder (MFP-2, manufactured by TDK), and carbon black (Mitsubishi Kasei Co., Ltd.) were used. Made, MA # 8) 2
1 part by weight is thoroughly mixed with a Henschel mixer and crushed, and then the cylinder part 180 ° C., cylinder head part 1
Melt kneading was performed using an extrusion kneader set to 70 ° C., the kneaded product was cooled and coarsely pulverized, then finely pulverized by a jet mill, and further classified by using an air classifier to obtain an average particle size of A binder type carrier having a size of 55 μm was used.

As the carrier C2, the surface of a ferrite carrier core (F-300 manufactured by Powdertech Co., Ltd.) is coated with a thermosetting silicone resin using a rolling fluid tank (Spiracoater manufactured by Okada Seiko Co., Ltd.), Average particle size is 50μ
The carrier which became m was used.

As the carrier C3, a ferrite carrier core (F-300, manufactured by Powdertech Co., Ltd.) was used, in which the surface was coated with polyethylene by a surface polymerization coating method to obtain an average particle diameter of 51 μm.

Then, the above Examples 1 to 6 and Comparative Example 1
The above carriers C1 to C3 were combined with the electrostatic latent image developing toners Nos. 5 to 5 as shown in Table 1 below.

Here, Examples 1 to 6 and Comparative Examples 1 to 5
In determining the charge amount [μC / g] and low chargeable toner amount [wt%] of each electrostatic latent image developing toner, Table 1 shows each electrostatic latent image developing toner and the above carrier. As described above, each carrier was added to each electrostatic latent image developing toner in a weight ratio of toner / carrier = 5/95, and these were put in a 50 cc plastic bottle and 120 rpm by a rotary mount. And rotated for 30 minutes to prepare a developer using each electrostatic latent image developing toner.

Then, 1 g of each of the developers thus prepared was weighed with a precision balance, and the electrostatic latent image developing toners of Examples 1 to 6 and Comparative Examples 1 to 5 using the apparatus shown in FIG. The amount of charge [μC / g] and the amount of low-chargeable toner [% by weight] were determined.

Here, when the charge amount [μC / g] of each toner is measured using the apparatus shown in FIG. 2, each developer measured as described above is uniformly distributed over the entire surface of the conductive sleeve 1. And the rotation speed of the magnet roll 2 provided in the conductive sleeve 1 was set to 100 rpm.

Then, a bias voltage of 3 KV is applied from the bias power source 3 in the opposite direction to the charging potential of the toner, the conductive sleeve 1 is rotated for 30 seconds, and the cylindrical electrode 4 is stopped when the conductive sleeve 1 is stopped. The potential Vm is read, and the cylindrical electrode 4 is removed from the conductive sleeve 1
The weight of the toner attached to the toner was weighed with a precision balance to obtain the average charge amount [μC / g] of each toner, and the results are shown in Table 1 below.

In measuring the low charge toner amount [wt%] of each toner, the conductive sleeve 1 is used.
The bias voltage is not applied to the ground and the measurement is performed in this state in the same manner as described above. The amount of toner on the cylindrical electrode 4 is measured with respect to the total amount of toner placed on the conductive sleeve 1. The amount of low-charged toner [wt%] of each toner is determined by measuring whether or not the toner has been blown, and the results are shown in Table 1 below.
It was shown to.

Further, also in carrying out image quality evaluation in the case of forming an image using each of the electrostatic latent image developing toners of Examples 1 to 6 and Comparative Examples 1 to 5, Examples 1 to 5 and Comparative Examples Each of the electrostatic latent image developing toners 1 to 5 is used in combination with each developer as described above, and an apparatus for performing the evaluation is a commercially available copying machine (Minolta Camera Co., EP- 570Z) was used.
When the image quality of each of the electrostatic latent image developing toners of Example 5 and Comparative Example 5 was evaluated, the fixing device of the copying machine (EP-570Z manufactured by Minolta Camera Co., Ltd.) was improved to an oil coating method. Was used.

Then, Examples 1 to 6 and Comparative Examples 1 to 5
Each of the developers using the electrostatic latent image developing toners of No. 1 is used in each of the above copying machines, and a printing endurance test of 10,000 sheets is performed by using each of the copying machines using a chart having a black ratio of 6%. The fogging of images formed in the initial stage and after printing 10,000 sheets was evaluated.

The image quality is evaluated as ◯ when the image has no fogging and is good, Δ when there is some fogging but is practically usable, and x when practically problematic.
The results are shown in Table 1 below.

[0164]

[Table 1]

As is clear from these results, when the electrostatic latent image developing toners of Examples 1 to 6 were used, the electrostatic latent image developing toners of Comparative Examples 1 to 5 were used. Compared with the case, the amount of low-chargeable toner was remarkably reduced, and fogging in the formed image was also small, so that a good image could be obtained.

With respect to each of the electrostatic latent image developing toners of Example 5 and Comparative Example 5, an image was formed on an OHP sheet by using the above copying machine, and the image fixed on the OHP sheet. Was projected using an OHP projector, and the vividness of the color in each projected image was visually evaluated. As a result, no matter which toner was used, the color reproduction was in a practically usable range.

[0167]

As described above in detail, in the electrostatic latent image developing toner according to the present invention, the charge control agent comprising the salicylic acid metal complex is immobilized on the surface of the core particle mainly composed of the thermoplastic resin. And / or in forming a film, inorganic fine particles whose surface is coated with an alkylpolysiloxane having active hydrogen together with the salicylic acid metal complex are immobilized and / or formed into a film on the surface of the core particle. As a result, the metal salicylate complex can be uniformly immobilized and / or formed into a film on the surface of the core particles in a state of being uniformly dispersed by the inorganic fine particles. Even for core particles of particle size,
The metal salicylate complex and the inorganic fine particles are now fixed and / or formed into a film in a state where the inorganic fine particles are uniformly dispersed.

As a result, in the toner for developing an electrostatic latent image according to the present invention, the salicylic acid metal complex is not unevenly processed, and the composition and the characteristic thereof are not greatly varied, and the charge controllability is excellent. , It becomes possible to obtain a toner for developing an electrostatic latent image that is stably charged, and when an image is formed using this toner for developing an electrostatic latent image, fogging occurs in the formed image. The toner is not scattered and the inside of the apparatus is not contaminated, and good image formation can be performed.

[Brief description of drawings]

FIG. 1 is a schematic explanatory view of a surface treatment apparatus used for mixing and agitating particles in producing toners for developing electrostatic latent images of Examples 1 and 2 and Comparative Examples 1 and 2.

FIG. 2 is a schematic explanatory diagram of an apparatus used to measure the charge amount and low-chargeable toner amount of each electrostatic latent image developing toner.

Claims (1)

[Claims] 1. At least a metal salicylate complex and inorganic fine particles whose surface is coated with an alkylpolysiloxane having active hydrogen are immobilized and / or formed on the surface of a core particle containing a thermoplastic resin as a main component. An electrostatic latent image developing toner characterized by being formed into a film.