JP2003241423A - Spheric toner containing antibacterial agent, two component developer, image forming device and method for forming image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a spheric toner or the like containing an antibacterial agent having an antibacterial property and capable of forming an image of high picture quality. <P>SOLUTION: The spheric toner containing an antibacterial agent has ≤140 shape factor SF1 and ≤1.4 average volume particle size distribution GSDv and contains an inorganic antibacterial agent near the surface of particles. The inorganic antibacterial agent in the toner contains at least one kind of antibacterial metal selected from silver, copper, zinc and titanium. The two- component developer comprises the above spheric toner containing the antibacterial agent and a carrier. An image body is formed by using the above spheric toner containing the antibacterial agent. An image forming device and a method for forming an image are presented by using the above spheric toner containing the antibacterial agent or the two-component developer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in various properties such as color developability and OHP transparency, and is suitable for use in image formation by electrophotography or the like, and has antibacterial properties for printed matter on which an image is formed. The present invention relates to an electrostatic charge image developing toner that can be applied, an electrostatic charge image developer containing the electrostatic charge image developing toner, and an image forming method using the electrostatic charge image developing toner.

[0002]

2. Description of the Related Art A method of visualizing image information through an electrostatic charge image, such as an electrophotographic method, is currently widely used in various fields. As the developer for electrophotography, a two-component developer composed of toner particles and carrier particles and a one-component developer containing magnetic toner particles or non-magnetic toner particles are known. In recent years, a thermoplastic resin and the like are melt-kneaded together with a pigment, a charge control agent, a release agent such as wax, and the like, and after cooling, the melt-kneaded product is finely pulverized and classified to produce desired toner particles. In addition to the method, a polymerized toner that realizes high image quality and high productivity by intentionally controlling the shape and surface composition of particles has been developed (JP-A-11-2922).

On the other hand, a printed matter on which an image is fixed by an electrophotographic method is likely to come into contact with an unspecified number of people depending on its use, and the demand for an antibacterial effect is increasing with the recent trend of hygiene. . Along with this, technical development such as papermaking by previously mixing an antibacterial agent in a paper material, molding by mixing an antibacterial agent with a resin (Japanese Patent Laid-Open No. 10-96195), and antibacterial effect on the surface of a paper or resin plate The method of applying the coating agent containing the agent or the method of applying the ink containing the antibacterial agent by the method such as gravure printing is widely used.
(JP-A-9-3799).

[0004]

Up to now, the antibacterial property imparting to the image forming medium has been studied mainly on papers, films, antibacterial inks and the like having an antibacterial function. Was few. Among them, JP-A-9
No. 106094 and Japanese Patent Application Laid-Open No. 8-314179 disclose inventions of toners having antibacterial properties.

However, since all the toners described in the above publications are manufactured by kneading and pulverizing the antibacterial agent with the toner raw material, the antibacterial agent is contained inside the toner, and as a result, the toner particle surface To expose a sufficient amount of antibacterial agent to impart antibacterial properties to
There was no choice but to increase the amount of antibacterial agent used, and the antibacterial performance was inefficient. Further, since the particle size of these pulverized toners is larger than the particle size of toners usually produced by the polymerization method, the image quality is inferior to that of the polymerized toner, and the amount of toner used is larger than that of the polymerization method. Therefore, there is a drawback in that the blending of the antibacterial agent has a great influence on the manufacturing cost.

[0006]

DISCLOSURE OF THE INVENTION In view of the above situation, the present inventors have made earnest studies and found that the following problems can be solved by the following constitution.

(1) A spherical toner containing an antibacterial agent having a shape factor SF1 of 140 or less and containing an inorganic antibacterial agent near the surface.

By using a spherical toner having a shape factor SF1 of 140 or less, the antibacterial agent can be efficiently applied in the vicinity of the toner surface. Further, since the spherical toner has an antibacterial agent in the vicinity of its surface, the antibacterial property of the toner image surface formed on the transfer target after heat fixing is higher than that of the toner in which the antibacterial agent is buried in the concave portion of the irregular surface. improves.

(2) Average volume particle distribution GSDv is 1.4
The antibacterial agent-containing spherical toner according to (1) below, which is as follows.

By using the toner having the above particle distribution range, the image becomes sharp and the image quality is improved.

(3) Emulsion aggregation method (a step of aggregating particles in a dispersion liquid in which particles containing at least resin particles are dispersed,
And the antibacterial agent-containing spherical toner according to (1) or (2) above, which further comprises a resin produced by using (1) in a toner produced from the step of heating and aggregating aggregated particles.

The resin particles produced by the above-mentioned emulsion aggregation method have a narrower particle distribution than the resin particles produced by other production methods. Therefore, when used in a toner or a developer,
There is an advantage that the image becomes clearer.

(4) The toner has an average volume particle diameter of 2 to 8 μm.
The antibacterial agent-containing spherical toner according to any one of (1) to (3) above, wherein m is m.

By using the toner having the above particle size, the image quality is improved and the amount of antibacterial agent consumed during image formation is also appropriate.

(5) The inorganic antibacterial agent contained in the toner is
The antibacterial agent-containing spherical toner according to any one of (1) to (4) above, which has at least one antibacterial metal selected from silver, copper, zinc, and titanium.

The above-mentioned inorganic antibacterial agent has a long lasting antibacterial performance and a high safety to the human body. Therefore, the inorganic antibacterial agent is environmentally friendly and almost permanently keeps the antibacterial property of the toner image formed on the surface of the transferred material. You can

(6) The antibacterial metal contained in the toner is at least one of ions, ultrafine metal particles and ultrafine metal complex particles.
The spherical toner containing an antibacterial agent according to any one of (1) to (5) above.

(7) The antibacterial agent-containing spherical toner as described in (1) above, wherein the antibacterial metal contained in the toner is supported on an inorganic substance, and the inorganic carrier is a phosphate compound.

The toners (6) and (7) have a high antibacterial effect because the antibacterial metal is more uniformly applied to the vicinity of the toner surface.

(8) The antibacterial agent-containing spherical toner as described in (1) above, wherein the content of the inorganic antibacterial agent in the toner is 0.01 to 10% by weight.

A desired antibacterial effect can be exhibited by the above-mentioned content of the inorganic antibacterial agent.

(9) A two-component developer containing the antibacterial agent-containing spherical toner according to any one of the above (1) to (8) and a carrier.

(10) An image body produced by using the spherical toner containing an antibacterial agent described in any one of (1) to (8) above.

(11) An image body produced by using the developer described in (9) above.

According to the above (9) to (11), it is possible to obtain a developer and an image body having high antibacterial properties.

(12) Latent image forming means for forming a latent image on the latent image carrier based on image data, and developing means for developing the formed latent image with a developer to form a toner image. And a transfer unit that transfers the toner image onto the transfer target, wherein the toner forming the toner image is the toner image forming apparatus described in (1) above.

(13) A latent image forming step of forming an electrostatic latent image on a latent image carrier, a developing step of developing the electrostatic latent image with toner or a developer to form a toner image, and the toner image In the image forming method, there is provided a transfer step of forming a transfer image by transferring the toner onto a transfer target, and a fixing step of fixing the transfer image transferred onto the transfer target. The image forming method is the toner containing an antibacterial agent described in any one of (1) to (8), wherein the developer is the two-component developer described in (9) above.

According to the image forming apparatus and the image forming method of the above (12) and (13), an image having high antibacterial property can be formed with an appropriate amount of the antibacterial agent.

[0029]

That is, the present invention has succeeded in incorporating an antibacterial agent into a toner produced by a polymerization method and having a uniform particle shape and a smooth surface. Hereinafter, the details of the invention will be described.

[Shape of Toner Particles] The spherical toner for electrophotography of the present invention has a spherical shape whose shape can be defined by the shape factor SF1 as follows.

[0031]

## EQU1 ## SF1 = (ML ² / A) × (π / 4) × 100 where ML: absolute maximum length of toner particles, A: projected area of particles

These can be digitized mainly by analyzing a microscope image or a scanning electron microscope image with an image analyzer. SF1 is regarded as a true sphere as it approaches 100, and as the value increases, it means that there is a large difference between the maximum length and the minimum length of toner particles, resulting in an elliptical shape.

The shape factor SF1 of the toner particles of the spherical toner for electrophotography of the present invention is 140 or less, preferably 110 or more, more preferably 110 to 130. If the shape factor SF1 of the toner particles exceeds 140, the image quality tends to deteriorate, while the shape factor SF1 of the toner particles tends to deteriorate.
In the case of toner particles having a value of less than 110, which is close to a true sphere, it is difficult to handle the toner and the fluidity of the toner is too good, so that image bleeding may occur. Further, by keeping the toner particles spherical, the amount of the antibacterial agent, which will be described later, is less embedded, and a sufficient amount of the antibacterial agent is exposed on the image surface. Therefore, in the case of an irregular toner having a toner particle shape factor SF1 exceeding 140, the antibacterial agent is likely to be embedded in the concave and convex portions of the surface, and the antibacterial function is deteriorated.

Average volume particle distribution G of toner particles of the present invention
SDv is 1.4 or less, preferably 1.3 or less, and more preferably 1.25 or less. When the particle distribution of the toner particles exceeds 1.4, the image quality is deteriorated because the particle diameters vary widely. In addition, it is difficult to give uniform antibacterial performance to each toner particle in manufacturing. As the index of particle distribution, the following average volume particle distribution GSDv can be simply used by using cumulative distributions D16 and D84.

[0035]

## EQU00002 ## Average volume particle distribution GSDv = (volume D84 / volume D16) ^0.5

The average volume particle size of the toner particles is 2 to 8 μm.
It is preferably m. More preferably, it is 2 to 7 μm. When the toner particle size exceeds 8 μm, not only the image quality deteriorates, but also the consumption amount of the toner used during image formation increases, and as a result, the amount of the antibacterial agent contained also increases. Furthermore, when the toner particle size is small, the specific surface area increases, so that the antibacterial performance can be more efficiently exhibited.

[Method for Producing Toner Particles] Next, a method for producing the spherical resin constituting the toner particles of the present invention will be described below. The method for producing the spherical resin constituting the toner of the present invention is not particularly limited, and examples thereof include emulsion polymerization aggregation method, suspension polymerization method, dispersion polymerization method and the like.
In particular, the emulsion polymerization agglomeration method, by mixing a resin dispersion of an ionic surfactant and an ionic surfactant of opposite polarity, to form agglomerated particles of the desired resin particle size by causing hetero-aggregation, On the other hand, a colorant dispersion liquid in which a colorant is dispersed in a solvent is prepared, a mixing step of mixing these, an aggregating step of forming agglomerated particles corresponding to a toner particle size, and a fusion of the agglomerated particles by heating. And a fusing step.

In addition to the agglomeration method described above, an emulsion agglomeration method using a metal compound has been proposed. For example, as a toner production method by an emulsion aggregation method using a metal compound, an aggregation method using a water-soluble inorganic metal salt having a divalent or higher charge as described in Japanese Patent No. 3107062 has been proposed. In this method, resin fine particles and the like are aggregated in an aqueous medium using an inorganic metal salt having a valence of 2 or more, and the particles are heated and fused at a glass transition temperature or higher.

In these manufacturing methods, the shape of the resin particles can be controlled from an amorphous shape to a spherical shape by selecting the heating temperature condition. In addition, after the aggregation step or the aggregation step,
It is possible to easily incorporate various additives into the toner by adding an inorganic antibacterial agent together with a release agent dispersion liquid such as wax.

As a result of the examination of the aggregating step and conditions, the present inventors have previously shifted the balance of the amounts of the ionic surfactants of the respective polarities in the aggregating step (that is, depending on the ionic surfactant). leave tilted either the balance of polarity in advance), to form a mother aggregated in the first stage below the glass transition temperature and then mixture was allowed to stabilize, the displacement polarity balance by the surfactant in the second stage Add a particle dispersion that has been treated with a surfactant in a polarity and amount to compensate, and if necessary, heat slightly below the glass transition temperature of the resin contained in the matrix or additional particles to stabilize at higher temperatures. After being made into a solid, the particles added in the second stage of the aggregate formation can be coalesced while being attached to the surface of the base aggregate particles by heating the glass transition temperature or higher.

Moreover, since the stepwise operation of these aggregations can be repeatedly carried out a plurality of times, so-called capsule-like particles are formed by gradually changing the desired composition and physical properties from the surface to the inside of the toner particles. The toner structure can be easily formed, and the toner structure control becomes extremely easy.

For example, in the case of a color toner using a multi-color toner, after the mother agglomerated particles are made of the resin particles and the pigment particles in the first step, the resin particle dispersion is added to form only the resin layer on the toner surface. By forming it, the influence of the pigment particles on the charging behavior can be minimized. This makes it possible to prevent differences in the charging characteristics depending on the type of pigment, and in the second step, if the glass transition temperature of the particles to be added is set to a high value, the capsules are coated with the toner to save heat. Property and fixability can be compatible. In addition, in the second step, by using a dispersion liquid of fine particles of an inorganic antibacterial agent, a toner structure encapsulated with the inorganic antibacterial agent can be formed after coalescence. Alternatively, if a release agent particle dispersion liquid such as wax is added in the second stage, and a resin or inorganic antibacterial agent particle dispersion liquid having high hardness is used in the third stage to form a shell on the outermost surface, the wax is exposed. The toner structure can be formed such that the wax effectively acts as a release agent during fixing while suppressing the above.

[Antibacterial Agent] The antibacterial agent in the present invention is preferably an inorganic antibacterial agent in view of antibacterial persistence and environmental safety, but it is limited to this as long as it satisfies the above antibacterial persistence and safety. Not a thing.

The inorganic antibacterial agent in the present invention is not particularly limited as long as it is an inorganic substance having an antibacterial action, but an antibacterial agent containing an antibacterial metal is preferable. Typical examples of the antibacterial metal generally include silver, copper, zinc, platinum, nickel, and titanium oxide having a photocatalytic action. Of these, the antibacterial metal preferably used is silver, zinc or titanium oxide having a strong antibacterial activity. Only one kind of these may be used, but two or more kinds of metals may be mixed and used. Here, as the titanium oxide having the photocatalytic action, for example, anatase type titanium oxide can be mentioned. In order to obtain the photocatalytic effect, it is desirable to add at least 5% by mass to the particles. Further, it is used in the range of 30% by weight or less. It is preferably 8% by mass or more. As the anatase type titanium oxide, those having an average primary particle size of 1 nm to 1000 nm can be used, and those having an average primary particle size of 10 nm to 50 nm are preferably used in terms of the catalytic effect. The specific surface area can be used in the range of 10~700m ² / g, preferably not less than 50 m ² / g. Further, any shape such as a spherical shape or a needle shape can be used. The photocatalyst may be used alone or in combination of two or more kinds, or may be used in combination with a porous material such as zeolite, silica gel, a fluororesin or the like.

[Method of Adding Antibacterial Agent to Toner Particles] The method of adding the above-mentioned inorganic antibacterial agent to toner particles will be described below.

(I) Method of chemically treating the surface of the antibacterial agent: When the resin has a polar group, the antibacterial metal ion is ion-exchanged, ion-coordinated or ion-coordinated with the resin polar group, and further deposited. Thereby, the antibacterial metal can be contained in the resin.

The polar group of the resin is not limited, and examples thereof include a carbonyl group, a primary amino group, a secondary amino group, a tertiary amino group, a quaternary amino group, a phosphoric acid group, a phosphoric acid ester group, a hydroxyl group, and a mercapto. Examples thereof include a group, a carboxyl group, an ether group, an ester group, a sulfonic acid group, a sulfonyl group, a sulfuric ester group and a cyano group. Among them, a carboxyl group, a sulfonic acid group, an amino group, a phosphoric acid group, and a cyano group antibacterial metal are easy to control the characteristics in fixing using an electrophotographic method.

The method of ion-exchange or ion-coordinate the antibacterial metal ion to the resin polar group may be any method as long as the compound containing the antibacterial metal ion is mixed with the resin having the polar group. For example, a method in which an antibacterial metal ion compound is dissolved in an organic solvent, an aqueous solvent or the like and brought into contact with a resin can be mentioned.

Further, the antibacterial metal complex compound coordinated with the polar group of the resin can be deposited on the resin as ultrafine metal complex particles by treating with the ligand compound. In this case, in addition to the antibacterial property being improved by microparticulation, dissociation of the antibacterial metal from the resin is unlikely to occur, so that the durability of the antibacterial effect is improved as compared with the case of only ion exchange or ion coordination.

There is no limitation on the ligand compound capable of depositing the metal complex compound coordinated with the antibacterial metal ion on the resin and the ion thereof. Examples of the ligand compound and its ion include pyrophosphoric acid, polyphosphoric acid, silicic acid, aluminic acid, tungstic acid, vanadic acid, molybdic acid,
Antimonic acid, bromine, chlorine, iodine, fluorine, ammonia, acetylacetone, adenine, adenosine triphosphate, 2-aminoethanol, 2-aminoethanethiol, imidazole, ethylamine, ethylenediamine,
Catechol, glycylglycine, glycine, acetic acid, dibenzo-18-crown-6, histidine, 2,2'-bipyridine, pyridine, 1,10-phenanthroline, phenol, o-benzenedicarboxylic acid, sulfur, chloric acid,
Examples thereof include bromic acid, iodic acid, sulfuric acid, sulfurous acid, thiosulfuric acid, thiocyanic acid, carbonic acid, oxalic acid, benzoic acid, phthalic acid, carboxylic acid, hydrocyanic acid, and ions derived from them.

It is also possible to deposit ultrafine metal particles on the resin by subjecting the polar group of the resin to ion exchange or coordination of the antibacterial metal ion and then reducing the resin. Also in this case, since the antibacterial metal becomes ultrafine particles, the exposed area of the antibacterial metal is increased, and thus the antibacterial effect is improved. In this case as well, the binding of the antibacterial metal to the resin becomes strong, so the durability of the antibacterial effect is increased.

The antibacterial metal ion coordinated to the resin can be reduced by a conventional method. As a preferable method, a reduction method by heating, which can reduce all the antibacterial metal ions ion-exchanged or coordinated with the resin to ultrafine metal particles, can be mentioned. The reducing agent is not limited, sodium borohydride, hydrazine, formalin, compounds containing an aldehyde group, hydrazine sulfate, hydrocyanic acid and its salts,
Method of reducing in solution using a reducing agent such as hyposulfite and its salt, thiosulfate, hydrogen peroxide, Rochelle salt, glucose, alcohol group-containing compound, hypophosphorous acid and its salt, and hydrogen, one Examples thereof include a method of heat treatment in a reducing atmosphere such as carbon oxide and hydrogen sulfide, a method of using a reducing atmosphere and an inert gas in combination, a method of irradiating light, or a method of combining these. At this time, there is no problem in adding a pH adjuster, a buffer, a stabilizer, a surfactant and the like.

In addition to these methods, when the resin has a polar group, a ligand ion capable of depositing and precipitating a metal complex compound is ion-exchanged, and then an antibacterial metal is distributed to this ligand ion. The metal complex compound can be deposited in the polymer particles. Further, the deposited metal complex compound can be reduced to ultrafine metal particles.

(Ii) Method of coating antibacterial agent:
As a method of adding the antibacterial metal when polymerizing the resin and incorporating the antibacterial metal in the resin, the timing and method of adding and mixing the antibacterial metal are not limited. Examples thereof include a method in which an antibacterial metal is mixed in a raw material monomer or a resin monomer solution and then polymerized, a method in which an intermediate of a polymerization reaction is mixed and polymerized, and a method in which a polymer is mixed. In particular, in the case of producing a resin by an emulsion polymerization aggregation method, an antibacterial metal is used in any step of a step of mixing a colorant dispersion with resin agglomerated particles, an agglomeration step of forming agglomerated particles, and a fusing step of fusing the agglomerated particles. Can be added. At this time, it is preferable to add the antibacterial metal in the aggregating step or after the aggregating step and before the fusing step because the antibacterial metal can be uniformly contained in the surface layer of the agglomerated particles.

(Iii) External addition method of antibacterial agent: Alternatively, the antibacterial metal may be supported on an inorganic material and then added to a resin. Here, the carrier carrying the antibacterial metal is not particularly limited, but examples thereof include alumina, zeolite, silica gel, phosphate compounds, calcium carbonate, calcium silicate, silicate glass, bentonite, and titanium oxide. it can. In particular, phosphate compounds are preferred because of their high safety and long-lasting antibacterial effect due to the low desorption of metal ions. Further, a preferable combination of the antibacterial metal and the inorganic carrier is a calcium phosphate compound or hydroxyapatite loaded with at least one of silver and zinc.

The method of supporting the antibacterial metal on the carrier is not particularly limited. Examples thereof include a method of supporting by physical adsorption or chemical adsorption, a method of supporting with a binder, a method of driving an antibacterial metal compound into a carrier and supporting it. In addition, there is also a method of forming a thin film of an antibacterial metal compound on the surface of an inorganic compound by a thin film forming method such as vapor deposition, dissolution precipitation reaction, and sputtering, and supporting the thin film.

As a method of incorporating an antibacterial agent made of an antibacterial metal supported on these inorganic carriers into toner particles, a method by external addition to the toner can be considered. External addition to the toner can be realized by a conventional method. For example, when the functional fine particles are externally added to the coating composition, as a method of adding, the coating composition is dried and then attached to the surface by a dry method using a mixer such as a V blender or a Hensiel mixer. A method may be used in which the fine particles are dispersed in a liquid and then added to a coating composition in the form of a slurry and dried to adhere to the surface, or as a wet method, a method in which a slurry is dried on a dry powder while being dried. By these methods, the antibacterial agent can be retained near the toner surface.

[Content of Antibacterial Agent in Toner Particles] The content of the antibacterial metal contained in the toner particles is 0.01 to 10% by weight based on the toner particles. When it is less than 0.01% by weight, sufficient antibacterial properties cannot be exhibited,
If it exceeds 10% by weight, the electric resistance required for the toner,
Characteristics such as cleaning property may be deteriorated. The more preferable content of the antibacterial metal is 0.03 to 3% by weight.

In the present invention, the antibacterial agent blended by externally adding after the polymerization step or the polymerization of the toner particles is a silicone treatment, a metal soap treatment, a fatty acid treatment, a surfactant treatment, or an acid, alkali or inorganic treatment. You may mix | blend, after performing the process by salt, and also these complex processes.

[Developer] The toner of the present invention and magnetic particles (carrier) may be mixed to form a two-component developer. Alternatively, when magnetic powder is mixed with the toner of the present invention and a magnetic developer or a developer containing no magnetic powder is used alone, it can be a one-component developer.

The toner and developer of the present invention may contain other constituents such as a colorant, a charge control agent, a release agent and a magnetic powder depending on the use and need thereof. Furthermore,
Toners and developers can be blended with one or more known additives in a range that does not affect the image forming property and antibacterial property. For example, a fluidizer, a fluidity aid, a cleaning aid, a flame retardant, a flame retardant aid, a preservative, a fungicide, an ultraviolet absorber, an ultraviolet shielding agent, a dispersant, a filler,
A binder or the like.

The resin used in the toner particles of the present invention is not particularly limited, but specifically, styrenes such as styrene, parachlorostyrene, α-methylstyrene; methyl acrylate, ethyl acrylate, n-acrylic acid. Acrylic monomers such as propyl, lauryl acrylate, 2-ethylhexyl acrylate; Methacrylic monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; Ethylenically unsaturated acid monomers such as acrylic acid, methacrylic acid and sodium styrene sulfonate; vinyl nitriles such as acrylonitrile and methacrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl methyl ketone and vinyl ethyl Vinyl ketones such as ketones and vinyl isopropenyl ketone; homopolymers such as monomers of olefins such as ethylene, propylene and butadiene, copolymers of two or more kinds of those monomers, or a mixture thereof. In addition, non-vinyl condensation resin such as epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, etc.
Or, a mixture of them and the vinyl resin, a graft polymer obtained by polymerizing a vinyl monomer in the coexistence of these, and the like can be mentioned. Among these, a styrene-based copolymer and a polyester-based resin are used as the resin preferable for exhibiting the characteristics of the toner.

The number average molecular weight of the resin preferable as the toner particles is 1500 to 100,000, and the preferable glass transition temperature is 40 to 100 ° C. Resin number average molecular weight is 1500
If the glass transition temperature is less than 40 ° C., or the glass transition temperature is less than 40 ° C., the toner may lack fluidity,
If it exceeds, a large amount of energy is required to transfer the image, which is not preferable from the viewpoint of environmental protection. More preferable number average molecular weight of the resin particles is 2000 to 100,000.

The color of the toner and / or developer of the present invention is not limited, and they may or may not contain a colorant. When a colorant is contained, the colorant used is not limited, and examples thereof include inorganic pigments, organic pigments, and various dyes, and these may be used alone or in combination.
Further, the following release agents and charge control agents may be used.

Examples of colorants and internal additives are carbon black, chrome yellow, Hansa yellow, benzidine yellow, slene yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red. , Brilliant anchormin 3B, brilliant anchormin 6
B, Daypon oil red, pyrazolone red, resole red, rhodamine B rake, rake red C, rose bengal, aniline blue, ultramarine blue,
Various pigments such as chalco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate, etc .; acridine-based, xanthene-based, azo-based, benzoquinone-based, azine-based, anthraquinone-based, thioindico-based, dioxazine-based, thiazine-based Coloring agents such as azomethine-based, indico-based, phthalocyanine-based, aniline black-based, polymethine-based, triphenylmethane-based, diphenylmethane-based, and thiazole-based dyes may be used alone or in combination of two or more. Further, ferrite, magnetite, reduced iron, cobalt, nickel, manganese, and other metals, alloys, or magnetic materials such as compounds containing these metals are used as internal additives, and quaternary ammonium salt compounds and nigrosine are used as charge control agents. It is possible to use various charge control agents that are normally used such as dyes composed of complex compounds, complexes of aluminum, iron, chromium, etc., and triphenylmethane pigments, but ionic strength that affects the stability of aggregation and coalescence. From the viewpoints of controlling the above and reducing the pollution of wastewater, materials that are not easily dissolved in water are preferable.

Examples of the releasing agent include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene, silicones having a softening point by heating, oleic acid amide, erucic acid amide, ricinoleic acid amide and stearic acid amide. Fatty acid amides and ester wax, carnauba wax, rice wax, candelilla wax, tree wax, plant wax such as jojoba oil, animal wax such as beeswax, montan wax, ozokerite, ceresin, paraffin wax, Minerals such as microcrystalline wax and Fischer-Tropsch wax, petroleum waxes, and modified products thereof can be used. These waxes are
A homogenizer or pressure discharge type disperser that can disperse in water together with a polyelectrolyte such as an ionic surfactant or a high molecular weight acid or high molecular weight, and is heated to a temperature above the melting point, and is subjected to strong shearing. Dispersions can be prepared.

As the charge control agent, various charge control agents usually used such as a quaternary ammonium salt compound, a nigrosine compound, a dye composed of a complex of aluminum, iron, chromium, or a triphenylmethane pigment can be used. But,
A material that is not easily dissolved in water is preferable from the viewpoints of controlling the ionic strength that affects the stability of aggregation and aggregation and reducing the pollution of wastewater.

After drying as in the case of ordinary toner, inorganic particles such as silica, alumina, titania and calcium carbonate and resin particles such as vinyl resin, polyester and silicone are sheared in a dry state and added to the surface. It can also be used as a fluidity aid or a cleaning aid.

Examples of surfactants used for emulsion polymerization, seed polymerization, pigment dispersion, resin particles, release agent dispersion, aggregation, or stabilization thereof include sulfuric acid ester salt type, sulfonic acid salt type, and phosphoric acid ester. -Based and soap-based anionic surfactants, amine-based and quaternary ammonium salt-based cationic surfactants, and polyethylene glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based nonionic interfaces It is also effective to use an activator in combination, and as a means for dispersion, a general one such as a ball mill having a rotary shearing homogenizer or a media, a sand mill and a dyno mill can be used.

The metal salt compound used in the aggregating step in the method for producing toner particles can be obtained by dissolving a general inorganic metal compound or a polymer thereof in a resin fine particle dispersion liquid. The constituent metal elements are 2A, 3A, 4A, 5A in the periodic table (long period table),
Any material having a charge of two or more valences belonging to groups 6A, 7A, 8, 1B, 2B, and 3B and capable of being dissolved in the form of ions in the aggregation system of resin fine particles may be used. Specific examples of preferable inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, calcium polysulfide. And the like, such as an inorganic metal salt polymer. Among them, aluminum salts and polymers thereof are particularly preferable. Generally, in order to obtain a sharper particle size distribution, the valence of the inorganic metal salt is 1 to 2 valences, 2 to 3 valences or more, and even if the valences are the same, polymerization type inorganic metal salt weights are high. Combined is more suitable.

[Image Forming Apparatus] Next, an image forming apparatus using the electrophotographic toner of the present invention or the electrophotographic developer of the present invention will be described. The image forming apparatus, a latent image forming means for forming a latent image on the latent image carrier based on image data, and the latent image formed is developed with a developer,
In an image forming apparatus having a developing unit for forming a toner image and a transferring unit for transferring the toner image onto a transfer target, the toner for forming the toner image is the antibacterial agent-containing spherical toner of the present invention.

[Image Forming Method] Further, in the image forming method using the electrophotographic toner of the present invention or the electrophotographic developer of the present invention, a latent image is formed to form an electrostatic latent image on a latent image carrier. A step of developing the electrostatic latent image with a toner or a developer to form a toner image, a transfer step of transferring the toner image onto a transfer target to form a transfer image, and the transfer target And a fixing step of fixing the transferred image transferred onto the electrophotographic toner, wherein the electrophotographic toner is the antibacterial agent-containing toner of the present invention, and the developer is the developer of the present invention.

In the above image forming apparatus and image forming method, the developer may be either a one-component type or a two-component type. In the case of a one-component system, as described above, the electrophotographic toner in which the magnetic powder is mixed with the toner of the present invention is used, and in the case of a two-component system, the antibacterial agent of the electrophotographic toner of the present invention is contained. An electrophotographic developer in which a toner and a carrier are mixed is used. As the above-mentioned means of the image forming apparatus and the above-mentioned steps of the image forming method, known means and steps in the image forming apparatus and the image forming method can be used.

As the latent image bearing member, for example, an electrophotographic photosensitive member and a dielectric recording member can be used. In the case of an electrophotographic photoreceptor, the surface of the electrophotographic photoreceptor is uniformly charged by a corotron charger, a contact charger, etc., and then exposed.
An electrostatic latent image is formed (latent image forming means, latent image forming step).
Next, the toner particles are attached to the electrostatic latent image by contacting or approaching a developing roll having a developer layer formed on the surface to form a toner image on the electrophotographic photosensitive member (a part of the transfer unit, the developing unit). Process). The formed toner image is transferred to the surface of a transfer target such as paper using a corotron charger or a contact charger (transfer means, transfer step). Further, the toner image transferred to the surface of the transfer target is thermally fixed by the fixing device to form a final toner image. During thermal fixing by the fixing device, a releasing agent is usually supplied to the fixing member in the fixing device in order to prevent offset and the like.

A roller or a belt can be used as the fixing member used in the thermocompression bonding. As the transfer target (recording member) for transferring the toner image, for example, plain paper used in electrophotographic copying machines, printers, etc., OHP sheets, and usable media differ depending on the specifications of the image forming apparatus. , Papers, resin films, cloths, and laminates thereof. A medium on which an image is formed is called an "image body" in the present application.

[0076]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The compositions shown in Table 1 below were obtained in Examples 1, 3,
4 and the resin particles of Comparative Example 1 were manufactured.

[0078]

[Table 1] An anionic surfactant Neogen R (registered trademark) (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: sodium dodecylbenzenesulfonate) was prepared by mixing and dissolving the constituents of the resin dispersion with this composition.
13 g of deionized water was dissolved in 555 g of ion-exchanged water, dispersed and emulsified in a flask, and slowly mixed for 10 minutes, while ion-exchanged water 4 of 9 g of ammonium persulfate was dissolved.
Nitrogen substitution was performed by charging 2.8 g. After that, the content in the flask was heated in an oil bath until the temperature reached 70 ° C. while stirring, and emulsion polymerization was continued for 6 hours to obtain a resin fine particle dispersion.

Preparation of pigment dispersion

[Table 2] Copper phthalocyanine pigment (manufactured by BASF): 100 g Anionic surfactant "Neogen R" (registered trademark): 15 g Ion-exchanged water: 200 g Above, the composition shown in Table 2 was mixed and dissolved, and the rotor-stator type homogenizer ( IKA Ultra Turrax)
Was dispersed for 10 minutes, and further dispersed with an ultrasonic disperser for 20 minutes to prepare a cyan pigment dispersion having a center diameter of 170 nm.

Preparation of Toner Particles Using the resin dispersion thus prepared , resin particles having the following composition were produced. The type of the resin particle dispersion used is shown in Table 3.

[0081]

[Table 3] Resin fine particle dispersion: 160 g Pigment dispersion: 30g Resin particle dispersion (additional): 40 g Release agent dispersion: 30 g Sanizole B50: 2.5g Deionized water: 800g

[Preparation of Toner Particles and Developer of Examples 1, 3, 4 and Comparative Example 1] All of the constituents of the above resin particles except for the resin particle dispersion (for addition) were round stainless steel flasks. Put it in the homogenizer (IKA
After thoroughly mixing and dispersing with Ultra Turrax T50 manufactured by K.K., 5 while stirring the flask in a heating oil bath.
Heated to 5 ° C. After holding at 55 ° C. for 30 minutes, the resin dispersion was slowly added, and the temperature of the heating oil bath was further raised to 56 ° C. and kept at that temperature for a certain period of time to obtain agglomerated particles. In addition, the resin dispersion liquid described in this description is shown in Table 1.
Table 4 shows the time used for the production of agglomerated particles.

[0083]

[Table 4]

Thereafter, 5N of 1N sodium hydroxide is added here.
After adding 2 g, the stainless steel flask was closed and heated to 96 ° C. while continuing stirring using a magnetic seal,
The aggregated particles were fused by holding for a certain period of time. The retention time and pH at that time are shown in Table 4. The volume average particle size (D ₅₀ ) of the fused particles was measured by a Coulter counter (TAI manufactured by Nikkaki Co., Ltd.).
I) was used for measurement. The fused particles were thoroughly washed with ion-exchanged water and then freeze-dried to obtain toner particles.

To the toner particles, 0.8 wt% of silica TS720 (manufactured by Cabot) and 0.5 wt% of Apacider C (silver carrying hydroxyapatite; manufactured by Sangi Co., Ltd.) were added and mixed, and then a ferrite core of 50 μm was added. A carrier coated with 1% by weight of polymethylmethacrylate (manufactured by Soken Kagaku Co., Ltd.) was adjusted and mixed so that the toner concentration was 8% by weight to prepare a developer.

[Preparation of Toner Particles and Developer of Example 2] Using the agglomerated particles produced as in Example 1 above,
Toner particles were obtained in the same manner except that the resin dispersion liquid used for producing the toner particles was as follows. 0.5 g of Apacider C (hydroxyapatite-supporting silver; made by Sangi Co., Ltd.) was added to 40 g of the resin dispersion liquid for addition, and thoroughly mixed and dispersed by a homogenizer (Ultra Turrax T50 made by LKA), and then dispersion for addition. Used as a liquid. The temperature of the heating oil bath in the aggregating step, the time of holding at that temperature, and the pH at that time are as shown in Table 4 above.

To the toner particles, 0.8 wt% of silica TS720 (manufactured by Cabot) was added and mixed, and then a carrier having a 50 μm ferrite core coated with 1 wt% of polymethylmethacrylate (manufactured by Soken Kagaku Co., Ltd.) was used.
A developer was prepared and mixed so as to have a weight percentage.

[Preparation of Toner Particles and Developer of Comparative Example 2]

[Table 5] Linear polyester resin: 90% by weight (linear polyester obtained from terephthalic acid / bisphenol A / ethylene oxide adduct / cyclohexanedimethanol) C.I. I. Pigment Blue: 4% by weight The above mixture was kneaded with an extruder (TEM48, manufactured by Toshiba Machine Co., Ltd.). The obtained kneaded product was cooled, crushed with a hammer mill, and then crushed with a jet mill. afterwards,
Toner particles were obtained by classification with an air classifier.

0.5% by weight of silica TS720 (manufactured by Cabot)) and 0.5% by weight of Apacider C (silver carrying hydroxyapatite; manufactured by Sangi Co., Ltd.) were added to and mixed with the toner particles in a Henschel mixer. 50 μm
A carrier in which 1 wt% of polymethylmethacrylate (manufactured by Soken Kagaku Co., Ltd.) was coated on the ferrite core of 1 was adjusted and mixed so that the toner concentration was 8 wt% to prepare a developer.

[Production Method of Toner Particles and Developer of Comparative Example 3]

[Table 6] Linear polyester resin: 90% by weight (linear polyester obtained from terephthalic acid / bisphenol A / ethylene oxide adduct / cyclohexanedimethanol) C.I. I. Pigment Blue: 4 wt% Apacider C: 0.5 wt% (Hydroxyapatite-supported silver; manufactured by Sangi Co., Ltd.) The above mixture was kneaded with an extruder (TEM48, manufactured by Toshiba Machine Co., Ltd.). The obtained kneaded product was cooled, crushed with a hammer mill, and then crushed with a jet mill. afterwards,
Toner particles were obtained by classification with an air classifier.

To the above toner particles, 0.5 wt% of silica TS720 (manufactured by Cabot) was added and mixed with a Henschel mixer, and a carrier having a 50 μm ferrite core coated with 1 wt% of polymethylmethacrylate (manufactured by Soken Chemical Co., Ltd.) was used as a toner. A developer was prepared by mixing and adjusting the concentration to be 8% by weight.

<Evaluation Method> (i) Shape Factor SF1: A microscopic image or a scanning electron microscopic image of toner particles was determined using a Luzex image analyzer (LUZEXIII, manufactured by Nicolet) based on the following formula.

[0093]

SF1 = (ML ² / A) × (π / 4) × 100 where ML: absolute maximum length of toner particles, A: projected area of particles

(Ii) Average volume particle distribution GSDv: The average volume particle diameter of the toner particles was measured as follows. The average volume particle diameter (D ₅₀ ) and the average volume particle distribution GSD were measured by a laser diffraction particle size distribution measuring device (LA-7 manufactured by Horiba, Ltd.).
00).

(Iii) Weight of toner: Using each of the developers manufactured as described above, ordinary non-coated full-color exclusive paper was used as an image forming medium, and the image area ratio was 100%.
A solid image having an area of 10 cm ² was prepared on the image forming medium. At the stage where the toner is unfixed, the image forming medium to which the toner is transferred is weighed, and after all the unfixed toner is removed by air blow, the weight of only the image forming medium is measured, and the image portion The toner weight per unit area (TMA: mg / cm ² ) was measured.

(Iv) Antibacterial Evaluation: <Sample> Each developer prepared as described above was molded into a flat plate molded body (thickness: 2 mm × 50 mm × 50 mm), disinfected with ethanol for disinfection, and thoroughly dried. In the same manner as the weight measurement of the toner and the developer, 10% of the image area ratio is set.
A solid image having an area of cm ² is formed on the image forming medium, and the image body is 50 mm × with the image fixing area in the center.
Paper cut to 50 mm was used as a sample.

<Test Method> First, the test method when a developer is used as a sample will be described. Using the developer prepared as described above as a sample, the viable cell count of E. coli after 24 hours at 35 ° C. was evaluated by the film adhesion method. Regarding the antibacterial effect, the antibacterial property was determined to be good by reducing the number of initially added bacteria to 1/100 or less as determined by the film adhesion method. Escherichia coli (ISO3301) was used as a test bacterium. To prepare the test bacterial solution, first, 5 mg of meat extract,
A normal broth medium was prepared by dissolving 10 mg of peptone and 5 mg of sodium chloride in 1 liter of distilled water.
Then, a solution was prepared by further diluting the broth medium 500 times with distilled water, and Escherichia coli was suspended in the solution so that the number of bacteria was 10 ⁶ per 1 ml.

0.5 ml of the bacterial solution was added dropwise to this sample, and a polyethylene film was adhered thereto and left at 35 ° C. for 24 hours. The bacteria attached to this sample and the coated film are SC
Using 9.5 ml of DLP medium (manufactured by Nippon Pharmaceutical Co., Ltd.), it was sufficiently poured into a sterile petri dish, and the viable cell count in 1 ml of this wash-out solution was determined by using a standard agar medium for measuring the number of bacteria (Nissui Co., Ltd.).
The product was measured by the agar plate dilution method, and the sterilization rate was calculated. This sterilization rate was calculated as the ratio of the viable cell count after 24 hours / the viable cell count at the start of the test, and evaluated by the following index.

[0099] ⊚: Sterilization rate 99.9% or more Δ: Sterilization rate 97% or more and less than 99.9% ×: Sterilization rate less than 97%

(V) Image evaluation: Using each developer prepared as described above, using a modified machine of V500 (manufactured by Fuji Xerox Co., Ltd.), the image quality was evaluated for uniformity of solid images and reproducibility of fine lines. went.

Uniformity of a solid image is obtained by applying a developer at a temperature of 22 ° C.
In an environment with a humidity of 55% and a final transfer material of Fuji Xerox J-coated paper, an image with an area ratio of 10% is set to 1
Outputs 0,000 sheets. Fine line reproducibility is line width 50μ on the photoconductor
An image of a fine line was formed so as to have a thickness of m, and the image was transferred and fixed. The thin line image of the fixed image on the transfer material is VH-62.
It was observed at a magnification of 175 times using a 00 Micro Hiscope (manufactured by Keyence Corporation). The solid uniformity and the fine line reproducibility of a solid image after outputting 100,000 sheets were evaluated using the following criteria.

⊚: There is no density unevenness in the solid image and the reproducibility of fine lines is good. Δ: There is slight density unevenness observed in the solid image, and / or unevenness at the edge portion of the fine line is observed. Density unevenness is observed in the solid image, and the uniformity of fine lines and the unevenness of the edge are conspicuous.

[0103]

[Table 7]

[0104]

The toner of the present invention is characterized by containing a component having antibacterial properties, and having a particle diameter within a certain fixed range, a narrow particle distribution, and a shape close to a true sphere. In addition to being capable of forming high-quality images, this toner is capable of efficiently imparting antibacterial properties to a toner, a developer containing the toner, and an image body formed by fixing these, in a small amount. it can.

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Claims (5)

[Claims] 1. An antibacterial agent-containing spherical toner having a shape factor SF1 of 140 or less and containing an inorganic antibacterial agent in the vicinity of the surface. 2. A two-component developer containing the antibacterial agent-containing spherical toner according to claim 1 and a carrier. 3. An image body prepared by using the antibacterial agent-containing spherical toner according to claim 1. Description: 4. A latent image forming means for forming a latent image on a latent image carrier based on image data, and a developing means for developing the formed latent image with a developer to form a toner image. An image forming apparatus comprising: a transfer unit that transfers the toner image onto a transfer-receiving member, wherein the toner that forms the toner image is the toner according to claim 1. 5. A latent image forming step of forming an electrostatic latent image on a latent image carrier; a developing step of developing the electrostatic latent image with toner or a developer to form a toner image; In an image forming method including a transfer step of forming a transfer image by transferring onto a transfer body, and a fixing step of fixing the transfer image transferred onto the transfer body, a toner forming the toner image is An image forming method comprising the toner according to claim 1.