JP5217318B2 - Developing roller and developing device using the same - Google Patents

Description

  The present invention relates to a developing roller and a developing device using the same.

  Electrophotographic image forming methods widely used at present are in contact with an electrostatic latent image formed on an electrostatic latent image carrier (usually an electrophotographic photosensitive member) with charged toner or through a narrow gap. The toner image on the electrostatic latent image carrier formed through the development process in which the electrostatic latent image is visualized with toner is transferred onto plain paper and then fixed to form a final image. Is.

  As a developing method for forming a toner image, a two-component developing system in which toner is charged and developed using a two-component developer composed of a carrier and toner, or a developing roller that transports the developer using only toner There is a one-component development system in which development is performed by charging with friction with a developer regulating member or the like. In this one-component development system, since no carrier is used, the development apparatus can be simplified, and in recent years, it has been widely used. In particular, with the trend of colorization in recent years, a non-magnetic one-component development method using a toner that does not contain a magnetic material is attracting attention because it can be colored.

  Unlike the two-component development method, this method does not use a carrier and charges the toner only by rubbing the toner against the charging member or by pressing it against the surface of the developing roller. In addition, there is a great merit that it can be made compact. As a result, there is also a feature that it can be easily applied to a color image forming apparatus that normally requires four or more developing mechanisms. In particular, in recent years, the weight reduction and downsizing of the apparatus have been actively promoted, and a developing method using a non-magnetic one-component developer has become mainstream in printers.

  As a developing roller in this non-magnetic one-component developing system, conventionally, for example, a roller in which an elastic layer using silicone rubber is formed on the outer periphery of a conductive shaft has been used. To charge the toner, a thin layer of toner is formed on the developing roller using a charging member such as a metal plate or a roller, and is rubbed against this, so the mechanism is extremely simple. Becomes a developer.

  In this developing roller, an elastic layer using a rubber-like elastic material such as silicone rubber is formed on the outer peripheral surface of a metallic or conductive resin shaft. In order to impart, a surface layer may be formed on the elastic layer. It is known to use fluororubber for the surface layer in order to prevent toner adhesion and fusion. In order to form a fluororubber layer on the elastic layer, it is necessary to improve adhesiveness, and an intermediate layer of a silane coupling agent is formed on the elastic layer surface, and further, fluororubber or the like as a main component is formed thereon. It is known to form a used coating layer (see, for example, Patent Document 1).

  Due to the recent downsizing of the apparatus and shortening of the printout time, the cycle of toner conveyance, charging, developing, and toner replacement, which are functions of the developing roller, has become faster and the load on the developing roller has increased.

  Since the developing roller having a configuration in which the coating layer is directly formed on the shaft does not absorb the impact of the developing roller configured to be installed via the elastic layer when force is applied to the coating layer from the outside, Adhesiveness between the shaft and the coating layer is required.

  In order to improve the adhesion between the shaft and the coating layer, studies have been made to provide an adhesive layer between the shaft and the coating layer (see, for example, Patent Document 2).

In addition, studies have been made on using stainless steel as a shaft and directly forming a coating layer thereon (see, for example, Patent Document 3).
JP-A-8-190263 JP-A-7-56434 JP 2002-14535 A

  However, the developing roller produced by directly forming the coating layer on the shaft described above has poor interlayer adhesion between the shaft and the coating layer, and when a large number of sheets are printed, the coating layer peels off, resulting in a high-quality toner image. I couldn't get it continuously.

  SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent developing roller having a good interlayer adhesion between a shaft and a coating layer and capable of continuously obtaining a high-quality toner image, and a developing device using the same.

  The subject of this invention is expressed by either of the structures described below.

1.
In a developing roller configured by directly forming a coating layer having a resin and a conductive agent on the outer periphery of a shaft made of at least an aluminum alloy,
The aluminum alloy contains 0.2 to 0.8% by mass of silicon element and 0.05 to 1.5% by mass of manganese element with respect to the total amount of aluminum alloy ,
A developing roller , wherein the resin is a siloxane-modified polyurethane resin .

2.
2. Said aluminum alloy contains 0.4-6.0 mass% of magnesium elements and 0.04-0.35 mass% of chromium elements with respect to the total amount of aluminum alloys, Development roller.

3 .
In a developing device having a developing roller formed by directly forming a coating layer having a resin and a conductive agent on the outer periphery of a shaft made of at least an aluminum alloy,
The aluminum alloy contains 0.2 to 0.8% by mass of silicon element and 0.05 to 1.5% by mass of manganese element with respect to the total amount of aluminum alloy ,
A developing device , wherein the resin is a siloxane-modified polyurethane resin .

4 .
It said aluminum alloy is 0.4 to 6.0 mass% elemental magnesium the aluminum alloy total, according to the 3, characterized in that the chromium element contains 0.04 to 0.35 wt% Development device.

  The developing roller of the present invention has an excellent effect that the interlayer adhesion between the shaft and the coating layer is good and a high-quality toner image can be continuously obtained.

  The inventors of the present invention have intensively studied a developing roller that improves the interlayer adhesion between the shaft and the coating layer and can continuously obtain a high-quality toner image.

  As a result of various studies, it has been found that when an appropriate amount of a specific element is mixed in an aluminum alloy as a shaft, the interlayer adhesion between the shaft and the coating layer is improved and a high-quality toner image is continuously obtained. It was.

  The reason why the high-quality toner image can be continuously obtained while satisfying the interlayer adhesion is that the element added to the aluminum alloy crystallizes on the surface as a eutectic depending on its content. However, it has not yet been theoretically elucidated.

  The present invention is characterized in that an aluminum alloy containing a certain amount of silicon element and manganese element is used as the material of the shaft. Furthermore, an aluminum alloy containing a certain amount of magnesium element and chromium element in addition to the above elements is preferred.

  The content of the element has a range suitable for each element. The silicon (Si) element is 0.2 to 0.8% by mass and the manganese (Mn) element is 0.05 to 1.5% with respect to the total amount of the aluminum alloy. % By mass.

  Further, the magnesium (Mg) element is preferably 0.4 to 6.0 mass%, and the chromium (Cr) element is preferably 0.04 to 0.35 mass.

  By setting the content of the element contained in the aluminum alloy within the above range, it is possible to improve interlayer adhesion and continuously obtain high-quality toner images.

  The elements contained in the aluminum alloy and the amount thereof can be measured by high frequency inductively coupled plasma emission spectroscopy.

  High frequency inductively coupled plasma emission spectroscopy (Inductively Coupled Plasma) is a method in which a solution sample in which a metal is dissolved in acid, alkali, or the like is sprayed into Ar plasma, and excited light is split into each wavelength and the light is dispersed. This is a method for quantifying the type and content of an element from its strength. This method has a linear relationship between light intensity and content from a minute range to a high concentration, and each element can be analyzed simultaneously.

  “ULTIMA2000 (manufactured by Horiba, Ltd.)” can be used as a measuring device for high-frequency inductively coupled plasma optical emission spectrometry.

  Hereinafter, the present invention will be described in detail.

<Configuration of developing roller>
The developing roller of the present invention is constructed by directly forming a coating layer having at least a resin and a conductive agent on the outer periphery of an aluminum alloy shaft containing at least a silicon element and a manganese element.

  FIG. 1 is a schematic sectional view showing an example of the developing roller of the present invention.

  In FIG. 1, 25 is a developing roller, 11 is a shaft, 12 is a coating layer, 13 is a lower layer, and 14 is an upper layer.

  The developing roller of the present invention has a coating layer 12 directly provided on a shaft 11 as shown in FIG. 1A, and a lower layer 13 provided directly on the shaft 11 as shown in FIG. It may be a coating layer 12 having a multilayer structure provided with. Each of the lower layer and the upper layer may be formed of a plurality of layers.

<Interlayer adhesion>
The developing roller of the present invention is characterized by a strong interlayer adhesion between the shaft and the coating layer.

  The interlayer adhesion between the shaft and the coating layer was measured and evaluated by the following method.

  FIG. 2 is a schematic diagram for explaining a method for measuring an interlayer adhesion force between a shaft and a coating layer.

  As shown in FIG. 2A, the developing roller 25 is cut along the outer periphery thereof with a width of 2.5 cm as indicated by a broken line X, as shown in FIG. A cut (broken line Y) is made in the direction of the shaft 11 with respect to 12, and the covering layer 12 is slightly peeled therefrom, and as shown in FIG. 2 (b), the end of the peeled covering layer 12 is pulled. The grip 5 was picked up and pulled up vertically (in the direction of the arrow Z), and the strength of the interlayer was measured by measuring how much force the cover layer began to peel off from the shaft. In the present invention, a precision universal testing machine “Autograph AGS (manufactured by Shimadzu Corporation)” was used as the tensile testing machine.

  Specifically, in the process of raising the coating layer at a speed of 100 mm / min and increasing the load capacity to 20 N, a load value that can raise the coating layer without increasing the load was obtained.

  Next, materials used for forming the developing roll of the present invention will be described.

"shaft"
The material of the shaft used in the present invention contains 0.2 to 0.8% by mass of silicon element, 0.05 to 1.5% by mass of manganese element with respect to the total amount of aluminum alloy, and further contains 0.001% of magnesium element. It preferably contains 4 to 6.0 mass% and 0.04 to 0.35 mass of chromium element.

The outer diameter of the shaft is preferably 5 to 30 mm, more preferably 10 to 20 mm. Since the shaft also serves as a member for leaking charges accumulated on the surface of the developing roller, the specific resistance is preferably 1 × 10 ⁴ Ω · cm or less. Specifically, in order to reduce the weight of the shaft, a hollow aluminum alloy sleeve (having a thickness of about 0.8 to 2.0 mm) with flanges attached to both ends is preferable. The specific resistance can be measured by a known method.

<Coating layer>
The coating layer is formed by applying a coating liquid prepared by appropriately blending a conductive agent (electronic conductive agent or ionic conductive agent), a resin, and, if necessary, a non-conductive filler to the outer peripheral surface of the shaft, and drying the coating solution. In some cases, it can be formed by heating and curing.

<Resin for coating layer>
The resin of the coating layer is not particularly limited, but specifically, siloxane-modified polyurethane resin, acrylic resin, urea resin, melamine resin, alkyd resin, phenol-modified / silicone-modified modified alkyd resin, oil A free alkyd resin, a silicone resin, a fluorine resin, a phenol resin, a polyamide resin, an epoxy resin, a polyester resin, a maleic acid resin, a urethane resin, and the like can be given. Of these, siloxane-modified polyurethane resin, acrylic resin, polyamide resin, and the like are preferably used from the viewpoint of self-film reinforcing property, toner charging property, and the like. Among these, it is particularly preferable to use a siloxane-modified polyurethane resin from the viewpoint of obtaining good abrasion resistance.

  The urethane resin is obtained by reacting a urethane raw material containing a polyhydroxy compound and an isocyanate compound. For example, the urethane resin is obtained by a method in which a prepolymer is subjected to a crosslinking reaction, or a polyol is obtained by a one-shot method. What was obtained by the method of making it react with an isocyanate cake etc. is mentioned.

  In this case, as a polyhydroxyl compound used when obtaining a urethane resin, a polyol used for production of a general flexible polyurethane foam or a urethane elastomer, for example, a polyether polyol having a polyhydroxyl group at a terminal, a polyester polyol, or a polyether In addition to polyester polyols, general polyols such as polyolefin polyols such as polybutadiene polyol and polyisoprene polyol, and so-called polymer polyols obtained by polymerizing ethylenically unsaturated monomers in polyols can be used. As the isocyanate compound, polyisocyanate used in the production of general flexible polyurethane foam and urethane elastomer, that is, tolylene diisocyanate (sometimes referred to as TDI), crude TDI, 4,4'-diphenylmethane. Diisocyanate (sometimes referred to as MDI), crude MDI, aliphatic polyisocyanate having 2 to 18 carbon atoms, alicyclic polyisocyanate having 4 to 15 carbon atoms, and mixtures and modified products of these polyisocyanates, such as partially polyol A prepolymer obtained by reacting with a polymer can be used. In particular, the mixing ratio of the polyisocyanate may be lowered for the purpose of reducing the universal hardness of the coating layer.

  Moreover, the urethane resin may be prepared using a one-pack type or two-pack type urethane raw material containing a polyhydroxyl compound and a polyisocyanate, and an epoxy resin or a melamine resin is used as a crosslinking agent as necessary. Also good.

  The polyamide resin is polyamide 6,6,6,6.10,6.12,11,12,12.12 and polyamide obtained by polycondensation between different types of polyamide monomers, from the viewpoint of workability. Alcohol-soluble ones are preferred. For example, those obtained by adjusting the molecular weight of a polyamide terpolymer or quaternary copolymer, or those obtained by methoxymethylating polyamide 6 or polyamide 12 to make them soluble in alcohol or water.

  The acrylic resin includes polyacrylate, polymethyl methacrylate, polymethyl ethacrylate, those obtained by substituting these side chain ends with a hydroxyalkyl group, and copolymers thereof.

  Monomers constituting the acrylic resin include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid. Examples include hexyl, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

  As the resin used in the present invention, a silicone copolymer polyurethane resin is more preferable. The silicone copolymer polyurethane resin can be synthesized from a compound having in its molecule a silicone skeleton having a polyfunctional isocyanate having two or more functional groups and a hydroxyl group having two or more functional groups.

  The silicone copolymer polyurethane resin is not particularly limited, but those disclosed in Japanese Patent Publication No. 7-33427 can be used.

  Examples of the siloxane-modified polyurethane resin include a polyurethane resin (1) obtained from a polyol, an isocyanate and a chain extender and having a functional group reactive with an epoxy group, and an epoxy compound having one hydroxyl group in one molecule ( A) (hereinafter simply referred to as an epoxy compound (A)) and an alkoxy obtained by reacting an alkoxy group-containing alkoxysilane partial condensate (2) obtained by a dealcoholization reaction between the alkoxysilane partial condensate (B). A group-containing siloxane-modified polyurethane resin can be used, but is not limited thereto.

  The functional group having reactivity with the epoxy group in the polyurethane resin (1) may be present at either the terminal or the main chain of the polyurethane resin (1). Examples of such functional groups include an acidic group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group, an amino group, a hydroxyl group, and a mercapto group. An acidic group and an amino group are preferable from the viewpoint of reactivity with an epoxy group and ease of imparting a functional group. The method for imparting an acidic group to the polyurethane resin (1) is not particularly limited. For example, the functional group can be imparted by using a compound having the aforementioned functional group as the chain extender or the polymerization terminator. .

  As a method for producing the polyurethane resin (1) used in the present invention, a one-stage method in which a polymer polyol, a diisocyanate compound and, if necessary, a chain extender and / or a polymerization terminator are reacted at once in a suitable solvent, A polymer polyol and a diisocyanate compound are reacted under an excess of isocyanate groups to prepare a prepolymer having an isocyanate group at the terminal of the polymer polyol, and then this is added to a chain extender in an appropriate solvent and, if necessary, And a two-stage method of reacting with a polymerization terminator. The two-stage method is preferred for the purpose of obtaining a uniform polymer solution. In these production methods, the solvent used is usually an aromatic solvent such as benzene, toluene or xylene; an ester solvent such as ethyl acetate or butyl acetate; methanol, ethanol, isopropanol, n-butanol, diacetone alcohol or the like. Alcohol solvents; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; other solvents such as dimethylformamide, dimethylacetamide, ethylene glycol dimethyl ether, tetrahydrofuran, and cyclohexanone can be used alone or in combination.

  The method for imparting amino groups to the polyurethane resin (1) is not limited. For example, polyamines may be reacted with the terminal isocyanate groups of the prepolymer so that the amino groups are excessive. The amount of the epoxy group-reactive functional group in the polyurethane resin (1) is not particularly limited, but it is usually preferably 0.1 to 20 KOHmg / g. When it is less than 0.1 KOHmg / g, the flexibility and heat resistance of the obtained polyurethane resin-silica hybrid are lowered, and when it exceeds 20 KOHmg / g, the water resistance of the polyurethane resin-silica hybrid tends to be lowered. In the polyurethane resin, those containing a urea bond are more preferable for interlayer adhesion.

  As described above, the epoxy group-containing alkoxysilane partial condensate (2) of the present invention is obtained by a dealcoholization reaction between the epoxy compound (A) and the alkoxysilane partial condensate (B).

  As the epoxy compound (A), the number of epoxy groups is not particularly limited as long as it is an epoxy compound having one hydroxyl group in one molecule. In addition, as the epoxy compound (A), the smaller the molecular weight, the better the compatibility with the alkoxysilane partial condensate (B), and the higher the heat resistance and adhesion imparting effect. Is preferred. Specific examples include monoglycidyl ethers having one hydroxyl group at the molecular end obtained by reacting epichlorohydrin with water, dihydric alcohol or phenol; epichlorohydrin and glycerin, pentaerythritol, etc. Polyglycidyl ethers having one hydroxyl group at the molecular end obtained by reacting with a trihydric or higher polyhydric alcohol of the above; one hydroxyl group at the molecular end obtained by reacting epichlorohydrin and amino monoalcohol Examples thereof include alicyclic hydrocarbon monoepoxides having one hydroxyl group in the molecule (for example, epoxidized tetrahydrobenzyl alcohol). Among these epoxy compounds, glycidol is most suitable in terms of heat resistance imparting effect, and is also optimal because of its high reactivity with the alkoxysilane partial condensate (2).

  Further, the alkoxysilane partial condensate (B) is obtained by hydrolyzing a hydrolyzable alkoxysilane monomer represented by the following general formula (a) in the presence of acid or alkaline water and partially condensing it. Is used.

Formula (a): R ¹ _p Si (OR ² ) _4-P
(In the formula, p represents 0 or 1. R ¹ represents a lower alkyl group, aryl group or unsaturated aliphatic residue which may have a functional group directly connected to a carbon atom. R ² represents a methyl group. Or an ethyl group, and R ² may be the same or different.
Specific examples of such hydrolyzable alkoxysilane monomers include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyl Trialkoxysilanes such as tripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, can give. In addition, as these alkoxysilane partial condensates (B), those exemplified above can be used without particular limitation. However, when two or more of these examples are used in combination, tetramethoxysilane is replaced with alkoxysilane. What was synthesized using 70 mol% or more of all alkoxysilane monomers constituting the partial condensate (B) is preferable. In addition, when the ratio of the silane skeleton contained in the polyurethane resin-silica hybrid is 1.0% by mass or more and 30.0% by mass or less, very stable adhesiveness is exhibited.

  The alkoxysilane partial condensate (B) is represented by, for example, the following general formula (b) or (c).

(In the general formula (b), R ¹ represents a lower alkyl group, an aryl group or an unsaturated aliphatic residue which may have a functional group directly connected to a carbon atom. R ² represents a methyl group or an ethyl group. R ² may be the same or different, and n is an integer.)

(In the general formula (c), the same .n as R ^1, R ² of R ^1, R ² is In formula (b) is an integer.)
<Electronic conductive agent>
Examples of the electronic conductive agent include various conductive metals or alloys such as carbon black, graphite, aluminum, copper, tin, and stainless steel, tin oxide, zinc oxide, indium oxide, titanium oxide, tin oxide antimony monoxide solid solution, tin oxide Various conductive metal oxides such as indium oxide solid solution, and fine powders such as insulating substances coated with these conductive materials can be used. Among these, carbon black is preferably used because it can be obtained relatively easily and good chargeability can be obtained.

  The type of carbon black is not particularly limited, and various conventionally known carbon blacks such as ketjen black, channel black, and furnace black can be used. The blending amount of carbon black is not particularly limited because it varies depending on the type of carbon black to be used, but it is usually preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the resin component. preferable. This blending amount is appropriately set according to the conductivity and universal hardness required for the coating layer.

<Ionic conductive agent>
As the ionic conductive agent, conventionally known inorganic ionic salts and organic ionic salts can be appropriately selected and used. Specifically, alkali metal halides such as Li, LiCl, NaI, NaBr, and KI, perchlorates such as LiClO ₄ , KCl1O ₄ , CuCl ₂ Mg (ClO ₄ ) ₂ , and thiocyanic acids such as LiSCN, NaSCN, and CsSCN Inorganic ion salts such as salts, aliphatic sulfonates, higher alcohol sulfates, higher alcohol phosphates, higher alcohol ethylene oxide addition sulfates, higher alcohol ethylene oxide addition phosphates, quaternary ammonium Examples thereof include organic ion salts such as salts and betaines. Among these, quaternary ammonium salts such as trimethyloctadecyl ammonium perchlorate, tetramethylammonium chloride, and benzyltrimethylammonium chloride are particularly preferable. These ionic conductive agents may be used alone or in combination of two or more.

  The compounding amount of the ionic conductive agent is not particularly limited and is appropriately selected according to various situations, but is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the resin component forming the coating layer, and 0.05 to 2 Part by mass is more preferable.

As a result, in the resistance region of 1 × 10 ⁴ to 1 × 10 ¹⁰ Ω · cm, there is little variation in the position of the electrical resistance, and the voltage dependence of the electrical resistance is small. A coating layer having low conductivity can be obtained.

  Next, production of the developing roller will be described.

《Shaft preparation》
A shaft produced using an aluminum alloy containing the element is used.

  The shaft is a hollow cylindrical conductive shaft with a small diameter (for example, outer diameter of 5 to 30 mm) and a thin wall thickness (for example, 0.5 to 2.0 mm) in order to make the image forming apparatus small, light, and low cost. What attached the flange is preferable.

<< Production of coating layer >>
As a means for directly forming the coating layer on the outer peripheral surface of the shaft, a coating solution obtained by dissolving and dispersing the above-described constituent materials (resin and conductive agent, and non-conductive filler as required) in an organic solvent is applied to the shaft. The method of apply | coating to is preferable. The resin component concentration of the coating solution is not particularly limited and may be appropriately adjusted according to the required layer thickness. However, the resin component concentration is 10% by mass or more from the dispersibility and stability of the solid in the coating solution. It is preferable that

  The solvent used for preparing the resin component concentration of the coating solution is not particularly limited as long as it can dissolve the resin component, and examples thereof include lower alcohols such as methanol, ethanol and isopropanol, and ketones such as methyl ethyl ketone. , Cyclohexane, toluene, xylene and the like are preferably used.

  Examples of the method for forming the coating layer include dipping, spraying, roll coating, and brushing depending on the viscosity of the resin component constituting the coating layer. Among these, the coating layer is formed uniformly. Easy dipping and spraying are preferred.

  1-30 micrometers is preferable and, as for the thickness of a coating layer, 5-20 micrometers is more preferable. The thickness of the coating layer is measured from a micrograph of the cross-sectional sample obtained by taking a cross-sectional sample including the coating layer from the developing roller.

  In addition, as a shaft, it is preferable to use what was made from the said aluminum alloy and processed into the hollow cylinder shape whose outer diameter is 5-30 mm and wall thickness is 0.8-2.0 mm.

  Next, a non-magnetic one-component developer (hereinafter also simply referred to as toner) that can be used for image formation using the developing roller according to the present invention will be described. The toner that can be used for image formation using the developing roller according to the present invention is either a so-called pulverized toner manufactured through a pulverizing / classifying process, or a so-called polymerized toner manufactured directly from a polymerization process for preparing resin particles. Can be used. Among these, in particular, the polymerized toner can be produced while controlling the particle size and shape of the toner during the production process, which is convenient for producing a toner having a small particle size having a uniform shape.

  By using toner with a small particle size that has a uniform shape, it is easy to form a high-resolution and high-definition image as required in digital image formation, and is particularly preferable for, for example, high-gradation pictorial full-color image formation. It is. It is expected that high-definition full-color image formation can be stably produced by combining with the developing roller according to the present invention.

  On the other hand, the polymerized toner includes an emulsion-association type toner in which particles are aggregated to form toner particles in the production process, but a small amount of the coagulant used in the aggregation process remains on the surface of the produced toner particles. It is also possible to do. There has been a concern about the influence on the residual charge on the surface of the developing roller due to such residue remaining on the surface of the developing roller.

  However, in the developing roller according to the present invention, even if image formation is repeated using polymerized toner, the residual charge on the surface of the developing roller does not increase, and good image formation can be achieved from the results of Examples described later. confirmed.

  Hereinafter, elements constituting a polymerized toner which is an example that can be used for image formation using the developing roller according to the present invention will be described.

(Monomer)
As the polymerizable monomer, a radically polymerizable monomer is an essential component, and a crosslinking agent can be used as necessary. Moreover, it is preferable to contain at least one radical polymerizable monomer having the following acidic group or radical polymerizable monomer having a basic group. (1) Radical polymerizable monomer The radical polymerizable monomer component is not particularly limited, and a conventionally known radical polymerizable monomer can be used. Moreover, it can be used combining 1 type (s) or 2 or more types so that the required characteristic may be satisfy | filled.

  Specifically, aromatic vinyl monomers, (meth) acrylic acid ester monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, diolefin monomers , Halogenated olefin monomers and the like can be used.

  Examples of the aromatic vinyl monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, p-ethyl styrene, p. -N-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, 2, Examples thereof include styrene monomers such as 4-dimethylstyrene and 3,4-dichlorostyrene and derivatives thereof.

  Examples of (meth) acrylic acid ester monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid. Examples include butyl, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

  Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl benzoate.

  Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like.

  Examples of the monoolefin monomer include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene and the like.

  Examples of the diolefin monomer include butadiene, isoprene, chloroprene and the like.

  Examples of the halogenated olefin monomer include vinyl chloride, vinylidene chloride, vinyl bromide and the like.

(2) Crosslinking agent As the crosslinking agent, a radical polymerizable crosslinking agent may be added to improve the properties of the toner. Examples of the radical polymerizable crosslinking agent include those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diallyl phthalate.

(3) Radical polymerizable monomer having acidic group or basic group As the radical polymerizable monomer having acidic group or radical polymerizable monomer having basic group, for example, a carboxyl group-containing monomer Amine-based compounds such as sulfonic acid group-containing monomers, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts can be used.

  Examples of the radical polymerizable monomer having an acidic group include carboxylic acid group-containing monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, maleic acid monobutyl ester, and maleic acid monoester. An octyl ester etc. are mentioned.

  Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, allyl sulfosuccinic acid, octyl allyl sulfosuccinate and the like.

  These may have a structure of an alkali metal salt such as sodium or potassium or an alkaline earth metal salt such as calcium.

  Examples of the radical polymerizable monomer having a basic group include amine compounds, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and quaternary ammonium salts of the above four compounds, 3-dimethylaminophenyl acrylate, 2-hydroxy-3-methacryloxypropyltrimethylammonium salt, acrylamide, N-butylacrylamide, N, N-dibutylacrylamide, piperidylacrylamide, methacrylamide, N-butylmethacrylamide, N-octadecylacrylamide Vinyl pyridine, vinyl pyrrolidone; vinyl-N-methylpyridinium chloride, vinyl-N-ethylpyridinium chloride, N, N-dia Methyl ammonium chloride, N, may be mentioned N- diallyl-ethyl chloride or the like.

  As the radical polymerizable monomer, it is preferable to use a radical polymerizable monomer having an acidic group or a radical polymerizable monomer having a basic group in an amount of 0.1 to 15% by mass of the whole monomer, The radical polymerizable cross-linking agent is preferably used in the range of 0.1 to 10% by mass with respect to the total radical polymerizable monomer, although it depends on its characteristics.

(Chain transfer agent)
For the purpose of adjusting the molecular weight, it is possible to use a commonly used chain transfer agent.

  The chain transfer agent is not particularly limited, and for example, octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, n-octyl-3-mercaptopropionic acid ester, carbon tetrabromide and styrene dimer are used.

(Polymerization initiator)
The radical polymerization initiator can be appropriately used as long as it is water-soluble. For example, persulfate (potassium persulfate, ammonium persulfate, etc.), azo compounds (4,4′-azobis-4-cyanovaleric acid and its salts, 2,2′-azobis (2-amidinopropane) salt, etc.), A peroxide compound etc. are mentioned.

  Furthermore, the radical polymerization initiator can be combined with a reducing agent as necessary to form a redox initiator. By using a redox initiator, the polymerization activity increases, the polymerization temperature can be lowered, and the polymerization time can be expected to be shortened.

  The polymerization temperature may be any temperature as long as it is equal to or higher than the lowest radical generation temperature of the polymerization initiator. For example, a range of 50 ° C. to 90 ° C. is used. However, it is also possible to polymerize at room temperature or slightly higher temperature by using a polymerization initiator that starts at room temperature, for example, a combination of hydrogen peroxide and a reducing agent (ascorbic acid or the like).

(Surfactant)
In order to perform polymerization using the above-mentioned radical polymerizable monomer, it is necessary to perform oil droplet dispersion in an aqueous medium using a surfactant. Although it does not specifically limit as surfactant which can be used in this case, The following ionic surfactant can be mentioned as an example of a suitable thing.

  Examples of ionic surfactants include sulfonates (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol-6 Sodium sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sodium sulfonate, etc.), sulfuric acid Ester salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate) Beam, calcium oleate and the like).

  Nonionic surfactants can also be used. Specifically, polyethylene oxide, polypropylene oxide, combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, sorbitan ester Etc. These are mainly used as an emulsifier at the time of emulsion polymerization, but may be used for other processes or purposes.

(Coloring agent)
Examples of the colorant include inorganic pigments, organic pigments, and dyes.

  A conventionally well-known thing can be used as an inorganic pigment. Specific inorganic pigments are exemplified below.

  Examples of the black pigment include carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black, and magnetic powder such as magnetite and ferrite.

  These inorganic pigments can be used alone or in combination as required. Moreover, the addition amount of a pigment is 2-20 mass% with respect to a polymer, Preferably 3-15 mass% is selected.

  Conventionally known organic pigments and dyes can also be used. Specific organic pigments and dyes are exemplified below.

  Examples of pigments for magenta or red include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. And CI Pigment Red 222.

  Examples of the orange or yellow pigment include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 156, and the like.

  Examples of pigments for green or cyan include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Green 7.

  As the dye, C.I. I. Solvent Red 1, C.I. I. Solvent Red 49, C.I. I. Solvent Red 52, C.I. I. Solvent Red 58, C.I. I. Solvent Red 63, C.I. I. Solvent Red 111, C.I. I. Solvent Red 122, C.I. I. Solvent Yellow 19, C.I. I. Solvent Yellow 44, C.I. I. Solvent Yellow 77, C.I. I. Solvent Yellow 79, C.I. I. Solvent Yellow 81, C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow 93, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow 103, C.I. I. Solvent Yellow 104, C.I. I. Solvent Yellow 112, C.I. I. Solvent Yellow 162, C.I. I. Solvent Blue 25, C.I. I. Solvent Blue 36, C.I. I. Solvent Blue 60, C.I. I. Solvent Blue 70, C.I. I. Solvent Blue 93, C.I. I. Solvent blue 95 etc. can be used and these mixtures can also be used.

  These organic pigments and dyes can be used alone or in combination as desired. Moreover, the addition amount of a pigment is 2-20 mass% with respect to a polymer, Preferably 3-15 mass% is selected.

(wax)
In the polymerized toner, wax may be contained in the toner particles. There is no particular limitation on the structure and composition of the wax itself. Low molecular weight polyolefin waxes such as polypropylene and polyethylene, paraffin wax, Fischer-Tropsch wax, ester wax and the like can be used.

  The addition amount is 1 to 30% by mass, preferably 2 to 20% by mass, and more preferably 3 to 15% by mass with respect to the whole toner.

  As a toner that can be used for image formation using the developing roller according to the present invention, a toner in which wax is dissolved is dispersed in water and polymerized to form particles in which wax is encapsulated in resin particles. The toner is preferably salted out / fused with the colorant particles to form a toner.

(Toner production method)
The toner of the present invention comprises a step of dispersing a monomer solution in which wax is dissolved in an aqueous medium, and then preparing resin particles containing a release agent by a polymerization method, and using the resin particle dispersion liquid in an aqueous medium. The step of fusing the resin particles in step, the step of filtering the obtained particles from an aqueous medium to remove the surfactant, the step of drying the obtained particles, and the external addition to the particles obtained by drying It is preferable to produce by a polymerization method composed of an external additive addition step of adding an agent and the like. Here, the resin particles may be colored particles. Further, non-colored particles can also be used as the resin particles. In this case, colored particles are formed by adding a colorant particle dispersion or the like to the resin particle dispersion and then fusing it in an aqueous medium.

  In particular, the method of fusing is preferably a method of salting out / fusing using resin particles produced by the polymerization step. When non-colored resin particles are used, the resin particles and the colorant particles can be salted out / fused in an aqueous medium.

  In addition to the colorant and the release agent, a charge control agent that is a component of the toner can be added as particles in this step.

  In addition, an aqueous medium means what consists of water as a main component, and contains water content 50 mass% or more here. Examples of those other than water include organic solvents that dissolve in water, and examples include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran.

  As a preferred polymerization method in the present invention, a monomer solution in which a release agent is dissolved in a monomer is dispersed in oil droplets by mechanical energy in an aqueous medium in which a surfactant having a critical micelle concentration or less is dissolved. A method may be mentioned in which a water-soluble polymerization initiator is added to the dispersion and radical polymerization is performed. In this case, an oil-soluble polymerization initiator may be added to the monomer.

  The disperser for performing the oil droplet dispersion is not particularly limited, and examples thereof include CLEARMIX, ultrasonic disperser, mechanical homogenizer, manton gourin, and pressure homogenizer.

  As described above, the colorant itself may be used after surface modification. In the surface modification method of the colorant, the colorant is dispersed in a solvent, and after the surface modifier is added therein, the temperature is raised and the reaction is performed. After completion of the reaction, the mixture is filtered, washed with the same solvent, repeatedly filtered and dried to obtain a pigment treated with a surface modifier.

  There is a method in which the colorant particles are prepared by dispersing a colorant in an aqueous medium. This dispersion is performed in a state where the surfactant concentration in water is equal to or higher than the critical micelle concentration (CMC).

  The disperser at the time of pigment dispersion is not particularly limited, but preferably a medium such as CLEARMIX, ultrasonic disperser, mechanical homogenizer, pressure disperser such as Manton Gorin or pressure homogenizer, sand grinder, Getzmann mill, diamond fine mill, etc. Type disperser.

  As the surfactant used here, the aforementioned surfactants can be used.

  In the step of salting out / fusion, a salting-out agent composed of an alkali metal salt or an alkaline earth metal salt is added as a flocculant having a critical coagulation concentration or more in water in which resin particles and colorant particles are present. Then, it is a step of performing fusion at the same time as the salting-out proceeds by heating to the glass transition point or more of the resin particles.

  Here, the alkali metal salt and the alkaline earth metal salt which are salting-out agents include lithium, potassium, sodium and the like as the alkali metal, and examples of the alkaline earth metal include magnesium, calcium, strontium and barium. Preferably, potassium, sodium, magnesium, calcium, and barium are used. Examples of the salt include chlorine salt, bromine salt, iodine salt, carbonate salt, sulfate salt and the like.

(Other additives)
In addition to the resin, the colorant, and the release agent, the toner may be added with a material that can impart various functions as a toner material. Specific examples include charge control agents. These components can be added simultaneously with the resin particles and the colorant particles in the salting-out / fusion step described above, and can be added by various methods such as a method of inclusion in the toner and a method of adding to the resin particles themselves.

  Similarly, various known charge control agents and those that can be dispersed in water can be used. Specific examples include nigrosine dyes, naphthenic acid or higher fatty acid metal salts, alkoxylated amines, quaternary ammonium salt compounds, azo metal complexes, salicylic acid metal salts or metal complexes thereof.

(External additive)
To the toner of the present invention, so-called external additives can be added and used for the purpose of improving fluidity, chargeability and cleaning property. These external additives are not particularly limited, and various inorganic fine particles, organic fine particles and lubricants can be used. Usually, the particles before the addition of these external additives are often called colored particles, and the particles after the addition are often called toners or toner particles. However, both may be toner or toner particles.

  A conventionally well-known thing can be used as an inorganic fine particle. Specifically, silica, titanium, alumina fine particles and the like having a number average primary particle diameter of 5 to 500 nm can be preferably used. These inorganic fine particles are preferably hydrophobic.

  Specifically, as silica fine particles, for example, commercially available products R-805, R-976, R-974, R-972, R-812, R-809 manufactured by Nippon Aerosil Co., Ltd., HVK-2150, H manufactured by Hoechst -200, commercially available products TS-720, TS-530, TS-610, H-5, MS-5 and the like manufactured by Cabot Corporation.

  Examples of the titanium fine particles include commercial products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., commercial products MT-100S, MT-100B, MT-500BS, MT-600, MT-600SS, and JA- 1. Commercial products TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T manufactured by Fuji Titanium Co., Ltd. Commercial products IT-S, IT-OA, IT-OB, IT- manufactured by Idemitsu Kosan Co., Ltd. OC etc. are mentioned.

  Examples of the alumina fine particles include commercial products RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd. and commercial products TTO-55 manufactured by Ishihara Sangyo Co., Ltd.

  As the organic fine particles, spherical organic fine particles having a number average primary particle diameter of about 10 to 2000 nm can be used. As this, a homopolymer such as styrene or methyl methacrylate or a copolymer thereof can be used.

  Examples of lubricants include, for example, zinc stearate, aluminum, copper, magnesium, calcium, etc., zinc oleate, manganese, iron, copper, magnesium, etc., zinc palmitate, copper, magnesium, calcium, etc. And salts of higher fatty acids such as zinc of linoleic acid, salts of calcium, etc., zinc of ricinoleic acid, salts of calcium, etc.

  The amount of these external additives added is preferably 0.1 to 5% by mass with respect to the toner.

  As a method for adding the external additive, various known mixing apparatuses such as a Turbuler mixer, a Henschel mixer, a Nauter mixer, and a V-type mixer can be used.

In the present invention, from the viewpoint of obtaining a high-quality toner image, those having a median diameter (D ₅₀ ) diameter of 3 to 9 μm on a volume basis prepared by a polymerization method are preferable.

  Next, the developing device and the full-color image forming apparatus according to the present invention will be described.

  FIG. 3 is a schematic sectional view showing an example of the developing device according to the present invention.

  The developing device 20 shown in FIG. 3 has a buffer chamber 26 adjacent to the developing roller 25, and a hopper 27 and the like adjacent to the buffer chamber 26.

  In the buffer chamber 26, a blade 28 as a toner regulating member is disposed in pressure contact with the developing roller 25. The blade 28 regulates the charge amount and adhesion amount of the toner on the developing roller 25. Further, it is possible to further provide an auxiliary blade 29 for assisting regulation of the toner charge amount and adhesion amount on the developing roller 25 on the downstream side of the blade 28 with respect to the rotation direction of the developing roller 25.

  A supply roller 30 is pressed against the developing roller 25. The supply roller 30 is driven to rotate in the same direction as the developing roller 25 (counterclockwise direction in the drawing) by a motor (not shown). The supply roller 30 has a conductive cylindrical base and a foam layer formed of urethane foam or the like on the outer periphery of the base.

  The hopper 27 contains toner T which is a non-magnetic one-component developer. The hopper 27 is provided with a rotating body 34 for stirring the toner T. A film-like conveying blade is attached to the rotating body 34, and the toner T is conveyed by the rotation of the rotating body 34 in the arrow direction. The toner T conveyed by the conveying blades is supplied to the buffer chamber 26 via a passage 32 provided in a partition wall that separates the hopper 27 and the buffer chamber 26. The shape of the conveying blade is bent while the toner T is conveyed in front of the rotation direction of the blade as the rotating body 34 rotates, and returns to a straight state when the left end of the passage 32 is reached. Thus, the toner T is supplied to the passage 32 by returning the shape of the blade straightly through the curved state.

  The passage 32 is provided with a valve 321 for closing the passage 32. This valve is a film-like member, one end of which is fixed to the upper side of the right side of the passage 32 of the partition wall. When the toner T is supplied from the hopper 27 to the passage 32, the valve 32 is pushed rightward by the pressing force from the toner T. Can be opened. As a result, the toner T is supplied into the buffer chamber 26.

  Further, a regulating member 322 is attached to the other end of the valve 321. The regulating member 322 and the supply roller 30 are arranged so as to form a slight gap even when the valve 321 closes the passage 32. The regulating member 322 adjusts so that the amount of toner accumulated at the bottom of the buffer chamber 26 does not become excessive, so that a large amount of toner T collected from the developing roller 25 to the supply roller 30 does not fall to the bottom of the buffer chamber 26. Adjusted to

  In the developing device 20, the developing roller 25 is rotationally driven in the arrow direction during image formation, and the toner in the buffer chamber 26 is supplied onto the developing roller 25 by the rotation of the supply roller 30. The toner T supplied onto the developing roller 25 is charged and thinned by the blade 28 and the auxiliary blade 29 and then conveyed to a region facing the image carrier to develop the electrostatic latent image on the image carrier. To be served. The toner that has not been used for development returns to the buffer chamber 26 as the developing roller 25 rotates, and is scraped and collected from the developing roller 25 by the supply roller 30.

  FIG. 4 is a schematic sectional view showing an example of a full-color image forming apparatus.

  In the full-color image forming apparatus shown in FIG. 4, a charging brush 111 and the like for uniformly charging the surface of the photosensitive drum 10 to a predetermined potential are provided around the photosensitive drum 10 that is rotationally driven.

  A laser scanning optical system 35 for scanning and exposing the photosensitive drum 10 charged by the charging brush 111 with a laser beam is provided. The laser scanning optical system 35 includes a laser diode, a polygon mirror, and an fθ optical element. As is well known, print data for each of yellow, magenta, cyan, and black is transferred from the host computer to the control unit. The laser scanning optical system 35 sequentially outputs the laser beam as a laser beam based on the print data for each color, scans and exposes the surface of the photosensitive drum 10, and thereby the static image for each color on the photosensitive drum 10. Electro latent images are sequentially formed.

  In addition, the full-color developing device 36 that performs full-color development by supplying toner of each color to the photosensitive drum 10 on which the electrostatic latent image is formed in this manner is provided with yellow, magenta, cyan, and black around the support shaft 33. Four color-developing units 31Y, 31M, 31C, and 31Bk each containing non-magnetic one-component toner are provided. The developing units 31Y, 31M, 31C, and 31Bk rotate around the support shaft 33, and the developing units 31Y, 31M, 31C, and 31Bk are rotated. It is guided to a position facing the photosensitive drum 10.

  Further, in each of the developing devices 31Y, 31M, 31C, and 31Bk in the full-color developing device 36, as shown in FIG. 4, the toner is formed on the outer peripheral surface of the developer carrying member (developing roller) 25 that rotates and conveys the toner. A regulating member is in pressure contact, and the toner regulating member regulates the amount of toner conveyed by the developing roller 25 and charges the conveyed toner. In the full-color developing device 36, two toner regulating members may be provided in order to appropriately regulate and charge the toner conveyed by the developing roller.

  Then, every time the electrostatic latent image of each color is formed on the photosensitive drum 10 by the laser scanning optical system 35 as described above, the full-color developing device 36 is rotated around the support shaft 33 as described above. Then, the developing devices 31Y, 31M, 31C, and 31Bk containing toner of the corresponding colors are sequentially guided to positions facing the photosensitive drum 10, and the developing rollers 25 in the developing devices 31Y, 31M, 31C, and 31Bk are moved. As described above, development is performed by sequentially supplying charged toner of each color toward the photosensitive drum 10 on which the electrostatic latent images of each color are sequentially formed.

  Further, an endless intermediate transfer belt 40 that is rotationally driven is provided as an intermediate transfer member 40 at a position downstream of the full-color developing device 36 in the rotation direction of the photosensitive drum 10. Is driven to rotate in synchronization with the photosensitive drum 10. The intermediate transfer belt 40 is pressed by a rotatable primary transfer roller 41 so as to come into contact with the photosensitive drum 10, and a portion of a support roller 42 that supports the intermediate transfer belt 40 includes: A secondary transfer roller 43 is rotatably provided, and the recording material S such as recording paper is pressed against the intermediate transfer belt 40 by the secondary transfer roller 43.

  Further, a cleaner 50 that scrapes off the toner remaining on the intermediate transfer belt 40 is provided in a space between the full-color developing device 36 and the intermediate transfer belt 40 so as to be able to contact and separate from the intermediate transfer belt 40. ing.

  Further, the paper feeding means 60 that guides the recording material S such as plain paper to the intermediate transfer belt 40 includes a paper feeding tray 61 that accommodates the recording material S and the recording material S that is accommodated in the paper feeding tray 61 one by one. The recording material S fed in synchronization with the paper feed roller 62 for feeding paper and the image formed on the intermediate transfer belt 40 is sent between the intermediate transfer belt 40 and the secondary transfer roller 43. The recording material S sent between the intermediate transfer belt 40 and the secondary transfer roller 43 in this way is pressed against the intermediate transfer belt 40 by the secondary transfer roller 43. The toner image is pressed and transferred from the intermediate transfer belt 40 to the recording material S.

  On the other hand, the recording material S on which the toner image is pressed and transferred as described above is guided to the fixing device 70 by the conveying means 66 constituted by an air suction belt or the like, and is transferred by the fixing device 70. The toner image is fixed on the recording material S, and then the recording material S is discharged onto the upper surface of the apparatus main body 100 through the vertical conveyance path 80.

  Next, the operation of forming a full color image using this full color image forming apparatus will be specifically described.

  First, the photosensitive drum 10 and the intermediate transfer belt 40 are rotationally driven in the respective directions at the same peripheral speed, and the photosensitive drum 10 is charged to a predetermined potential by the charging brush 111.

  The photosensitive drum 10 thus charged is exposed to a yellow image by the laser scanning optical system 35 to form an electrostatic latent image of the yellow image on the photosensitive drum 10. The yellow image is developed by supplying the yellow toner charged by the toner regulating member as described above from the developing device 31Y in which the yellow toner is accommodated in the photosensitive drum 10, and the yellow toner image is thus formed. The intermediate transfer belt 40 is pressed against the body drum 10 by the primary transfer roller 41, and the yellow toner image formed on the photosensitive drum 10 is primarily transferred to the intermediate transfer belt 40.

  After the yellow toner image is transferred to the intermediate transfer belt 40 in this way, the full-color developing device 36 is rotated around the support shaft 33 as described above, and the developing device 31M containing magenta toner is exposed to light. As in the case of the yellow image described above, the magenta image is exposed to the photosensitive drum 10 charged by the laser scanning optical system 35 to form an electrostatic latent image. The electrostatic latent image is developed by a developing device 31M containing magenta toner, and the developed magenta toner image is primarily transferred from the photosensitive drum 10 to the intermediate transfer belt 40. Black image exposure, development, and primary transfer are sequentially performed, and yellow, magenta, cyan, and black toner images are sequentially superimposed on the intermediate transfer belt 40. To form a full color toner image.

  When the final black toner image is primarily transferred onto the intermediate transfer belt 40, the recording material S is fed between the secondary transfer roller 43 and the intermediate transfer belt 40 by the timing roller 63, and the secondary transfer roller. The recording material S is pressed against the intermediate transfer belt 40 by 43, and the full color toner image formed on the intermediate transfer belt 40 is secondarily transferred onto the recording material S.

  When the full-color toner image is secondarily transferred onto the recording material S in this way, the recording material S is guided to the fixing device 70 by the conveying means 66, and the full-color toner transferred by the fixing device 70 is transferred. The image is fixed on the recording material S, and then the recording material S is discharged onto the upper surface of the apparatus main body 100 through the vertical conveyance path 80. Reference numeral 112 denotes a cleaning device.

  The present invention will be specifically described below with reference to examples, but the embodiments of the present invention are not limited to these examples.

Production of Development Roller A development roller was produced by the following procedure.

《Shaft preparation》
As the shaft, an aluminum alloy containing the metal element described in Table 1 is used, and a hollow cylindrical tube having an outer diameter and a thickness described in Table 1 and Table 2 is produced, and a flange is formed at the end of the hollow cylindrical tube. The thing which attached was prepared. This is referred to as “shafts 1 to 31”.

<Preparation of coating solution for coating layer formation>
(Preparation of coating layer forming coating solution 1)
100 mass of alkoxy group-containing siloxane-modified polyurethane resin (referred to as urethane resin) obtained by the method described in JP-A No. 2002-220431 (see P36) and having an Si content of 6.0 mass% in terms of silica mass. A part was dissolved in a mixed solvent of 400 parts by mass of methyl ethyl ketone and 300 parts by mass of isopropyl alcohol. In this solution, a crosslinked urethane resin having 30 parts by mass of carbon black (volume resistivity 1 × 10 ⁻¹ Ωcm, number average primary particle size 50 nm), 1.0 part by mass of tetramethylammonium chloride, and 20 μm of number average median diameter (D ₅₀ ). 20 parts by mass of particles were mixed and dispersed to prepare “Coating Layer Forming Coating Liquid 1”.

100 parts by mass of an alkoxy group-containing siloxane-modified polyurethane resin (referred to as urethane resin) having a Si content of 6.0% by mass in terms of silica obtained by the following method is mixed with 400 parts by mass of methyl ethyl ketone and 300 parts by mass of isopropyl alcohol. Dissolved in solvent. In this solution, a crosslinked urethane resin having 30 parts by mass of carbon black (volume resistivity 1 × 10 ⁻¹ Ωcm, number average primary particle size 50 nm), 1.0 part by mass of tetramethylammonium chloride, and 20 μm of number average median diameter (D ₅₀ ). 20 parts by mass of particles were mixed and dispersed to prepare “Coating Layer Forming Coating Liquid 1”.

(Preparation of an alkoxy group-containing siloxane-modified polyurethane resin having a Si content of 6.0% by mass in terms of silica)
A reactor equipped with a stirrer, a thermometer and a nitrogen gas inlet tube was charged with 1000 parts by mass of polyester polyol (manufactured by Kuraray Co., Ltd., “Kuraray Polyol P2010”, number average molecular weight 2000) and 278 parts by mass of isophorone diisocyanate, and a nitrogen stream The mixture was reacted at 100 ° C. for 6 hours to obtain a prepolymer having a free isocyanate value of 3.44%, and 548 parts by mass of methyl ethyl ketone was added thereto to obtain a uniform solution of a urethane prepolymer. Subsequently, 1000 parts by mass of the urethane polymer solution was added in the presence of a mixture consisting of 71.8 parts by mass of isophorone diamine, 4.0 parts by mass of di-n-butylamine, 906 parts by mass of methyl ethyl ketone, and 603 parts by mass of isopropyl alcohol. The mixture was reacted at 0 ° C. for 3 hours to obtain a polyurethane resin solution (hereinafter referred to as polyurethane resin (1A)). The polyurethane resin (1A) had a resin solid content of 30% by mass and an amine value of 1.2 KOH mg / g. Furthermore, after heating 500 mass parts of said polyurethane resin (1A) to 50 degreeC to the same reaction apparatus, 17.5 mass parts of epoxy group containing alkoxysilane partial condensates (2A) obtained by the following manufacture example 1 And reacted for 4 hours at 60 ° C. under a nitrogen stream to obtain an alkoxy group-containing silane-modified polyurethane resin. The epoxy group equivalent of the epoxy group-containing alkoxysilane partial condensate (2A) / the equivalent of the amino group of the urethane resin (1A) (equivalent ratio) = 2, Si in the solid residue in the alkoxy group-containing silane-modified polyurethane resin The content was 6.0% by mass in terms of silica weight.

Production Example 1 (Production of epoxy group-containing alkoxysilane partial condensate)
In a reactor equipped with a stirrer, a water separator, a thermometer and a nitrogen gas introduction tube, 250.0 parts by mass of glycidol and a tetramethoxysilane partial condensate (manufactured by Tama Chemical Co., Ltd., trade name “methyl silicate 56”, Si The average number of 10) 2675.4 parts by mass was charged, and the temperature was raised to 90 ° C. while stirring under a nitrogen stream, and then 0.5 parts by mass of dibutyltin dilaurate was added as a catalyst and reacted. During the reaction, methanol was distilled off using a water separator, and the reaction was cooled when the amount reached about 125 parts by mass. Subsequently, about 5 parts by mass of methanol remaining in the system was removed under reduced pressure at 13 kPa for about 10 minutes. In this way, an epoxy group-containing alkoxysilane partial condensate (2A) was obtained. In addition, the equivalent of the hydroxyl group of the epoxy compound at the time of preparation / the equivalent of the alkoxyl group of the alkoxysilane condensate (equivalent ratio) = 0.05, and the equivalent of the epoxy group is 830 parts by mass / eq.

(Preparation of coating layer forming coating solution 2)
Carbon black (volume resistivity 1 × 10 ⁻¹ Ωcm, number average primary particle size 50 nm) 40 parts by mass in a solution obtained by dissolving 100 parts by mass of acrylic resin (Sumipex LG: manufactured by Sumitomo Chemical Co., Ltd.) in 700 parts by mass of methyl ethyl ketone, Disperse 5.0 parts by mass of benzyltrimethylammonium chloride and 30 parts by mass of crosslinked acrylic resin particles having a number average median diameter (D ₅₀ ) of 20 μm for 2 hours using a sand mill to prepare “Coating Layer Forming Coating Liquid 2”. did.

(Preparation of coating layer forming coating solution 3)
Carbon black (volume resistivity 1 × 10 ⁻¹ ) was added to a solution obtained by dissolving 100 parts by mass of a polyamide resin (Toresin MF-30: manufactured by Nagano Chemtex) in a mixed solvent of 400 parts by mass of methanol and 300 parts by mass of 1-butanol. 40 parts by mass of Ωcm, number average primary particle size 50 nm), 3.0 parts by mass of benzyltrimethylammonium chloride, and 10 parts by mass of crosslinked acrylic resin particles having a number average median diameter (D ₅₀ ) of 20 μm are dispersed for 2 hours using a sand mill. Thus, “Coating layer forming coating solution 3” was prepared.

<< Preparation of developing roller 1 >>
(Coating layer formation)
“Coating layer forming coating solution 1” is spray coated on the outer peripheral surface of “shaft 3” and then dried at 120 ° C. for 1 hour to form a coating layer having a thickness of 15 μm after drying. Was made.

<< Preparation of developing rollers 2-31 >>
The “shaft 1” and “coating layer forming coating solution 1” used in the production of the developing roller 1 were similarly developed except that the shaft and the coating layer forming coating solution were changed as shown in Tables 1 and 2. Rollers 2-31 "were produced.

  Tables 1 and 2 show the outer diameter and thickness of the prepared shafts, the elements and amounts contained, and the coating liquid No. for coating layer formation. Write.

Toner preparation (non-magnetic one-component developer)
A toner was prepared according to the following procedure.
(1) Preparation of “resin particle dispersion 1” In a flask equipped with a stirrer, 72.0 parts by mass of pentaerythritol tetrastearate, 115.1 parts by mass of styrene, 42.0 parts by mass of n-butyl acrylate, And it added to the monomer liquid mixture which consists of 10.9 mass parts of methacrylic acid, and it heated and dissolved at 80 degreeC.

  On the other hand, 7.08 parts by mass of an anionic surfactant (sodium dodecylbenzenesulfonate: SDS) was dissolved in 2760 parts by mass of ion-exchanged water in a separable flask equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introduction apparatus. The surfactant solution thus prepared was added, and the temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream. Next, the monomer solution (80 ° C.) is mixed and dispersed in the surfactant solution (80 ° C.) by a mechanical disperser “CLEARMIX (M Technique Co., Ltd.)” having a circulation path, An emulsified liquid in which emulsified particles (oil droplets) having a uniform dispersed particle diameter were dispersed was prepared.

An initiator solution in which 0.84 parts by mass of a polymerization initiator (potassium persulfate: KPS) was dissolved in 200 parts by mass of ion-exchanged water was added to this dispersion, and this system was heated at 80 ° C. for 3 hours. The polymerization reaction was carried out with stirring. A solution prepared by dissolving 7.73 parts by mass of a polymerization initiator (KPS) in 240 parts by mass of ion-exchanged water was added to the obtained reaction solution. After 15 minutes, the temperature was adjusted to 80 ° C., and then 383.6 masses of styrene. Part mixture, 140.0 parts by mass of n-butyl acrylate, 36.4 parts by mass of methacrylic acid, and 12 parts by mass of n-octyl mercaptan was added dropwise over 100 minutes, and the system was added at 80 ° C for 60 minutes. After heating and stirring, the system was cooled to 40 ° C. to prepare “resin particle dispersion 1” (hereinafter referred to as “latex (1)”) containing wax.
(2) Production of “Colorant Dispersion Bk” On the other hand, 9.2 parts by mass of sodium n-dodecyl sulfate was stirred and dissolved in 160 parts by mass of ion-exchanged water. While stirring this solution, 20 parts by mass of carbon black “Mogal L (manufactured by Cabot)” as a colorant is gradually added, and then a mechanical disperser “Claremix (manufactured by M Technique Co., Ltd.)” is added. A “colorant dispersion liquid Bk” was prepared by dispersion treatment. The particle diameter of the colorant particles in “Colorant Dispersion Bk” was measured with an electrophoretic light scattering photometer “ELS-800 (manufactured by Otsuka Electronics Co., Ltd.)”, and the mass average particle diameter was 120 nm.
(3) Production of “colored particle 1Bk” In a reaction vessel (four-necked flask) equipped with a temperature sensor, a cooling pipe, a stirring device (having two stirring blades, an intersection angle of 20 °), and a shape monitoring device, 1250 parts by mass of “resin particle dispersion 1” (in terms of solid content), 2000 parts by mass of ion-exchanged water, and the total amount of “colorant dispersion 1” were adjusted to an internal temperature of 25 ° C. A 5 mol / liter sodium hydroxide aqueous solution was added to adjust the pH to 10.0. Next, an aqueous solution in which 52.6 parts by mass of magnesium chloride hexahydrate was dissolved in 72 parts by mass of ion-exchanged water was added over 10 minutes at 25 ° C. with stirring. Thereafter, the temperature increase was started immediately, and this system was heated to 95 ° C. over 5 minutes (temperature increase rate: 14 ° C./min).

In this state, the particle size of the aggregated particles was measured with “Multisizer 3 (manufactured by Beckman Coulter)”, and when the volume-based median diameter (D ₅₀ ) reached 6.5 μm, 115 parts by mass of sodium chloride was added. An aqueous solution dissolved in 700 parts by mass of ion-exchanged water was added to stop particle growth. Furthermore, after heating and stirring for 8 hours at a liquid temperature of 90 ° C. (stirring rotation speed: 120 rpm) and continuing aging, the system was cooled to 30 ° C. at 10 ° C./min. The pH was adjusted to 3.0 by addition and stirring was stopped.

The produced particles are filtered, washed repeatedly with ion-exchanged water, classified in liquid using a centrifugal separator, and then dried using a flash jet dryer to give “colored particles 1Bk” having a water content of 1.0 mass%. Was generated.
(4) Preparation of “Colorant Dispersion Y” In the preparation of “Colorant Dispersion Bk”, except that 20 parts by mass of pigment “CI Pigment Yellow 74” was used instead of 20 parts by mass of carbon black. “Colorant dispersion Y” was prepared by the same procedure. When the particle diameter of the colorant particles in “Colorant Dispersion Liquid Y” was measured using an electrophoretic light scattering photometer “ELS-800 (manufactured by Otsuka Electronics Co., Ltd.)”, the mass average particle diameter was 120 nm.
(5) Preparation of “Colorant Dispersion Liquid M” In the preparation of “Colorant Dispersion Liquid Bk”, 20 parts by mass of quinacridone-based magenta pigment “CI Pigment Red 122” was used instead of 20 parts by mass of carbon black. A “colorant dispersion M” was prepared in the same manner except that. When the particle diameter of the colorant particles in “Colorant Dispersion Liquid M” was measured using an electrophoretic light scattering photometer “ELS-800 (manufactured by Otsuka Electronics Co., Ltd.)”, the mass average particle diameter was 120 nm.
(6) Preparation of “Colorant Dispersion C” In preparation of “Colorant Dispersion Bk”, 20 parts by mass of phthalocyanine-based cyan pigment “CI Pigment Blue 15: 3” was used instead of 20 parts by mass of carbon black. “Colorant dispersion C” was prepared in the same manner as described above except that it was used. When the particle diameter of the colorant particles in “Colorant Dispersion C” was measured using an electrophoretic light scattering photometer “ELS-800 (manufactured by Otsuka Electronics Co., Ltd.)”, the mass average particle diameter was 120 nm.
(7) Preparation of “Colored Particle 1Y” In the preparation of “Colored Particle 1Bk”, “Colored Particle 1Bk” was prepared in the same manner as in “Colored Particle 1Bk”, except that “Colorant Dispersion Liquid Y” was used instead of “Colorant Dispersion Liquid Bk”. 1Y "was produced.
(8) Preparation of “Colored Particles 1M” In the preparation of “Colored Particles 1Bk”, “Colored Particles 1Bk” was prepared in the same procedure except that the entire amount of “Colorant Dispersion Liquid M” was used instead of the total amount of “Colorant Dispersion Liquid Bk”. 1M "was produced.
(9) Production of “Colored Particle 1C” In the production of “Colored Particle 1Bk”, “Colored Particle 1Bk” was prepared in the same manner as in “Colored Particle 1Bk” except that “Colorant Dispersion Liquid Bk” was used instead of “Colorant Dispersion Liquid Bk”. 1C "was produced.
(10) Preparation of Toner In each of the colored particles, 0.8 parts by mass of hydrophobic silica having a number average primary particle size of 12 nm and a hydrophobicity of 65, a number average primary particle size of 30 nm, and a hydrophobicity of 55 0.5 part by mass of hydrophobic titania was added and mixed with a Henschel mixer to prepare a toner. These are referred to as “toner 1Bk, toner 1Y, toner 1M, and toner 1C”.

<Interlayer adhesion evaluation>
The interlayer adhesive force between the shaft and the coating layer of the developing roller produced above was measured by the above measuring method and evaluated according to the following evaluation criteria.

Evaluation criteria The load that begins to be peeled off is sufficiently satisfactory when the load is 10.0N or higher. The load that begins to be peeled off is less than 4.0N to 10.0N. If the starting load is less than 4.0N, it is not suitable for practical use.

<Evaluation>
Evaluation of the developing roller was carried out by modifying the color laser printer “Magicor 2430DL (manufactured by Konica Minolta Business Technologies)” so that an image can be formed using the developing device equipped with the developing roller prepared above. The prepared four-color (toner 1Bk, toner 1Y, toner 1M, and toner 1C) nonmagnetic one-component developers were sequentially loaded, and 3000 sheets were printed in a high temperature and high humidity (30 ° C., 80% RH) environment.

  The initial performance evaluation of the developing roller was performed by printing 10 A4-size originals with a pixel rate of 20% (full color mode of 5% for each color of yellow, magenta, cyan, and black). evaluated.

  Thereafter, 5000 sheets were printed using an original having an image area of 2% (full color mode of 0.5% for each color of yellow, magenta, cyan, and black).

  The performance evaluation after printing 5000 sheets was done by printing 10 A4 size originals with the same pixel ratio 20% (5% each color of yellow, magenta, cyan and black) as the initial performance evaluation, and the toner image quality ( Image density, halftone image) and film peeling were evaluated. In addition, the evaluation is ◎ and ○ are acceptable.

<Coating layer peeling>
The coating layer was peeled off by taking out the developing roller after completion of printing 5000 sheets, and visually evaluating the state of the coating layer peeling.

A: No peeling of the coating layer was observed. O: A little peeling of the coating layer was observed at the edge of the coating layer, but there was no problem in practical use. X: A peeling of the coating layer was observed at the edge of the coating layer.

<Image density>
The image density was evaluated by measuring the density of the solid black image portion at the initial stage and after printing 5000 sheets, using a reflection densitometer “RD-918 (manufactured by Macbeth)”. The image density is 1.25 or higher.

Evaluation Criteria Solid Black Image Density 1.40 or Higher Excellent Level Solid Black Image Density 1.25 or Higher, Less than 1.40 Good Black Solid Image Density Less than 1.25 Practical Problem Level to become.

<Density unevenness of halftone images (including black spots and white spots)>
Density unevenness of the halftone image was evaluated by visually observing a print after completion of printing 5000 sheets.

Evaluation Criteria A: Uniform image without density unevenness in the halftone part ○: There are streaky thin density unevenness, black spots, and white spots in the halftone part, but there is no practical problem ×: In the halftone part There are several streaky density irregularities, black spots, and white spots, which is a practical problem.

  Tables 3 and 4 show the evaluation results.

As shown in Tables 3 and 4, “Developing rollers 1 to 7, 11 to 14, 16 to 19 ” of Examples 1 to 15 corresponding to the present invention have interlayer adhesion, peeling of the coating layer, image density, and half. While the density unevenness of the tone image was satisfactory, the “developing rollers 20 to 31” of Comparative Examples 1 to 12 outside the present invention had problems in any of these evaluation items, and this book It was confirmed that the effects of the invention were not expressed.

FIG. 1 is a schematic sectional view showing an example of the developing roller of the present invention. FIG. 2 is a schematic diagram for explaining a method for measuring an interlayer adhesion force between a shaft and a coating layer. It is a cross-sectional schematic diagram showing an example of the developing roller of the present invention. It is a schematic sectional drawing which shows an example of a full-color image forming apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Photosensitive drum 11 Shaft 12 Covering layer 13 Lower layer 14 Upper layer 20 Developing device 25 Developing roller 26 Buffer chamber 27 Hopper 28 Restricting blade 29 Auxiliary blade 30 Supply roller T Toner 32 Passage 321 Valve 322 Restricting member 34 Rotating body

Claims (4)

In a developing roller configured by directly forming a coating layer having a resin and a conductive agent on the outer periphery of a shaft made of at least an aluminum alloy,
The aluminum alloy contains 0.2 to 0.8% by mass of silicon element and 0.05 to 1.5% by mass of manganese element with respect to the total amount of aluminum alloy ,
A developing roller , wherein the resin is a siloxane-modified polyurethane resin . The aluminum alloy contains 0.4 to 6.0% by mass of magnesium element and 0.04 to 0.35% by mass of chromium element with respect to the total amount of the aluminum alloy. Development roller. In a developing device having a developing roller formed by directly forming a coating layer having a resin and a conductive agent on the outer periphery of a shaft made of at least an aluminum alloy,
The aluminum alloy contains 0.2 to 0.8% by mass of silicon element and 0.05 to 1.5% by mass of manganese element with respect to the total amount of aluminum alloy,
A developing device , wherein the resin is a siloxane-modified polyurethane resin . Said aluminum alloy is 0.4 to 6.0 mass% elemental magnesium the aluminum alloy total, according to claim 3, characterized by containing 0.04 to 0.35 wt% chromium element Development device.

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