JP2015125283A - Developing device, developing method, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developing device and a developing method enabling the suppression of inversion fogging under a high-temperature and high-humidity and the suppression of fogging immediately after the consumption of toner under a low-temperature and low-humidity environment; and an image forming apparatus and an image forming method including the same.SOLUTION: A developing device has a toner, a toner carrier, and a toner regulating member carried on the toner carrier. The toner has toner particles and inorganic fine particles, and the toner particles contains a binder resin, a magnetic body, and a sulfonic acid-based polymer. When the abundance of carbon atoms present on the surface of the toner particles is A, and the abundance of sulfur atoms present on the surface is E, E is 0.09 atomic% or more and 0.37 atomic% or less, and E/A is 0.0010 or more and 0.0040 or less. The toner carrier has a base substance, an elastic layer, and a surface layer including a urethane resin, and the urethane resin has a partial structure derived from the reaction of polyisocyanate with a compound represented by a structural formula (1).

Description

  The present invention relates to a developing device, a developing method, an image forming apparatus, and an image forming method using electrophotography.

  Although many methods are known as electrophotographic methods, generally, an electrostatic latent image is formed on an electrostatic latent image carrier using a photoconductive substance by various means. Next, the electrostatic latent image is developed with toner to form a toner image, and the toner image is transferred to a recording medium such as paper. Thereafter, the toner image is fixed on the recording medium by heat and / or pressure to obtain a copy. Examples of such an image forming apparatus using electrophotography include a copying machine and a printer.

  These printers and copiers have recently moved from analog to digital, and are required to have excellent electrostatic latent image reproducibility and high resolution. In particular, miniaturization of printers is also strongly demanded.

  Conventionally, printers are connected to a network and many people use them for printing. However, in recent years, the demand for printing PCs and printers on personal desks and printing at hand has increased. For this purpose, it is necessary to save the space of the printer, and there is a strong demand for downsizing the printer.

  Even in such a compact printer, there is a great demand for high image quality and little change in image quality (high durability) even after long-term use.

  Here, paying attention to downsizing of the printer, the downsizing of the fixing device and the downsizing of the developing device are mainly effective for downsizing. In particular, the latter occupies a considerable part of the volume of the printer, and it can be said that downsizing of the developing device is essential for downsizing of the printer.

  Considering the development method, the printer development method includes a two-component development method and a one-component development method. In the sense of compactness, the one-component development method is suitable. This is because the developing method does not use a carrier.

  Next, considering the downsizing of the developing device adopting the one-component developing system, it is effective to reduce the diameter of the electrostatic latent image carrier or the toner carrier in order to downsize the developing device. Further, from the viewpoint of high image quality, a developing method in which the toner carrier and the electrostatic latent image carrier are arranged in contact (contact arrangement) (hereinafter also referred to as “contact development method”) is preferable.

  However, the contact development method in which the diameter of the toner carrier is reduced increases the load on the toner and tends to cause deterioration in image quality when used for a long time. This is because, for example, the diameter of the toner carrier is reduced, so that the number of times of passing through a toner supply member or a toner regulating member (hereinafter also simply referred to as “regulating member”) arranged in contact with the toner carrier is increased. This is because the contact pressure at the development contact portion increases because the curvature increases. The development contact portion is a portion where the electrostatic latent image carrier and the toner carrier are in contact (contact).

  Conventionally, the toner supply member is rotated in the same direction as the toner carrier, and the moving directions at the contact portions of the two are often opposite to each other. This is because it is easy to scrape off the toner that has not been used for development and to supply new toner, and to achieve high image quality.

  As described above, the method in which the toner carrier and the toner supply member rotate in the same direction is easy to obtain high image quality, but the moving directions at the contact portions of the two are opposite to each other. There has been a problem that toner is likely to deteriorate.

  On the other hand, in recent years, for the purpose of reducing the load on the toner and enhancing the durability, both are rotated so that the moving directions at the contact portion of the toner carrier and the toner supply member are opposite to each other, A method with little fluctuation in image quality is used even for long-term use. Alternatively, there is an attempt to improve durability by not using a toner supply member (see Patent Documents 1 and 2).

  However, when these development methods are combined with a reduction in the diameter of the toner carrier, unique problems tend to be apparent. This is a problem called reversal fog in a high temperature and high humidity environment (40.0 ° C., 90% RH) and post-black fog in a low temperature and low humidity environment (15 ° C., 10% RH).

  First, reversal fog is a phenomenon in which a non-image area is developed by a component having a low internal charge value of toner on a toner carrying member or a reversed component at a development contact portion. In particular, when the diameter of the toner carrier is reduced, the area of the development contact portion is reduced, and the contact pressure received by the toner at the development contact portion increases. Therefore, when the electrostatic latent image carrier is brought into contact with the electrostatic latent image carrier, the difference between the charging bias applied to the electrostatic latent image carrier and the developing bias applied to the toner carrier causes the electrostatic latent image carrier to change from the toner carrier. Electric charge leaks easily. When the charge leaks at the development contact portion, the polarity of the charge value of the toner is reversed, and an image defect that develops in the non-image area occurs.

  Here, when considering the reversal fog, the reversal fog is caused by the fact that charge is easily transferred between the toner on the toner carrier and the toner carrier at the development contact portion. In a high-temperature and high-humidity environment, the resistance value of the toner is reduced, so that reversal fog is likely to occur.

  As a technique for suppressing the transfer of charge between the toner and the toner carrier, an attempt has been proposed to increase the toner resistance value by adding insulating fine particles to the toner (see Patent Document 3). In addition, there has been proposed a technique for suppressing charge transfer at the development contact portion by appropriately designing the charging characteristics of the toner and the toner carrier (see Patent Document 4).

  However, in these methods, the effect is insufficient in the post-black fog in a low temperature and low humidity environment, and there is room for improvement.

  The post-black fog is a phenomenon in which the toner on the toner carrier immediately after the toner is consumed (also referred to as “after black”) is developed (attached) to the non-image area. It is. By suppressing transfer of charge between the toner and the toner carrier, reversal fogging in a high-temperature and high-humidity environment is suppressed, but there is a tendency that the regulating member cannot efficiently sufficiently charge the toner. . For this reason, the toner having a broad charge distribution is supplied to the toner carrier, and the post-black fog in a low temperature and low humidity environment tends to deteriorate. Similarly, when insulating fine particles are added to the toner, since the charge cannot be efficiently exchanged between the regulating member and the toner, the fogging after black in a low temperature and low humidity environment tends to deteriorate.

  As described above, it is still necessary to adjust the charging characteristics of the toner and the toner carrier to achieve both the suppression of the reverse fogging in the high temperature and high humidity environment and the suppression of the black post fogging in the low temperature and low humidity environment. There was room.

JP 2005-173484 A JP 2006-154093 A JP 2010-139818 A JP 2006-58904 A

  An object of the present invention is to provide a developing device, a developing method, an image forming apparatus, and an image forming method capable of suppressing reversal fogging in a high temperature and high humidity environment and suppressing black post fogging in a low temperature and low humidity environment. is there.

The present invention relates to a developing device for developing an electrostatic latent image formed on the surface of an electrostatic latent image carrier and forming a toner image on the surface of the electrostatic latent image carrier.
The developing device is
Toner for developing the electrostatic latent image;
A toner carrier for carrying the toner, and
A regulating member for regulating the layer thickness of the toner carried on the toner carrier;
Have
The toner has toner particles and inorganic fine particles;
The toner particles are
Binder resin,
Magnetic material and
A polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group,
Containing
When the amount of carbon atoms present on the surface of the toner particles measured by X-ray photoelectron spectroscopy is A, and the amount of sulfur atoms present on the surface of the toner particles is E,
E is 0.09 atomic% or more and 0.37 atomic% or less,
E / A which is a ratio of E to A is 0.0010 or more and 0.0040 or less,
The toner carrier is
Substrate,
An elastic layer, and
Surface layer containing urethane resin,
Have
The urethane resin is
A compound represented by the following structural formula (1);
Polyisocyanate,
A developing device having a partial structure derived from the above reaction.

(In structural formula (1),
n is an integer of 1 or more and 4 or less, each R ³ independently represents any one selected from the group consisting of the following (a) to (c):
(A) a hydroxyalkyl group having 2 to 8 carbon atoms,
(B) an aminoalkyl group having 2 to 8 carbon atoms,
(C) a group represented by the following structural formula (2),
R ⁴ represents an alkylene group having 2 to 4 carbon atoms. )

(In structural formula (2),
m is an integer of 2 to 3,
R ⁵ represents an alkylene group having 2 to 5 carbon atoms. )
The present invention also relates to a developing method for developing a latent electrostatic image formed on the surface of an electrostatic latent image carrier using a developing device to form a toner image on the surface of the electrostatic latent image carrier.
The developing device is
Toner for developing the electrostatic latent image;
A toner carrier for carrying the toner, and
A regulating member for regulating the layer thickness of the toner carried on the toner carrying body;
The toner has toner particles and inorganic fine particles;
The toner particles are
Binder resin,
Magnetic material and
A polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group,
Containing
When the amount of carbon atoms present on the surface of the toner particles is A and the amount of sulfur atoms present on the surface is E,
E is 0.09 atomic% or more and 0.37 atomic% or less,
E / A which is a ratio of E to A is 0.0010 or more and 0.0040 or less,
The toner carrier is
Substrate,
An elastic layer, and
Surface layer containing urethane resin,
Have
The urethane resin is
A compound represented by the structural formula (1),
Polyisocyanate,
A developing method characterized by having a partial structure derived from the above reaction.

The present invention also provides an electrostatic latent image carrier,
An image exposure apparatus for forming an electrostatic latent image on the surface of the electrostatic latent image carrier; and
A developing device for developing the electrostatic latent image formed on the surface of the electrostatic latent image carrier;
In an image forming apparatus having
The developing apparatus is an image forming apparatus according to the present invention.

The present invention also provides an image exposure step for forming an electrostatic latent image on the surface of the electrostatic latent image carrier, and
A developing step of developing the electrostatic latent image formed on the surface of the electrostatic latent image carrier;
In an image forming method having
The image forming method is characterized in that the developing step is performed by the developing method of the present invention.

  According to the present invention, it is possible to provide a developing device, a developing method, an image forming apparatus, and an image forming method capable of suppressing reversal fogging in a high temperature and high humidity environment and suppressing black post fogging in a low temperature and low humidity environment. it can.

Schematic sectional view showing an example of an image forming apparatus according to the present invention Schematic sectional view showing an example of a developing device according to the present invention Schematic sectional view showing an example of an image forming apparatus having a developing device according to the present invention Schematic sectional view showing an example of a developing device according to the present invention

The developing device of the present invention is a developing device for developing an electrostatic latent image formed on the surface of an electrostatic latent image carrier and forming a toner image on the surface of the electrostatic latent image carrier.
The developing device is
Toner for developing the electrostatic latent image;
A toner carrier for carrying the toner, and
A regulating member for regulating the layer thickness of the toner carried on the toner carrying body;
The toner has toner particles and inorganic fine powder;
The toner particles are
Binder resin,
Magnetic material and
A polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group,
Containing
When the amount of carbon atoms present on the surface of the toner particles measured by X-ray photoelectron spectroscopy is A, and the amount of sulfur atoms present on the surface of the toner particles is E,
E is 0.09 atomic% or more and 0.37 atomic% or less,
E / A which is a ratio of E to A is 0.0010 or more and 0.0040 or less,
The toner carrier is
Substrate,
An elastic layer, and
Surface layer containing urethane resin,
Have
The urethane resin is
A compound represented by the following structural formula (1);
Polyisocyanate,
It has the partial structure derived from reaction of this.

(In structural formula (1),
n is an integer of 1 or more and 4 or less, each R ³ independently represents any one selected from the group consisting of the following (a) to (c):
(A) a hydroxyalkyl group having 2 to 8 carbon atoms,
(B) an aminoalkyl group having 2 to 8 carbon atoms,
(C) a group represented by the following structural formula (2),
R ⁴ represents an alkylene group having 2 to 4 carbon atoms. )

(In structural formula (2),
m is an integer of 2 to 3,
R ⁵ represents an alkylene group having 2 to 5 carbon atoms. )
When the present inventors examined in detail,
A toner carrier containing the specific urethane resin in the surface layer;
Binder resin,
Magnetic material and
A polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group (hereinafter, also referred to as “sulfonic acid polymer”),
A toner having a specific amount of carbon atoms and sulfur atoms on the surface;
It has been found that the use of the above in combination enables the suppression of reversal fog in a high-temperature and high-humidity environment and the suppression of post-black fog in a low-temperature and low-humidity environment.

  The reason for this will be described below.

  First, regarding reversal fogging in a high-temperature and high-humidity environment, the following two conditions are considered necessary in order to obtain a stable image in a high-temperature and high-humidity environment where the resistance of the toner tends to decrease.

  The first is that the charge control resin on the surface of the toner that becomes a leak site is controlled to an appropriate amount.

  Second, there is almost no charge transfer between the toner and the toner carrier at the development contact portion.

The first leak site is to reduce the amount of charge control resin on the surface of the toner particles that affects the charge amount of the toner. The toner used in the present invention employs a sulfonic acid polymer as a charge control resin. When the amount of carbon atoms present on the surface of the toner particles measured by X-ray photoelectron spectroscopy is A and the amount of sulfur atoms is E,
E is 0.09 atomic% or more and 0.37 atomic% or less,
It is important that E / A, which is the ratio of E to A, is 0.0010 or more and 0.0040 or less. The E and E / A indicate the amount of the sulfonic acid polymer present on the surface of the toner particles.

  The sulfonic acid polymer has a sulfonic acid structure in the molecule, and the sulfonic acid structure has a plurality of lone electron pairs. As a result, the toner containing a large amount of the sulfonic acid polymer leaks from the electrostatic latent image carrier at the development contact portion. That E and E / A are within the scope of the present invention indicates that there is little sulfonic acid-based polymer present on the surface of the toner particles serving as leak sites, and leakage is unlikely to occur.

  Regarding the suppression of charge transfer between the toner and the toner carrier at the second development contact portion, the electrostatic interaction between the toner carrier and the toner is related.

  The specific urethane resin contained in the surface layer of the toner carrier has a partial structure derived from the reaction between the compound represented by the structural formula (1) and polyisocyanate. A nitrogen atom (N) is present at the center of the compound of the structural formula (1). And since a nitrogen atom has a lone pair (lawe pair), the compound shown by Structural formula (1) is a Lewis base. The Lewis base has an electron donating property, and an attractive force due to Coulomb force acts between the Lewis base and a sulfonic acid polymer that is a Lewis acid. For this reason, free electrons in the toner on the toner carrier are reduced, and leakage from the electrostatic latent image carrier to the toner carrier can be suppressed even at the developing contact portion where the potential difference is large.

  As described above, the toner used in the present invention has a leakage site because the above E and E / A derived from the sulfonic acid polymer on the surface of the toner particles are controlled within the scope of the present invention. Can be reduced. The toner carrier includes a urethane resin having a partial structure derived from the reaction between the compound represented by the structural formula (1) and the polyisocyanate on the surface layer, and the sulfonic acid polymer on the surface of the toner particles. An attractive force works between and the number of free electrons. By these two synergistic effects, it is possible to suppress reversal fogging even in a high-temperature and high-humidity environment where it is difficult to control charging at the development contact portion.

  Next, post black fogging in a low temperature and low humidity environment will be described.

  The toner is transported by the toner carrier, and at the portion where the toner regulating member and the toner carrier abut (hereinafter also referred to as “regulator”), the toner is transported by the toner carrier and pressed from the regulating member. Pressure works. The restricting portion is a portion where the thickness of the toner carried on the toner carrier is restricted by the restricting member. As a result of the pressing force from the regulating member, the toner on the surface of the toner carrier is conveyed while being exchanged so as to be mixed. Further, when the toner is replaced at the regulating portion, the toner comes into contact with the toner carrier and is rubbed. As a result, the toner becomes charged.

  As described above, the toner carrier used in the present invention includes a urethane resin having a partial structure derived from the reaction between the compound represented by the structural formula (1) and the polyisocyanate on the surface layer. Has a donating property. For this reason, when the toner carrying member and the toner are rubbed, the exchange of electrons is performed very quickly. For this reason, it is possible to increase the charge rising value of the toner. Furthermore, the toner used in the present invention contains a sulfonic acid polymer, the E is 0.09 atomic% or more and 0.37 atomic% or less, and the E / A is 0.0010 or more and 0.0040. It is as follows. As a result, electrostatic aggregation of toner present in the vicinity of the regulating portion can be suppressed, and electrons can be exchanged efficiently when rubbed against the toner carrier. If the E is 0.09 atomic% or more and the E / A is 0.0010 or more, the charge rising can be improved as described above, which is preferable from the viewpoint of fog suppression. On the other hand, when E is 0.37 atomic% or less and E / A is 0.0040 or less, electrostatic aggregation of toner in the vicinity of the regulating portion can be suppressed.

  In addition, when the compound represented by the structural formula (1) reacts with isocyanate, a crosslinked structure in which a number of urethane groups or urea groups are formed is formed around the structure of the compound represented by the structural formula (1). . As a result, the microscopic hardness is high, and even when the toner is regulated by the regulating unit, the toner is less likely to sink into the surface of the toner carrier, and the toner rolling property is improved.

  In general, a low molecular weight and polyfunctional compound tends to make it difficult for all functional groups to react due to steric hindrance.

  However, in the compound represented by the structural formula (1), the reactivity of the terminal hydroxyl group or amino group is increased due to the amino skeleton in the molecule, so that the generation of unreacted components is reduced. As a result, the uniformity in charging can be improved and the uniformity of the crosslinked structure can be enhanced.

  As described above, the toner used in the present invention is a toner that is less likely to cause electrostatic aggregation in the vicinity of the restricting portion and is efficiently charged with the restricting portion. Can be suppressed.

  From the above, it has become possible to achieve both high levels of suppression of reversal fog in a high temperature and high humidity environment and suppression of post-black fog in a low temperature and low humidity environment.

  The acid value of the sulfonic acid polymer used in the present invention is preferably 6.0 mgKOH / g or more and 25.0 mgKOH / g or less, more preferably 10.0 mgKOH / g or more and 20.0 mgKOH / g or less. . This is because the dispersibility of the sulfonic acid polymer in the toner particles is improved when the acid value of the sulfonic acid polymer is within the above range.

  When the sulfonic acid polymer is added to the toner particles, the amount of the sulfonic acid polymer is 0.1 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin. It is more preferable that it is 0.4 parts by mass or more and 10.0 parts by mass or less.

  When the sulfonic acid polymer is added to the outside of the toner particles, the amount of the sulfonic acid polymer is preferably 0.1 parts by mass or more and 1.0 part by mass or less with respect to 100 parts by mass of the toner. More preferably, it is 0.3 parts by mass or more and 0.8 parts by mass or less.

  Thus, by controlling the amount of the sulfonic acid polymer, it becomes easy to control the E and E / A, and the effects of the present invention can be obtained more remarkably.

The sulfonic acid polymer used in the present invention is
A sulfonic acid-containing (meth) acrylamide monomer containing a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group in the molecule;
With other monomers,
From the viewpoint of improving development stability such as charging stability and durability stability, it is preferable that the above copolymer. The sulfonic acid-containing (meth) acrylamide monomer is a compound formed by bonding a sulfonic acid derivative and (meth) acrylamide. As such a sulfonic acid-containing (meth) acrylamide monomer, 2-acrylamido-2-methylpropanesulfonic acid and 2-methacrylamide-2-methylpropanesulfonic acid are preferable from the viewpoint of chargeability.

  The E and E / A can be controlled by controlling the amount of the sulfonic acid-containing (meth) acrylamide monomer contained in the sulfonic acid polymer and the amount of the sulfonic acid polymer. Specifically, the greater the amount of the sulfonic acid-containing (meth) acrylamide monomer contained in the sulfonic acid polymer, and the greater the amount of the sulfonic acid polymer, the above E and E / A increase. Tend to.

  The other monomer is not particularly limited as long as it is a compound that can be polymerized with the sulfonic acid-containing (meth) acrylamide monomer. Examples of such other monomers include monofunctional polymerizable monomers and polyfunctional polymerizable monomers.

As a monofunctional polymerizable monomer,
styrene;
α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn- Styrene derivatives such as hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene;
Methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate Acrylic polymerizable monomers such as N-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate Methacrylic polymerizable monomers such as n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate;
Methylene aliphatic monocarboxylic acid ester;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate;
Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether;
Examples thereof include vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2'-bis [4- (acryloxy-diethoxy) phenyl] propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis [4- (methacryloxy-diethoxy) phenyl] propane, Examples include 2,2′-bis [4- (methacryloxy polyethoxy) phenyl] propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like.

  Among these, the copolymer with styrene and / or (meth) acrylic acid ester is excellent in dispersion of the sulfonic acid-containing (meth) acrylamide monomer in the sulfonic acid polymer. As a result, a toner having a uniform charge amount and excellent charging characteristics can be obtained, which is preferable.

  Polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, dispersion polymerization, and ionic polymerization can be used as the method for producing the sulfonic acid polymer used in the present invention. Among these, it is preferable to produce a sulfonic acid polymer by solution polymerization because the method is simple and it is easy to uniformly disperse the sulfone-containing (meth) acrylamide monomer.

The polymer having the sulfonic acid-containing (meth) acrylamide monomer has a structure represented by the following general formula.
XCONHR (SO ₃ ) n · mYk
(In the general formula,
X represents a polymer site derived from the polymerizable monomer,
R represents an alkyl group having 1 to 6 carbon atoms,
Y represents a counter ion or an ester group,
k is the valence of the counter ion,
m and n are integers;
n = k × m. )
Examples of the counter ion or ester group include hydrogen ion, sodium ion, potassium ion, calcium ion, ammonium ion, methyl group, ethyl group, and butyl group. Among these, hydrogen ions are preferable.

  A polymer containing a component derived from sulfonic acid-containing (meth) acrylamide has high polarity. Therefore, by incorporating such a polymer into the toner particles, the charge transfer speed at the time of friction charging of the toner particles is improved, and also in the developing device according to the present invention, the charge rising in a low temperature and low humidity environment is improved. be able to. The degree of this effect is adjusted by adjusting the amount of the sulfonic acid polymer relative to the binder resin in the toner particles and the proportion of the component derived from the sulfonic acid-containing (meth) acrylamide in the sulfonic acid polymer. be able to. As a result of obtaining the above-described charging characteristics, it is possible to obtain a toner in which reversal fogging in a high-temperature and high-humidity environment and post-black fogging in a low-temperature and low-humidity environment are suppressed in image formation.

  The toner used in the present invention preferably contains an amorphous polyester resin.

  The toner used in the present invention preferably has a core-shell structure having a core and a shell.

The shell is
The amorphous polyester resin, and
It is preferable to contain a polymer or copolymer having the sulfonic acid group, sulfonic acid group or sulfonic acid ester group.

  The acid value of the amorphous polyester resin is preferably 0.1 mgKOH / g or more and 5.0 mgKOH / g or less.

  In the present invention, the “core-shell structure” refers to a structure in which the shell covers the surface of the core. “Coating” means that the surface of the core is covered with a shell.

  When the amorphous polyester resin has an acid value of 0.1 mgKOH / g or more and 5.0 mgKOH / g or less, the fluidity of the toner in the regulation part is improved, and the fogging after black in a low temperature and low humidity environment is further improved. It is suppressed.

  In addition, when the amorphous polyester resin has an acid value of 0.1 mgKOH / g or more, it is easily compatible with the sulfonic acid polymer when the shell is formed on the surface of the core, and the above E and E / A It becomes easy to control. On the other hand, when the acid value of the amorphous polyester resin is 5.0 mgKOH / g or less, it becomes possible to produce an amorphous polyester resin having a uniform composition, and dispersibility when forming a shell is improved. . Thereby, when a shell is formed with the amorphous polyester resin, a uniform shell can be formed.

  As a result, the fluidity of the toner in the restricting portion is improved, and the post-black fogging in a low temperature and low humidity environment is further suppressed.

  When the toner has a core-shell structure, and the amorphous polyester resin and the sulfonic acid polymer are contained in the shell, the charge rising of the toner is improved and the durability of the toner is improved.

  The amorphous polyester resin can be obtained by polycondensing a polyhydric alcohol that is an alcohol component and a polyvalent carboxylic acid that is an acid component.

  Further, the amount of the amorphous polyester resin in the toner particles is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the toner particles. When the amount of the amorphous polyester resin is within the above range, leak sites existing on the surface of the toner particles can be reduced, and reversal fogging in a high temperature and high humidity environment can be further suppressed.

  As the amorphous polyester resin, a saturated polyester resin, an unsaturated polyester resin, or both of them can be used.

  Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6- Hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, butenediol, octenediol, cyclohexenedimethanol, hydrogenated bisphenol A, bisphenol derivatives represented by the following formula (1-1) And hydrogenated products of the following formula (1-1), diols represented by the following formula (1-2), and the like.

[Where:
R represents an ethylene group or a propylene group;
x is an integer of 1 or more,
y is an integer of 1 or more,
The average value of x + y is 2 or more and 10 or less. ]

The amorphous polyester resin is
A polyhydric alcohol (alcohol component) containing 80 mol% or more (more preferably 90 mol% or more) of a propylene oxide adduct of bisphenol A;
A polyvalent carboxylic acid (acid component);
An amorphous polyester resin obtained by polycondensation of is preferred. Moreover, it is preferable that the propylene oxide average addition mole number of a bisphenol A propylene oxide adduct is 1.8-2.1. 80% by mole or more of the polyhydric alcohol is a bisphenol A propylene oxide adduct, and the average added mole number is 1.8 or more and 2.1 or less. Will improve. And the dispersibility of a sulfonic acid-type polymer improves. As a result, it is possible to efficiently apply charge to the toner in the restricting portion, and the post-black fogging in a low temperature and low humidity environment is further suppressed.

As the acid component,
Benzene dicarboxylic acid or its anhydride such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride;
Alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or anhydrides thereof;
A succinic acid substituted with an alkyl group or an alkenyl group having 6 to 18 carbon atoms or an anhydride thereof;
Examples thereof include unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid, or anhydrides thereof.

  As the alcohol component, polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, and oxyalkylene ethers of novolak type phenol resins may be used. Moreover, you may use polyvalent carboxylic acid, such as trimellitic acid, pyromellitic acid, 1,2,3,4-butanetetracarboxylic acid, benzophenone tetracarboxylic acid, or its anhydride as an acid component.

  The amorphous polyester resin is an amorphous polyester resin obtained by polycondensing 45 mol% to 55 mol% of an alcohol component and 45 mol% to 55 mol% of an acid component in all components. It is preferable that

  The amorphous polyester resin may be a catalyst such as a metal such as tin, titanium, antimony, manganese, nickel, zinc, lead, iron, magnesium, calcium, germanium, or a compound containing these metals. Can be manufactured. Among these catalysts, it is preferable to use a titanium-based catalyst.

  An amorphous polyester resin obtained by polycondensation of an alcohol component and an acid component using a titanium-based catalyst is likely to be a homogeneous polyester resin, so that variation among toner particles is reduced. The toner particle shell can be configured uniformly.

  The toner particles used in the present invention are preferably toner particles produced by suspension polymerization in an aqueous medium. As a method of obtaining toner particles having a core-shell structure, there is a method of embedding shell fine particles in a core. Further, as a preferred method, there is a method of utilizing the acid value or hydrophilicity of the amorphous polyester resin for shell and the sulfonic acid polymer in an aqueous medium. Specifically, it is a method in which an amorphous polyester resin and a sulfonic acid polymer are unevenly distributed at the interface with water, that is, in the vicinity of the surface of the toner particles to form a shell. By producing in an aqueous medium, the smoothness of the surface of the toner particles can be improved, and the fluidity at the regulating part can be improved.

  The weight average particle diameter (D4) of the toner used in the present invention is preferably 5.0 μm or more and 12.0 μm or less, and more preferably 5.5 or more and 11.0 μm or less. If the weight average particle diameter (D4) is 5.0 μm or more and 12.0 μm or less, the fluidity becomes better and the electrostatic latent image can be developed more faithfully. For this reason, a good image excellent in dot reproducibility can be obtained.

  In the toner used in the present invention, the ratio of the weight average particle diameter (D4) to the number average particle diameter (D1), D4 / D1, is preferably 1.30 or less, and more preferably 1.25 or less. preferable. D4 / D1 being 1.30 or less means that the toner particle size distribution is sharp.

  As described above, it is important that the toner used in the present invention has high fluidity at the regulating portion. The fluidity also depends on the toner particle size. The smaller the particle size, the higher the adhesion force, and the lower the fluidity. The larger the particle size, the lower the adhesion force and the fluidity. For this reason, if the particle size distribution is sharp, variations in the adhesion of individual toners are reduced, toner replacement at the restricting portion is easily improved, and toner charging characteristics can be made uniform.

  The average circularity of the toner used in the present invention is preferably 0.950 or more. If the average circularity of the toner is 0.950 or more, the toner has a spherical shape or a shape close to it, excellent in fluidity, easy to obtain uniform triboelectric chargeability, and after black in a low temperature and low humidity environment. Fog is further suppressed. Further, in the circularity distribution of the toner, the mode circularity is preferably 0.98 or more from the viewpoint of fluidity and uniform triboelectric charging.

  The glass transition temperature (Tg) of the toner used in the present invention is preferably 40.0 ° C. or higher and 70.0 ° C. or lower. When the glass transition temperature is 40.0 ° C. or higher and 70.0 ° C. or lower, the storage stability and durability of the toner can be improved while maintaining good fixability.

  Examples of the binder resin for the toner particles used in the present invention include vinyl resins and polyester resins.

In particular,
Homopolymers of styrene and substituted products thereof such as polystyrene and polyvinyltoluene;
Styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, Styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-methacrylic acid Dimethylaminoethyl acid copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene -Maleic acid copolymerization , Styrene - styrene copolymer and maleic acid ester copolymer. In addition, polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin, and the like are also included. These can be used alone or in combination of two or more. Among these, a styrene copolymer and a polyester resin are preferable from the viewpoint of development characteristics and fixability.

  The toner particles used in the present invention may contain a release agent in order to improve fixability. The content of the release agent in the toner particles is preferably 1.0% by mass or more and 30.0% by mass or less, and 3.0% by mass or more and 25.0% by mass or less with respect to the binder resin. It is more preferable.

  If content of a mold release agent is 1.0 mass% or more, the low temperature offset inhibitory effect will become high. If it is 30.0% by mass or less, the long-term storage stability is improved, the seepage of the toner particles to the surface is suppressed, the adverse effect on the charging uniformity of the toner is suppressed, and the regulation is less likely to occur. .

As a mold release agent,
Petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam and derivatives thereof;
Montan wax and its derivatives;
Hydrocarbon wax and its derivatives by Fischer-Tropsch process;
Polyolefin waxes such as polyethylene and derivatives thereof;
Natural waxes such as carnauba wax and candelilla wax and their derivatives;
Etc. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. In addition, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, acid amide waxes, ester waxes, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes and the like can also be used as mold release agents.

  Further, the melting point defined by the maximum endothermic peak temperature at the time of temperature rise measured by a differential scanning calorimeter (DSC) of these release agents is preferably 60 ° C. or higher and 140 ° C. or lower, and 65 ° C. or higher and 120 ° C. or lower. It is more preferable that it is below ℃. If the melting point is 60 ° C. or higher, the viscosity of the toner is unlikely to decrease, and fusion to the toner carrier is less likely to occur. When the melting point is 140 ° C. or lower, the low-temperature fixability is hardly lowered.

  The melting point of the release agent is the peak top of the endothermic peak when measured by DSC. Moreover, the measurement of the peak top of the endothermic peak is performed according to ASTM D 3417-99. For these measurements, for example, DSC-7 manufactured by PerkinElmer, DSC2920 manufactured by TA Instruments, and Q1000 manufactured by TA Instruments can be used. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. As a measurement sample, an aluminum pan is used, and an empty pan is set as a control and measured.

  The toner particles used in the present invention contain a magnetic material. The content of the magnetic substance in the toner particles is preferably 20 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the binder resin.

  The content of the magnetic substance in the toner particles can be measured using a thermal analysis device manufactured by Perkin Elmer, TGA7. The measurement method is as follows.

  In a nitrogen atmosphere, the toner is heated from room temperature to 900 ° C. at a temperature rising rate of 25 ° C./min. The weight loss mass% between 100 ° C. and 750 ° C. is the amount of the binder resin, and the remaining mass is approximately the amount of the magnetic material.

  The magnetic material is preferably composed mainly of magnetic iron oxide such as triiron tetroxide and γ-iron oxide, and may contain elements such as phosphorus, cobalt, nickel, copper, magnesium, manganese, aluminum, and silicon.

The BET specific surface area of the magnetic material by the nitrogen adsorption method is preferably ² m ² / g or more and 30 m ² / g, and more preferably 3 m ² / g or more and 28 m ² / g or less.

  The shape of the magnetic body includes a polyhedron, an octahedron, a hexahedron, a sphere, a needle, and a scaly shape, but a polyhedron, an octahedron, a hexahedron, a sphere, and the like having a low anisotropy increase the image density. It is preferable from the viewpoint.

  The volume average particle diameter (DV) of the magnetic material is preferably 0.10 μm or more and 0.40 μm or less. If the volume average particle diameter (DV) of the magnetic material is 0.10 μm or more and 0.40 μm or less, the dispersibility of the magnetic material in the toner particles is improved, and the coloring power of the toner is improved.

  The volume average particle diameter (DV) of the magnetic material can be measured using a transmission electron microscope. Specifically, the toner particles to be observed are sufficiently dispersed in the epoxy resin, and then cured in an atmosphere at a temperature of 40 ° C. for 2 days to obtain a cured product. The obtained cured product is used as a flaky sample by a microtome, and the particle diameters of 100 magnetic bodies in the field of view are measured with a transmission electron microscope (TEM) with a photograph with a magnification of 10,000 to 40,000 times. Then, the volume average particle diameter (DV) is calculated based on the equivalent diameter of a circle equal to the projected area of the magnetic material. It is also possible to measure the particle size with an image analyzer.

  The magnetic body can be manufactured, for example, by the following method.

  An aqueous solution containing ferrous hydroxide is prepared by adding an alkali such as sodium hydroxide to the ferrous salt aqueous solution in an amount equivalent to or greater than the iron component. While maintaining the pH of the prepared aqueous solution at pH 7 or higher, air was blown in, while the aqueous solution was heated to 70 ° C. or higher, ferrous hydroxide was oxidized, and seed crystals serving as the core of the magnetic iron oxide particles were formed. First generate.

  Next, an aqueous solution containing 1 equivalent of ferrous sulfate is added to the slurry-like liquid containing seed crystals based on the amount of alkali added previously. The pH of the liquid is maintained at 5 or more and 10 or less, and the reaction of ferrous hydroxide is advanced while blowing air to grow magnetic iron oxide particles with the seed crystal as a core. At this time, it is possible to control the shape and magnetic properties of the magnetic material by selecting an arbitrary pH, reaction temperature, and stirring conditions. As the oxidation reaction proceeds, the pH of the liquid shifts to the acidic side, but the pH of the liquid is preferably not less than 5. A magnetic substance can be obtained by filtering, washing, and drying the magnetic substance-containing liquid thus obtained by a conventional method.

  In the present invention, when the toner particles are produced by a polymerization method such as a suspension polymerization method, the surface of the magnetic material is preferably subjected to a hydrophobic treatment. In the case of hydrophobizing treatment by a dry method, a coupling agent is added to the magnetic material which has been washed, filtered and dried, and then hydrophobized. When the hydrophobization treatment is performed in a wet state, after the oxidation reaction is completed, the dried product is redispersed, or after the oxidation reaction is completed, the iron oxide body obtained by washing and filtering is not dried, but is dried. It is redispersed in an aqueous medium, a coupling agent is added, and a hydrophobic treatment is performed. Specifically, while sufficiently stirring the redispersion, a silane coupling agent is added, and after hydrolysis, the temperature is increased, or the pH of the dispersion is adjusted to an alkaline region after hydrolysis, thereby hydrophobizing. I do. Among these, from the viewpoint of carrying out a uniform hydrophobizing treatment, it is preferable to carry out the hydrophobizing treatment after completion of the oxidation reaction, by filtering, washing, and drying without reslurry as it is.

Examples of the coupling agent used in the hydrophobic treatment of the magnetic material include a silane coupling agent and a titanium coupling agent. Among these, silane coupling agents are preferable, and those represented by the following general formula (A) are more preferable.
R _m SiY _n (A)
[In general formula (A),
R represents an alkoxy group,
m is an integer of 1 to 3,
Y represents a functional group such as an alkyl group, vinyl group, epoxy group, (meth) acryl group,
n is an integer of 1 to 3,
m + n = 4. ]
Examples of the silane coupling agent represented by the general formula (A) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane , Vinyltriacetoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyl Rudiethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, trimethylmethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, hydroxypropyl Examples include trimethoxysilane, n-hexadecyltrimethoxysilane, and n-octadecyltrimethoxysilane. Moreover, these hydrolysates etc. are mentioned.

Among these, from the viewpoint of imparting high hydrophobicity to the magnetic material, an alkyltrialkoxysilane coupling agent represented by the following general formula (B) is preferable.
_{C p H 2p + 1 -Si- (} OC q H 2q + 1) 3 (B)
[In general formula (B),
p is an integer of 2 to 20,
q is an integer of 1 or more and 3 or less. ]
If p in the above formula is 2 or more, it becomes easy to sufficiently impart hydrophobicity to the magnetic material, and if p is 20 or less, coalescence of the magnetic materials can be suppressed. When q is 3 or less, the reactivity of the silane coupling agent is unlikely to decrease, and the hydrophobicity is easily performed sufficiently. Therefore, p in the general formula (B) is more preferably an integer of 3 to 15, and q is more preferably an integer of 1 to 2.

  The amount of the coupling agent to be used is preferably 0.9 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the magnetic substance. It is also preferable to adjust the amount of the coupling agent according to the surface area of the magnetic material, the reactivity of the coupling agent, and the like.

  In the present invention, other colorants may be used in addition to the magnetic substance. Examples of the colorant used in combination with the magnetic material include various dyes and pigments, and besides these, magnetic or nonmagnetic inorganic compounds. Specific examples include ferromagnetic metal particles such as cobalt and nickel, or alloys obtained by adding chromium, manganese, copper, zinc, aluminum, rare earth elements, and the like to these. Further, particles such as hematite, titanium black, nigrosine dye / pigment, carbon black, phthalocyanine and the like can be mentioned. These are also preferably used after hydrophobizing the surface.

  When the toner particles used in the present invention are produced by a pulverization method, for example, toner components such as a binder resin, a colorant, and a release agent and other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. . Then, melt and knead using a heat kneader such as a heating roll, kneader, and extruder to disperse or dissolve the above materials, cool and solidify, pulverize, classify, and perform surface treatment as necessary Thus, toner particles can be obtained. Either the classification or the surface treatment may be performed first. In the classification step, it is preferable to use a multi-division classifier from the viewpoint of production efficiency.

  The pulverization step can be performed by a method using various pulverization apparatuses such as a mechanical impact type and a jet type. Further, in order to obtain a toner (toner particles) having a preferable circularity used in the present invention, it is preferable to further heat and pulverize, or to perform an auxiliary mechanical impact treatment. Further, a hot water bath method in which finely pulverized (classified if necessary) toner particles are dispersed in hot water, a method of passing in a hot air stream, or the like may be used.

  Examples of the method for applying a mechanical impact force include a method using a mechanical impact type pulverizer such as a kryptron system manufactured by Kawasaki Heavy Industries, Ltd. or a turbo mill manufactured by Turbo Industry. Further, as a method adopted by a device such as a mechano-fusion system manufactured by Hosokawa Micron, there is a method of applying a mechanical impact force to the toner by pressing the toner against the inside of the casing by a high-speed rotating blade by a centrifugal force. .

  The toner particles used in the present invention are preferably contained in a shell containing a sulfonic acid polymer on the surface. In order to obtain such a toner by the above pulverization method, first, a core is prepared by the above pulverization method. Thereafter, the sulfonic acid polymer is externally added to the core to adhere to the surface of the core.

  Thereafter, using a device such as Meteole Inbo (manufactured by Nippon Pneumatic Kogyo Co., Ltd.), it is possible to obtain a toner particle having a shell containing a sulfonic acid polymer on the surface by performing hot air treatment.

  The toner particles used in the present invention can also be produced by a pulverization method as described above, but the toner particles obtained by this pulverization method are generally irregular in shape and tend to increase the total energy. It is in. Therefore, the toner particles used in the present invention are preferably produced in an aqueous medium such as a dispersion polymerization method, an association aggregation method, a dissolution suspension method, or a suspension polymerization method, and among these, the suspension polymerization method is more preferable. preferable.

  In the suspension polymerization method, a polymerizable monomer and a colorant (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives) are dissolved or dispersed in the polymerizable monomer. A composition is obtained. Thereafter, this polymerizable monomer composition is added to a continuous phase (for example, an aqueous medium (which may contain a dispersion stabilizer if necessary)). Then, particles of the polymerizable monomer composition are formed in the continuous phase (in the aqueous medium), and the polymerizable monomer contained in the particles is polymerized. This is a method for obtaining toner particles. A toner obtained by suspension polymerization (hereinafter, also referred to as “polymerized toner”) is preferable because the shape of individual toner particles is almost spherical, and the total energy tends to be low. Furthermore, since the toner has a relatively uniform charge amount distribution, an improvement in image quality can be expected.

  The following are mentioned as a polymerizable monomer used for manufacture of a polymerization toner.

As a polymerizable monomer,
Styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene;
Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, Acrylic esters such as phenyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic acid And methacrylic acid esters such as dimethylaminoethyl and diethylaminoethyl methacrylate. Other examples include polymerizable monomers such as acrylonitrile, methacrylonitrile, and acrylamide. These polymerizable monomers can be used alone or in combination of two or more. Among the polymerizable monomers described above, it is preferable to use styrene or a styrene derivative alone or in combination of a plurality of types from the viewpoints of development characteristics and durability of the toner. As other polymerizable monomers, acrylic acid esters and methacrylic acid esters are preferable.

  As the polymerization initiator used when the toner is produced by the polymerization method, those having a half-life of 0.5 hours or more and 30.0 hours or less during the polymerization reaction are preferable. Further, when the polymerization reaction is carried out in an amount of 0.5 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer, preferable strength and melting characteristics can be given to the toner.

As a specific polymerization initiator example,
2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile;
Benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butylperoxy 2-ethylhexanoate, t-butylperoxypivalate And peroxide polymerization initiators.

  When the toner is produced by the polymerization method, a crosslinking agent may be used, and the preferable amount is 0.01 parts by mass or more and 5.00 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. .

Here, as the crosslinking agent, a compound having two or more polymerizable double bonds is preferably used.
Aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene;
Carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, etc .;
Divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone;
A compound having three or more vinyl groups may be used alone or in combination.

  In the method of producing a toner by suspension polymerization, the above-described toner composition or the like is added to the polymerizable monomer as necessary, and uniformly dissolved or dispersed by a disperser such as a homogenizer, a ball mill, or an ultrasonic disperser. To obtain a polymerizable monomer composition. Then, the polymerizable monomer composition is added and suspended in an aqueous medium containing a dispersion stabilizer. At this time, it is easier to sharpen the particle size of the obtained toner particles by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to obtain a desired toner particle size all at once. As the addition time of the polymerization initiator, it may be added together with other additives in the polymerizable monomer, or added before the polymerizable monomer composition is added to the aqueous medium and suspended. Also good. Further, a polymerization initiator may be added immediately after forming the polymerizable monomer composition particles and before starting the polymerization reaction.

  After the particles of the polymerizable monomer composition are formed, stirring may be performed using a stirrer to such an extent that the particle state is maintained in the aqueous medium and the suspension and sedimentation of the particles are suppressed.

When the toner is produced by suspension polymerization, various surfactants, organic dispersants, and inorganic dispersants can be used as a dispersion stabilizer. Among these, inorganic dispersants can be preferably used because they are difficult to produce ultrafine powder that is difficult to handle and because of their steric hindrance, dispersion stability is obtained. Examples of such inorganic dispersants are:
Polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, hydroxyapatite;
Carbonates such as calcium carbonate and magnesium carbonate;
Inorganic salts such as calcium metasilicate, calcium sulfate, barium sulfate;
Examples thereof include inorganic compounds such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

  These inorganic dispersants are preferably used in an amount of 0.2 to 20.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Moreover, the said dispersion stabilizer can be used individually or in combination of multiple types. Further, a surfactant may be used in combination.

  In the step of polymerizing the polymerizable monomer, the polymerization temperature is set to 40 ° C or higher, and generally 50 ° C to 90 ° C. When the polymerization is carried out in this temperature range, the release agent to be sealed inside is precipitated by phase separation, and the encapsulation into the toner particles becomes more complete.

  After the polymerization of the polymerizable monomer is completed, the obtained polymer particles are filtered, washed, and dried to obtain toner particles. The toner particles can be obtained by mixing the toner particles with inorganic fine particles as described later, if necessary, and adhering them to the surface of the toner particles. It is also possible to insert a classification step in the manufacturing process (before mixing of the inorganic fine particles) to cut coarse powder and fine powder contained in the toner particles.

  In the toner of the present invention, it is preferable that inorganic fine particles or inorganic fine particles subjected to hydrophobic treatment are externally added (externally added) to the toner particles as a fluidity improver. As the inorganic fine particles, titanium oxide fine particles, silica fine particles, and alumina fine particles are preferable, and among these, silica fine particles are more preferable.

The inorganic fine particles used in the toner of the present invention preferably have a specific surface area by nitrogen adsorption measured by BET method of 30 m ² / g or more, more preferably 50 m ² / g or more and 400 m ² / g or less.

  The amount of the inorganic fine particles relative to the toner particles is preferably 0.2 parts by mass or more and 3.0 parts by mass or less, and 0.2 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the toner particles. Is more preferable. When the amount of the inorganic fine particles is in the above range, the toner can be given good fluidity and the fixing property is hardly inhibited.

  Next, the toner carrier used in the present invention will be described.

The toner carrier used in the present invention is:
Substrate,
An elastic layer, and
Surface layer containing urethane resin,
Have
The urethane resin is
A compound represented by the structural formula (1),
Polyisocyanate,
It has a partial structure derived from this reaction.

  One embodiment of a toner carrier according to the present invention is shown in FIG.

  In the conductive roller 1 (toner carrier) shown in FIG. 1, an elastic layer 3 is formed so as to cover the outer peripheral surface of a columnar or hollow cylindrical conductive substrate 2. The surface layer 4 is formed so as to cover the outer peripheral surface of the elastic layer 3.

<Substrate>
The base body 2 functions as an electrode and a support member of the conductive roller 1,
Metals or alloys such as aluminum, copper alloys, stainless steel;
Iron plated with chromium or nickel;
It is made of a conductive material such as a synthetic resin having conductivity.

<Elastic layer>
The elastic layer 3 gives the conductive roller elasticity necessary for forming a contact portion having a predetermined width at the contact portion between the conductive roller 1 and the electrostatic latent image carrier.

  The elastic layer 3 is preferably formed of a rubber material.

Rubber materials include ethylene-propylene-diene copolymer rubber (EPDM), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), natural rubber (NR), isoprene rubber (IR), styrene-butadiene rubber (SBR). ), Fluoro rubber, silicone rubber, epichlorohydrin rubber, hydride of NBR, urethane rubber and the like.
These can be used alone or in combination of two or more.

  Among these, silicone rubber is preferable because it does not easily cause compression set in the elastic layer even when another member (a regulating member (regulating blade) or the like) abuts over a long period of time. Examples of the silicone rubber include a cured product of addition-curable silicone rubber. Furthermore, since the adhesiveness with the surface layer mentioned later is excellent, the cured | curing material of addition curing type dimethyl silicone rubber is more preferable.

In the elastic layer 3, you may contain various additives, such as an electroconductivity imparting agent, a nonelectroconductive filler, a crosslinking agent, and a catalyst as needed. As a conductivity imparting agent,
Carbon black;
Fine particles of conductive metals such as aluminum and copper;
Examples thereof include fine particles of conductive metal oxide such as zinc oxide, tin oxide, and titanium oxide. Among these, carbon black is preferable because it can be obtained relatively easily and good conductivity can be obtained.

  When carbon black is used as the conductivity-imparting agent, it is blended in an amount of 2 to 50 parts by mass with respect to 100 parts by mass of rubber in the rubber material.

  Examples of the non-conductive filler include particles such as silica, quartz particles, titanium oxide, zinc oxide, and calcium carbonate.

  Examples of the crosslinking agent include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and dicumyl peroxide.

  As the catalyst, various commonly used catalysts can be used.

<Surface layer>
The surface layer 4 is a resin layer mainly composed of a urethane resin. A urethane resin is obtained by reaction of a polyol and polyisocyanate. Specifically, it can be synthesized as follows.

  First, a polyol component such as polyether polyol or polyester polyol is reacted with polyisocyanate to obtain an isocyanate group-terminated prepolymer.

  Subsequently, the urethane resin which concerns on this invention can be obtained by making an isocyanate group terminal prepolymer react with the compound which has a structure of Structural formula (1).

  Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

As polyester polyol,
A diol component such as 1,4-butanediol, 3-methyl-1,4-pentanediol, neopentyl glycol, a triol component such as trimethylolpropane,
Dicarboxylic acids such as adipic acid, phthalic anhydride, terephthalic acid, hexahydroxyphthalic acid,
And polyester polyols obtained by the condensation reaction.

  In addition to the above, polyolefin polyols such as polybutadiene polyol and polyisoprene polyol, hydrogenated products thereof, and polycarbonate polyol can be used.

  These polyol components may be prepolymerized as necessary in advance by chain extension with isocyanates such as 2,4-tolylene diisocyanate (TDI), 1,4-diphenylmethane diisocyanate (MDI), and isophorone diisocyanate (IPDI). Also good.

  The number average molecular weight of the polyether polyol and polyester polyol is preferably 1000 or more and 4000 or less. If the number average molecular weight of the polyol is 1000 or more and 4000 or less, the amount of hydroxyl groups relative to the molecular weight is relatively large, so that the reactivity with isocyanate is high, and the number of unreacted components is reduced. Is better.

As an isocyanate compound to be reacted with these polyol component and the compound represented by the structural formula (1),
Aliphatic polyisocyanates such as ethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI);
Cycloaliphatic polyisocyanates such as isophorone diisocyanate (IPDI), cyclohexane 1,3-diisocyanate, cyclohexane 1,4-diisocyanate;
Aromatic isocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), polymeric diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate and the like can be mentioned. . These copolymers, isocyanurate bodies, TMP adduct bodies, biuret bodies, and block bodies thereof can also be used.

  Among these, aromatic isocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and polymeric diphenylmethane diisocyanate are preferable.

  Regarding the mixing ratio of the polyol component and the isocyanate compound to be reacted with the compound represented by the structural formula (1), the ratio of the isocyanate group to 1.0 of each hydroxyl group is 1.0 or more and 2.0 or less. preferable.

  A compound represented by the structural formula (1) is used for the surface layer of the toner carrier used in the present invention. As described above, by using this compound, it is possible to maintain a good rolling property of the toner and to improve the charging property of the toner.

  The compound represented by the structural formula (1) will be described in detail. The compound represented by the structural formula (1) represents a polyfunctional polyol or terminal amino compound having an amine structure in the molecule.

  When n in the structural formula (1) is 1 or more and 4 or less, that is, a structure having 4 or more and 7 or less hydroxyl groups or amino groups which are reactive functional groups, a crosslinked structure by a urethane group or a urea group It is well formed and the microscopic hardness is improved. As a result, good rolling properties of the toner can be maintained.

  Next, according to studies by the present inventors, this effect is exhibited when the number of hydroxyl groups or amino groups of the compound represented by the structural formula (1) is 4 or more and 7 or less. Therefore, the number of terminal functional groups of the compound represented by the structural formula (1) may be at least 4, and the same effect can be obtained even if the rest is substituted with an alkyl group.

In the structural formula (1), each R ³ independently represents any one selected from the group consisting of the following (a) to (c).

(A) a hydroxyalkyl group having 2 to 8 carbon atoms,
(B) an aminoalkyl group having 2 to 8 carbon atoms,
(C) a group represented by the structural formula (2),
When R ³ is a hydroxyalkyl group, the number of carbon atoms is 1 or more and 8 or less, and when R ³ is an aminoalkyl group, the number of carbon atoms is 2 or more and 8 or less. It is easy to form and is preferable.

Structural formula (2) represents a group in which the terminal having a repeating unit of a so-called ether is a hydroxyl group. Also when R ³ is a group represented by the structural formula (2), for the same reason, R ⁵ is an alkylene group having 2 to 5 carbon atoms, and m, which is the number of ether repeats, is 2 or more and 3 or less. It is preferable that

In Structural Formula (1), R ⁴ is an alkylene group having 2 to 4 carbon atoms. When R ⁴ is an alkylene group having 2 to ⁴ carbon atoms, the chargeability of the toner carrier is improved. This is considered to be because when R ⁴ is an alkylene group having 2 or more and 4 or less carbon atoms, it has an appropriate size as a molecule, so that the dispersibility upon reaction with isocyanate is good.

Of the compounds represented by the structural formula (1), those represented by the structural formula (3) are preferable. That is, in the compound represented by the structural formula (1), n is 1 or 2, R ³ is each independently an alkylene group having 2 to 3 carbon atoms, and R ⁴ is an alkylene group having 2 carbon atoms. Preferably there is.

  In the urethane resin including a partial structure derived from the structural formula (3) having a functional group value of 5 (pentafunctional), the distance between the urethane groups is in the most preferable range, and therefore, the rolling property of the toner at the regulating portion is high. It becomes favorable and is particularly preferable.

(In structural formula (3),
n is 1 or 2,
R ⁶ each independently represents an alkylene group having 2 to 3 carbon atoms,
R ⁷ represents an alkylene group having 2 carbon atoms. )
In the present invention, the structure formed by the reaction of the compound represented by the structural formula (1) and the polyisocyanate has a structure in which R ³ is (a) a hydroxyalkyl group having 2 to 8 carbon atoms, or
(C) In the case of the group represented by the structural formula (2), a structure having a urethane group at the terminal of the structural formula (1) is obtained.

Further, when R ³ is (b) an aminoalkyl group having 1 to 8 carbon atoms, a structure having a urea group at the end of the structural formula (1) is obtained.

  The surface layer 4 preferably has conductivity. Examples of the method for imparting conductivity include addition of an ionic conductive agent and conductive fine particles to the surface layer 4. Among these, conductive fine particles that are inexpensive and have little resistance fluctuation in the environment are preferable, and among these, carbon black is more preferable from the viewpoints of conductivity imparting and reinforcing properties. If the conductive fine particles are carbon black having a primary particle diameter of 18 nm or more and 50 nm or less and a DBP oil absorption of 50 mL / 100 g or more and 160 mL / 100 g or less, a good balance of conductivity, hardness and dispersibility is preferable. It is preferable that the content rate of electroconductive fine particles is 10 to 30 mass% with respect to 100 mass parts of resin components which form a surface layer.

  When surface roughness is required for the toner carrier, fine particles for controlling roughness may be added to the surface layer 4. The fine particles for roughness control preferably have a volume average particle size of 3 μm or more and 20 μm or less. Moreover, it is preferable that the addition amount of the particle added to the surface layer is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin solid content of the surface layer. As the fine particles for roughness control, fine particles such as polyurethane resin, polyester resin, polyether resin, polyamide resin, acrylic resin, and phenol resin can be used.

  Examples of the method for forming the surface layer 4 include spraying with paint, dipping, and roll coating. The dip coating method for overflowing paint from the upper end of the dip tank as described in JP-A-57-5047 is simple and excellent in production stability as a method for forming a surface layer.

  Next, the developing device of the present invention will be described in detail with reference to the drawings.

  FIG. 2 is a schematic cross-sectional view showing an example of the developing device of the present invention. FIG. 3 is a schematic sectional view showing an example of an image forming apparatus in which the developing device of the present invention is incorporated.

  2 or 3, the electrostatic latent image carrier 5 on which the electrostatic latent image is formed is rotated in the direction of the arrow R1. The toner carrier 7 rotates in the direction of the arrow R2 to convey the toner 19 to the developing area where the toner carrier 7 and the electrostatic latent image carrier 5 are opposed to each other. Further, a toner supply member 8 is in contact with the toner carrier, and the toner 19 is supplied to the surface of the toner carrier by rotating in the direction of arrow R3.

  Around the electrostatic latent image carrier 5, a charging roller 6, a transfer member (transfer roller) 10, a cleaner container 11, a cleaning blade 12, a fixing device 13, a pickup roller 14, and the like are provided. The electrostatic latent image carrier 5 is charged by the charging roller 6. Exposure (image exposure) is performed by irradiating the electrostatic latent image carrier 5 with laser light (image exposure light) by a laser generator (image exposure apparatus) 16, and electrostatic latent image corresponding to the target image is obtained. An image is formed. The electrostatic latent image on the electrostatic latent image carrier 5 is developed with toner in the developing device 9 to obtain a toner image. The toner image is transferred onto a transfer material (paper) 15 by a transfer member (transfer roller) 10 in contact with the electrostatic latent image carrier 5 via the transfer material. The transfer of the toner image to the transfer material may be performed via an intermediate transfer member. The transfer material (paper) 15 on which the toner image is placed is conveyed to the fixing device 13 and fixed on the transfer material (paper) 15. In addition, the toner 19 partially remaining on the electrostatic latent image carrier 5 is scraped off by the cleaning blade 12 and stored in the cleaner container 11.

  In the charging step of the developing device of the present invention, the electrostatic latent image carrier and the charging roller form a contact portion to contact each other, and a predetermined charging bias is applied to the charging roller to apply the surface of the electrostatic latent image carrier. It is preferable to use a contact charging device that charges the battery to a predetermined polarity and potential. By performing contact charging in this manner, stable and uniform charging can be performed, and generation of ozone can be reduced. It is more preferable to use a charging roller that rotates in the same direction as the electrostatic latent image carrier in order to maintain uniform contact with the electrostatic latent image carrier and perform uniform charging.

  As a preferable process condition when using a charging roller, a contact pressure of the charging roller is 4.9 N / m or more and 490.0 N / m or less, and a DC voltage or a voltage obtained by superimposing an AC voltage on a DC voltage is applied. Conditions can be exemplified.

  The peak-to-peak voltage of the AC voltage is preferably 0.5 kVpp to 5.0 kVpp, and the AC frequency is preferably 50 Hz to 5 kHz. As the DC voltage, the absolute value of the voltage is preferably 400 V or more and 1700 V or less.

  The material of the charging roller is an elastic material such as ethylene-propylene-diene polyethylene (EPDM), urethane, butadiene acrylonitrile rubber (NBR), silicone rubber, or isoprene rubber. Examples thereof include a rubber material in which a conductive substance such as a product is dispersed, and those obtained by foaming these materials. It is also possible to adjust the resistance using an ion conductive material without dispersing the conductive substance or in combination with the conductive substance.

  Examples of the core bar used for the charging roller include aluminum and SUS. The charging roller is disposed in pressure contact with the electrostatic latent image carrier as a member to be charged with a predetermined pressing force, and a charging contact portion that is a contact portion between the charging roller and the electrostatic latent image carrier is provided. Let it form.

  Next, the contact transfer process preferably used in the present invention will be specifically described.

  The contact transfer process is to electrostatically transfer the toner image to the recording medium while the electrostatic latent image carrier is in contact with the transfer member to which a voltage having a polarity opposite to that of the toner is applied via the recording medium. The contact pressure of the transfer member is preferably a linear pressure of 2.9 N / m or more, and more preferably 19.6 N / m or more. When the linear pressure as the contact pressure is 2.9 N / m or more, it is difficult for the recording medium to be transported and to cause transfer failure.

  In the present invention, it is preferable that the thickness of the toner layer on the toner carrying member is regulated by contacting the toner carrying member with the regulating member through the toner. In this way, high image quality with reduced fog can be obtained. A regulating blade is generally used as the regulating member that comes into contact with the toner carrier, and can be suitably used in the present invention.

As the regulation blade,
Rubber elastic body such as silicone rubber, urethane rubber, NBR;
Synthetic resin elastic body such as polyethylene terephthalate;
A metal elastic body such as a phosphor bronze plate or a SUS plate can be used, and a composite body thereof may be used. Further, a charge control substance such as resin, rubber, metal oxide, or metal is applied to an elastic support such as rubber, synthetic resin, or metal elastic body in order to control the chargeability of the toner. You may use what was attached to hit. Among these, a material in which a resin and rubber are bonded to a metal elastic body so as to come into contact with a contact portion with the toner carrier is preferable.

  As a material of the member to be bonded to the metal elastic body, a material that is easily charged to positive polarity such as urethane rubber, urethane resin, polyamide resin, and nylon resin is preferable.

  The base, which is the upper side of the regulation blade, is fixedly held on the developing device side, and the lower side is bent against the elastic force of the blade in the forward or reverse direction of the toner carrier to carry the toner. It is brought into contact with the body surface with an appropriate elastic pressing force.

  The contact pressure between the regulating blade and the toner carrying member is preferably 1.30 N / m or more and 245.0 N / m or less, preferably 4.9 N / m or more and 118. More preferably, it is 0 N / m or less. If the contact pressure is 1.30 N / m or more, the toner can be applied more uniformly, and fogging and scattering are less likely to occur. When the contact pressure is 245.0 N / m or less, it is difficult for a large pressure to be applied to the toner, and the toner does not easily deteriorate.

The amount of toner on the toner carrying member (toner layer), it is preferably, 3.0 g / ^{m 2} or more 14.0 g / ^{m 2} or less is 2.0 g / ^{m 2} or more 15.0 g / ^{m 2} or less It is more preferable.

If the amount of toner on the toner carrier is 2.0 g / m ² or more, a sufficient image density can be easily obtained. If the amount of the toner on the toner carrier is 15.0 g / m ² or less, it is difficult for regulation failure to occur, and uniform chargeability is easily obtained, so that fog can be further suppressed.

  In the present invention, the amount of toner on the toner carrier can be changed by changing the surface roughness (Ra) of the toner carrier, the free length of the regulating blade, the contact pressure of the regulating blade, and the like.

As a method for measuring the amount of toner on the toner carrier, first, a cylindrical filter paper is attached to a suction port having an outer diameter of 6.5 mm. This is attached to a vacuum cleaner, sucking the toner on the toner carrying member while sucking it, and dividing the amount of sucked toner (g) by the sucked area (m ² ) to obtain the amount of toner on the toner carrying member. .

  In the present invention, the outer diameter of the toner carrier is preferably 8.0 mm or greater and 14.0 mm or less. The smaller the outer diameter of the toner carrier, the better from the viewpoint of making the developing device compact, but the larger the outer diameter, the better from the viewpoint of good developability and suppression of fogging.

  The surface roughness of the toner carrier used in the present invention is a center line average roughness Ra in the standard of JIS B 0601: 1994, and is preferably 0.3 μm or more and 5.0 μm or less, and 0.5 μm or more. More preferably, it is 4.5 μm or less.

  If Ra is not less than 0.3 μm and not more than 5.0 μm, a sufficient amount of toner can be obtained, the amount of toner on the toner carrier can be easily regulated, and it becomes difficult to cause a regulation failure. The amount tends to be uniform.

  The measurement of the centerline average roughness Ra in accordance with JIS B 0601: 1994 surface roughness standards of the surface of the toner carrier is performed using a surf coder SE-3500 manufactured by Kosaka Laboratory. The measurement conditions were a cut-off of 0.8 mm, an evaluation length of 4 mm, a feed rate of 0.5 mm / s, and measurement for 9 points (3 points in the circumferential direction for each of 3 points equally spaced in the axial direction). And the average value was taken.

  In order to make the surface roughness of the toner carrier in the present invention in the above range, for example, the polishing state of the surface layer of the toner carrier is changed, or spherical carbon particles, carbon fine particles, graphite, resin fine particles, etc. are used as the surface layer. The method of making it contain is mentioned.

  In the present invention, the developing step is preferably a step of forming a toner image by applying a developing bias to the toner carrier and transferring the toner to the electrostatic latent image on the electrostatic latent image carrier. The development bias may be a DC voltage or a voltage obtained by superimposing an AC voltage on a DC voltage.

  Examples of the waveform of the AC voltage include a sine wave, a rectangular wave, and a triangular wave. Further, a pulse wave formed by periodically turning on / off a DC power supply can be used. In this way, a bias that periodically changes the voltage value can be used as the waveform of the AC voltage.

  In the present invention, when a method of conveying toner by magnetism is used without using a toner supply member, it is preferable to arrange a magnet inside the toner carrier (reference numeral 21 in FIG. 4). In this case, the toner carrier preferably has a fixed magnet having multiple poles therein, and preferably has 3 or more and 10 or less poles.

  Next, a method for measuring physical properties of the toner used in the present invention will be described.

<Average particle size and particle size distribution of toner>
The weight average particle diameter (D4) of the toner is calculated as follows.

  As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion exchange water so that the concentration becomes 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

  The specific measurement method is as follows.

  (1) Put 200 mL of the above electrolytic solution into a glass 250 mL round bottom beaker dedicated to Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.

  (2) Put 30 mL of the above electrolytic solution into a glass 100 mL flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. 0.3 mL of a diluted solution obtained by diluting 3) with ion-exchanged water.

  (3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikkei Bios Co., Ltd.) having an electrical output of 120 W is prepared. Put 3.3 L of ion exchange water in the water tank of the ultrasonic dispersing machine, and add 2 mL of Contaminone N into this water tank.

  (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

  (5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In addition, in ultrasonic dispersion | distribution, it adjusts so that the water temperature of a water tank may be 10 to 40 degreeC.

  (6) To the round bottom beaker of the above (1) installed in the sample stand, the electrolyte aqueous solution of the above (5) in which the toner is dispersed is dropped using a pipette, and the measured concentration is adjusted to 5%. Measurement is performed until the number of measured particles reaches 50,000.

  (7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the “analysis / volume statistic (arithmetic average)” screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Calculation method of the ratio (E / A) of (E) to the abundance (E) of sulfur atoms present on the surface of toner particles and the abundance (A) of carbon atoms present on the surface of toner particles>
The E and E / A are calculated based on the analysis result of surface composition analysis by X-ray photoelectron spectroscopy (ESCA). The ESCA apparatus and measurement conditions are as follows.
Apparatus used: 1600S type X-ray photoelectron spectrometer manufactured by PHI (Physical Electronics Industries, Inc.) Measurement conditions: X-ray source MgKα (400 W), spectral region 800 μmφ
In the present invention, the surface atomic concentration (atomic%) is calculated from the measured peak intensity of each element using a relative sensitivity factor provided by PHI.

  The ranges of the measurement peak top of each element used for measurement are carbon atoms: 283 to 293 eV, iron atoms: 706 to 730 eV, and sulfur atoms: 166 to 172 eV.

  As the measurement sample, toner particles are used. When an external additive is added to the toner, the toner is washed with a solvent that does not dissolve the toner, such as isopropanol, and the external additive is removed. Measure.

<Method for measuring acid value of resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample.

  The acid value of the binder resin is measured according to JIS K 0070-1992. Specifically, it measures according to the following procedures.

(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), and ion exchanged water is added to make 100 mL to obtain a phenolphthalein solution.

  7 g of special grade potassium hydroxide is dissolved in 5 mL of water, and ethyl alcohol (95% by volume) is added to make 1 L. In order to avoid contact with carbon dioxide, etc., it is placed in an alkali-resistant container and left for 3 days, followed by filtration to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution is as follows. 25 mL of 0.1 mol / L hydrochloric acid is placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution is added, titrated with the potassium hydroxide solution, and the potassium hydroxide required for neutralization. Determine from the amount of solution. As the 0.1 mol / L hydrochloric acid, one prepared according to JISK8001-1998 is used.

(2) Operation (A) Main test 2.0 g of the pulverized binder resin sample is precisely weighed into a 200 mL Erlenmeyer flask, and 100 mL of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. . Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator lasts for 30 seconds.

(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).

(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (mL) of potassium hydroxide solution in blank test, C: addition amount (mL) of potassium hydroxide solution in final test, f: potassium hydroxide Solution factor, S: sample (g).

  Hereinafter, the present invention will be described more specifically with reference to production examples and examples, but these do not limit the present invention in any way. In addition, all the parts in the following mixing | blending show a mass part.

(Preparation of base 2)
The substrate 2 was prepared by applying a primer (trade name, DY35-051; manufactured by Toray Dow Corning) on a 6 mm diameter cored bar made of SUS304 and baking it.

(Production of elastic roller)
The base 2 prepared as described above was placed in a mold, and an addition type silicone rubber composition in which the following materials were mixed was injected into a cavity formed in the mold.
-100 parts by mass of liquid silicone rubber material (trade name, SE6724A / B; manufactured by Toray Dow Corning)
-15 parts by mass of carbon black (trade name, Toka Black # 4300; manufactured by Tokai Carbon Co., Ltd.)
-0.2 parts by mass of silica particles as heat resistance imparting agent,
-Platinum catalyst 0.1 mass part.

  An addition-type silicone rubber composition mixed with the materials shown in Table 1 below was injected into a cavity formed in the mold. Subsequently, the mold was heated to cure and cure the silicone rubber at a temperature of 150 ° C. for 15 minutes. The substrate on which the cured silicone rubber layer was formed on the peripheral surface was removed from the mold, and then the substrate was further heated at a temperature of 180 ° C. for 1 hour to complete the curing reaction of the silicone rubber layer. Thus, an elastic roller D-1 in which a silicone rubber elastic layer having a diameter of 12 mm was formed so as to cover the outer peripheral surface of the substrate 2 was produced.

(Preparation of surface layer 4)
The synthesis example for obtaining the polyurethane surface layer of this invention is shown below.

(Synthesis of isocyanate group-terminated prepolymer A-1)
Polypropylene glycol polyol (trade name: Exenol 4030; manufactured by Asahi Glass Co., Ltd.) with respect to 17.7 parts by mass of tolylene diisocyanate (TDI) (trade name: Cosmonate T80; manufactured by Mitsui Chemicals) in a reaction vessel under a nitrogen atmosphere. 100.0 g was gradually added dropwise while maintaining the temperature in the reaction vessel at 65 ° C. After completion of the dropping, the reaction was carried out at a temperature of 65 ° C. for 2 hours. The obtained reaction mixture was cooled to room temperature to obtain an isocyanate group-terminated prepolymer A-1 having an isocyanate group content of 3.8% by weight.

(Synthesis of isocyanate group-terminated prepolymer A-2)
100 parts of butylene adipate-based polyol (trade name: NIPPOLAN 4010; manufactured by Nippon Polyurethane Industry Co., Ltd.) with respect to 33.8 parts by mass of polymeric MDI (trade name: Millionate MR, manufactured by Nippon Polyurethane Industry Co., Ltd.) in a reaction vessel under a nitrogen atmosphere The temperature in the 0.0 g reaction vessel was gradually dropped while maintaining the temperature at 65 ° C. After completion of the dropping, the reaction was carried out at a temperature of 65 ° C. for 2 hours. The obtained reaction mixture was cooled to room temperature to obtain an isocyanate group-terminated prepolymer A-2 having an isocyanate group content of 4.3% by weight.

(Synthesis of amino compound (compound represented by structural formula (1)))
(Synthesis of amino compound B-1)
100.0 parts by mass (1.67 mol) of ethylenediamine and 100 parts by mass of pure water were heated to 40 ° C. while stirring in a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device, and a temperature controller. . Next, while maintaining the reaction temperature at 40 ° C. or lower, 425.3 parts by mass (7.35 mol) of propylene oxide was gradually added dropwise over 30 minutes. The reaction was further stirred for 1 hour to obtain a reaction mixture. The obtained reaction mixture was heated under reduced pressure to distill off water, whereby 426 g of amino compound B-1 was obtained.

(Synthesis of amino compound B-2)
Amino compound B-2 was obtained in the same manner as in the synthesis example of amino compound B-1, except that the blending amount of propylene oxide and the reaction time were changed as shown in Table 1 below.

(Synthesis of amino compound B-3)
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, and a temperature controller, 100.0 parts by mass (0.97 mol) of diethylenetriamine and 100 parts by mass of ethanol were heated to 40 ° C. while stirring. Next, 235.0 parts by mass (5.34 mol) of ethylene oxide was gradually added dropwise over 30 minutes while maintaining the reaction temperature at 60 ° C. or lower. The reaction was further stirred for 1 hour to obtain a reaction mixture. The obtained reaction mixture was heated under reduced pressure to distill off ethanol to obtain 276 g of amino compound B-3.

(Synthesis of amino compound B-4)
Amino compound B-4 was obtained in the same manner as in the synthesis example of amino compound B-3 except that ethylene oxide was changed to 2-methyl-tetrahydrofuran and the blending amount and reaction time were changed as shown in Table 1.

(Synthesis of amino compound B-5)
In a reaction vessel equipped with a stirrer, thermometer, reflux tube, dropping device and temperature controller, add 100.0 parts by mass of tetraethylenepentamine (0.53 mol) and 100 parts by mass of ethanol to 40 ° C while stirring. Warm up. Next, 851.5 parts by mass (4.08 mol) of 8-bromo-1-octanol was gradually added dropwise over 30 minutes while maintaining the reaction temperature at 40 ° C. or lower. The reaction was further stirred for 1.5 hours to obtain a reaction mixture. The obtained reaction mixture was heated under reduced pressure to distill off ethanol to obtain 1288 g of amino compound B-5.

(Synthesis of amino compound B-6)
While stirring, 100.0 parts by mass (1.14 mol) of butylenediamine and 100 parts by mass of ethanol were heated to 40 ° C. in a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device, and a temperature controller. . Next, 215.0 parts by mass (5.02 mol) of ethyleneimine was gradually added dropwise over 30 minutes while maintaining the reaction temperature at 40 ° C. or lower. The reaction was further stirred for 1 hour to obtain a reaction mixture. The obtained reaction mixture was heated under reduced pressure to distill off ethanol to obtain 216 g of amino compound B-6.

(Synthesis of Amino Compound B-7)
Amino compound B-7 was obtained in the same manner as in the synthesis example of amino compound B-6 except that ethyleneimine was changed to 8-bromo-1-aminooctane and the blending amount was changed as shown in Table 1. .

The structure of the obtained amino compound is shown in Table 2. In the table, n represents the number of repeating amino structural units of the structural formula (1), and m represents the number of repeating ethers when R ³ is the structural formula (2). The number of groups in the table represents the number of terminal hydroxyl groups or terminal amino groups that the amino compound has in one molecule.

<Preparation of Toner Carrier 1>
As a material of the surface layer 4, with respect to 617.9 parts by mass of the isocyanate group-terminated prepolymer A-1,
34.2 parts by mass of amino compound B-1
Carbon black (trade name, MA230; manufactured by Mitsubishi Chemical Corporation) 117.4 parts by mass, and
130.4 parts by mass of urethane resin fine particles (trade name, Art Pearl C-400; manufactured by Negami Kogyo Co., Ltd.)
Were stirred and mixed.

  Next, methyl ethyl ketone (hereinafter also referred to as “MEK”) was added so that the total solid content ratio was 30% by mass, and then mixed in a sand mill. Subsequently, the viscosity was further adjusted to 10 cps or more and 13 cps or less with MEK to prepare a coating material for forming a surface layer.

  The elastic roller D-1 produced previously was immersed in the coating material for surface layer formation, the coating film of the said coating material was formed on the surface of the elastic layer of the elastic roller D-1, and it was dried. Further, a heat treatment was performed at a temperature of 150 ° C. for 1 hour to provide a surface layer having a film thickness of 15 μm so as to cover the outer peripheral surface of the elastic layer, and thus a toner carrier 1 was produced.

<Preparation of toner carrier 2-7>
A coating material for forming a surface layer was prepared in the same manner as the preparation of the toner carrier 1 except that the material shown in Table 3 below was used as the material for the surface layer 4. Then, each of the coating materials was applied to the elastic roller D-1 in the same manner as the preparation of the toner carrier 1, dried and heated to prepare toner carriers 2 to 7.

<Preparation of Toner Carrier 8>
As a material of the surface layer 4, with respect to 632.8 parts by mass of the isocyanate group-terminated prepolymer A-2,
19.5 parts by mass of pentaerythritol,
Carbon black (trade name, MA230; manufactured by Mitsubishi Chemical Corporation) 117.4 parts by mass, and
130.5 parts by mass of urethane resin fine particles (trade name, Art Pearl C-400; manufactured by Negami Kogyo Co., Ltd.)
Were stirred and mixed.

  Thereafter, the coating material for forming the surface layer according to the toner carrier 8 was prepared in the same manner as the method for preparing the coating material for forming the surface layer according to the production of the toner carrier 1. This surface layer forming coating was applied to the surface of the silicone rubber elastic layer of the elastic roller D-1 in the same manner as the preparation of the toner carrier 1, and dried to form a surface layer, whereby a toner carrier 8 was produced.

<Preparation of Toner Carrier 9>
As a material of the surface layer 4, with respect to 351.6 parts by mass of isocyanate group-terminated prepolymer A-2,
300.5 parts by mass of a polypropylene glycol-based polyol (trade name: Exenol 230; manufactured by Asahi Glass Co., Ltd.)
Carbon black (trade name, MA230; manufactured by Mitsubishi Chemical Corporation) 117.4 parts by mass, and
130.5 parts by mass of urethane resin fine particles (trade name, Art Pearl C-400; manufactured by Negami Kogyo Co., Ltd.)
Were stirred and mixed.

  Thereafter, the coating material for forming the surface layer according to the toner carrier 9 was prepared in the same manner as the method for preparing the coating material for forming the surface layer related to the production of the toner carrier 1. This surface layer forming coating was applied to the surface of the silicone rubber elastic layer of the elastic roller D-1 in the same manner as the preparation of the toner carrier 1 and dried to form a surface layer, whereby a toner carrier 9 was produced.

<Manufacture of magnetic body 1>
In a ferrous sulfate aqueous solution, 1.1 equivalent of a caustic soda solution with respect to iron atoms, P ₂ O _{5 in} an amount of 0.15% by mass in terms of phosphorus atoms with respect to iron atoms, silicon with respect to iron atoms An aqueous solution containing ferrous hydroxide was prepared by mixing SiO ₂ in an amount of 0.50% by mass in terms of atoms. The pH of the aqueous solution was set to 7.5, and an oxidation reaction was performed at 85 ° C. while blowing air to prepare a slurry liquid having seed crystals.

  Next, after adding an aqueous ferrous sulfate solution to this slurry so as to have 1.1 equivalents with respect to the initial alkali amount (sodium component of caustic soda), the slurry is maintained at pH 7.4 and air is blown into it. While proceeding the oxidation reaction, a slurry liquid containing magnetic iron oxide was obtained. After filtration and washing, the water-containing slurry was once taken out. At this time, a small amount of water-containing sample was collected and the water content was measured. Next, this water-containing sample was put into another aqueous medium without being dried, stirred and redispersed with a pin mill while circulating the slurry, and the pH of the redispersed liquid was adjusted to 5.0. Then, 1.5 parts by mass of n-hexyltrimethoxysilane was added to 100 parts by mass of magnetic iron oxide with stirring (the amount of magnetic iron oxide was calculated as a value obtained by subtracting the water content from the water-containing sample), and water was added. Decomposition was performed. Thereafter, the mixture was sufficiently stirred and dispersed with a pin mill while circulating the slurry, and the pH of the dispersion was adjusted to 8.6 to perform a hydrophobic treatment. The obtained hydrophobic magnetic material is filtered with a filter press, washed with a large amount of water, dried at 100 ° C. for 15 minutes, and then at 90 ° C. for 30 minutes. A magnetic material 1 having a (DV) of 0.22 μm was obtained.

<Production of sulfonic acid polymer 1>
To a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device,
As a solvent, 250 parts of methanol, 150 parts of 2-butanone and 100 parts of 2-propanol,
As monomers, 87 parts of styrene, 12 parts of butyl acrylate and 7 parts of 2-acrylamido-2-methylpropanesulfonic acid (hereinafter also referred to as “AMPS”) were added and heated to reflux temperature with stirring. A solution obtained by diluting 0.45 part of t-butylperoxy-2-ethylhexanoate as a polymerization initiator with 20 parts of 2-butanone was added dropwise thereto over 30 minutes, and stirring was continued for 5 hours. Further, a solution obtained by diluting 0.28 part of t-butylperoxy-2-ethylhexanoate with 20 parts of 2-butanone was added dropwise over 30 minutes, and the mixture was further stirred for 5 hours to complete the polymerization.

  The polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less using a cutter mill equipped with a 150 mesh screen. The glass transition temperature (Tg) of the obtained polymer was 70 ° C. The composition of the resulting sulfonic acid polymer 1 is shown in Table 4.

<Production of sulfonic acid polymers 2 to 6>
In the production of the sulfonic acid polymer 1, sulfonic acid polymers 2 to 6 were obtained in the same manner as the sulfonic acid polymer 1, except that the monomers used were changed to those shown in Table 4. The composition of the obtained sulfonic acid polymer is shown in Table 4.

  In addition, the number in a table | surface shows a mass part number.

* 1: Methyl sulfonate is 2-acrylamido-2-methylpropane sulfonic acid methyl ester <Production of amorphous polyester resin 1>
A monomer component other than trimellitic anhydride shown in Table 5 in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe is put in a molar ratio shown in Table 5 and water generated at 230 ° C. under a nitrogen stream. The mixture was allowed to react for 10 hours while distilling off. At this time, as a catalyst, 0.25 part of a titanium-based catalyst (titanium dihydroxybis (triethanolaminate)) was added to 100 parts of the total monomer of acid and alcohol.

  Next, the reaction was carried out under a reduced pressure of 20 mmHg. When the acid value reached 1 mgKOH / g, the mixture was cooled to 180 ° C., trimellitic anhydride was added at a molar ratio shown in Table 5, and the reaction was performed for 2 hours under atmospheric pressure sealing The amorphous polyester resin 1 was obtained by taking out, cooling to room temperature, and pulverizing. Table 5 shows the physical properties of the obtained amorphous polyester resin 1.

<Manufacture of amorphous polyester resins 2-8>
Amorphous polyester resins 2 to 8 were obtained in the same manner as in Production Example 1 of the amorphous polyester resin except that the monomer components and the blending were changed as shown in Table 5. Table 5 shows the composition and physical properties of the obtained amorphous polyester resins 2 to 8.

<Production Example of Toner 1>
After adding 450 parts by mass of 0.1 M Na ₃ PO ₄ aqueous solution to 720 parts by mass of ion-exchanged water and heating to 60 ° C., 67.7 parts by mass of 1.0 M CaCl ₂ aqueous solution was added, and a dispersing agent was added. An aqueous medium containing was obtained.
・ Styrene 78.0 mass parts ・ N-butyl acrylate 22.0 mass parts ・ Divinylbenzene 0.48 mass parts ・ Sulphonic acid polymer 11.5 mass parts ・ Magnetic substance 170.0 mass parts ・ Amorphous polyester resin 15.0 parts by mass The above formulation was uniformly dispersed and mixed using an attritor (Mitsui Miike Chemical Co., Ltd.) to obtain a polymerizable monomer composition. This polymerizable monomer composition was heated to 60 ° C., 10 parts by mass of paraffin wax (melting point: 72 ° C.) was added thereto, mixed and dissolved, and then the polymerization initiator 2,2′-azobis (2 , 4-dimethylvaleronitrile) was dissolved in an amount of 4.5 parts by mass.

The polymerizable monomer composition was put into the aqueous medium, and the mixture was granulated by stirring at 12,000 rpm for 10 minutes in a TK homomixer (Special Machine Industries Co., Ltd.) in an N ₂ atmosphere at 60 ° C. . Thereafter, the mixture was reacted at 70 ° C. for 5 hours while stirring with a paddle stirring blade. After completion of the reaction, the suspension was cooled, washed with hydrochloric acid and then filtered and dried to obtain toner particles 1.

The toner particles 1 were treated with 100 parts by mass and silica particles having a primary particle size of 12 nm with hexamethyldisilazane and then with silicone oil, and the treated silica particles having a BET specific surface area value of 120 m ² / g 0.5 mass Part was put into a Henschel mixer FM10C (Mitsui Miike Chemical Co., Ltd.) and mixed at 4000 rpm for 6 minutes to obtain toner 1. The obtained toner particles 1 had a weight average particle diameter (D4) of 8.0 μm. The production conditions and physical properties of the toner particles 1 are shown in Table 6.

<Manufacture of toners 2-18>
In the production of the toner particles 1, toner particles 2 to 15 were obtained in the same manner as in the production of the toner particles 1, except that the shell resin and the sulfonic acid polymer were changed as shown in Table 6. Table 6 shows the compositions and physical properties of the toners 2 to 15.

<Example 1>
(Image forming device)
A Canon printer LBP7700C was modified and used for image output evaluation. As a modification point, as shown in FIG. 2, the toner supply member of the developing device is rotated in the reverse direction to the toner carrier, and the voltage application to the toner supply member is turned off. The contact pressure was adjusted so that the width of the contact portion between the toner carrier and the electrostatic latent image carrier was 1.1 mm. By doing in this way, it becomes possible to evaluate regulation defects strictly. Moreover, the voltage application to the regulating member (blade) was also turned off, and modifications were made so as to strictly evaluate fogging in a high temperature and high humidity environment.

  The developing device thus modified was charged with 100 g of toner 1 and a toner carrying member 2 was used to produce a developing device. The developed developing device was set in a black station, and 3000 sheets of images were output in a high temperature and high humidity environment (40 ° C./95% RH) and a low temperature and low humidity environment (15 ° C./10% RH). In addition, the image output test was performed by continuous paper passing using a horizontal line with a printing rate of 2% as an image.

  As a result, a clear image without fogging was obtained under a high temperature and high humidity environment, and a good image without fogging was obtained even under a low temperature and low humidity environment. Table 7 shows the evaluation results.

  The evaluation methods of the respective evaluations performed in the examples and comparative examples of the present invention and the judgment criteria thereof will be described below.

<Inverted fog>
A white image was output at the initial stage of image output and after 3000 images were output, and the reflectance was measured using REFECTMETERMODELTC-6DS manufactured by Tokyo Denshoku. On the other hand, the reflectance of the transfer paper (standard paper) before white image formation was measured in the same manner. A green filter was used as the filter. The fog was calculated from the reflectance before and after the white image output using the following formula.
Fog (reflectance) (%) = reflectance of standard paper (%)-reflectance of white image sample (%)
The standard for determining fog is as follows.
A: Very good level (fogging less than 1.0%)
B: Good level (fogging of 1.0% to less than 1.5%)
C: Level that is not a problem in practical use (fog 1.5% to less than 2.5%)
D: Acceptable level (Fog 2.5% or more and less than 3.5% or less)
E: Unpreferable level for practical use (fogging of 3.5% or more)
<Black fogging>
The reflectance of the white image immediately after outputting the black image after the initial image output and 3000 image outputs was measured using REFECTMETERMODELTC-6DS manufactured by Tokyo Denshoku. On the other hand, the reflectance of the transfer paper (standard paper) before white image formation was measured in the same manner. A green filter was used as the filter. The fog was calculated from the reflectance before and after the white image output using the following formula.
Fog (reflectance) (%) = reflectance of standard paper (%)-reflectance of white image sample (%)
The standard for determining fog is as follows.
A: Very good level (fogging less than 1.0%)
B: Good level (fogging of 1.0% to less than 1.5%)
C: Level that is not a problem in practical use (fog 1.5% to less than 2.5%)
D: Acceptable level (Fog 2.5% or more and less than 3.5% or less)
E: Unpreferable level for practical use (fogging of 3.5% or more)
<Examples 2 to 22>
A developing device was produced by combining the toner and the toner carrier as shown in Table 7, and the image output of each developing device was evaluated in the same manner as in Example 1. As a result, in all developing devices, good results were obtained for both fogging in a high temperature and high humidity environment and poor regulation in a low temperature and low humidity environment before and after the durability test. Table 7 shows the evaluation results.

<Reference Examples 1-3>
A developing device was produced by combining the toner and the toner carrier as shown in Table 7, and the image output of each developing device was evaluated in the same manner as in Example 1. As a result, in all the developing devices, the fogging in the high temperature and high humidity environment and the poor regulation in the low temperature and low humidity environment before and after the durability test were practically satisfactory. Table 7 shows the evaluation results.

<Comparative Examples 1 and 2>
A developing device was produced by combining the toner and the toner carrier as shown in Table 7, and the image output of each developing device was evaluated in the same manner as in Example 1. As a result, in any of the developing devices, the poor regulation under the low temperature and low humidity environment was practically no problem, but the fog under the high temperature and high humidity environment was bad. Table 7 shows the evaluation results.

<Preparation of Toner Carrier 10>
(Preparation of substrate)
As the substrate 2, a primer (trade name, DY35-051; manufactured by Toray Dow Corning) was applied and baked on a ground aluminum cylindrical tube having an outer diameter of 10 mm (diameter) and an arithmetic average roughness Ra of 0.2 μm.

(Production of elastic roller)
The base prepared as described above was placed in a mold, and an addition type silicone rubber composition in which the following materials were mixed was injected into a cavity formed in the mold.
Liquid silicone rubber material (trade name, SE6724A / B; manufactured by Toray Dow Corning) 100 parts by mass,
Carbon black (trade name, Toka Black # 4300; manufactured by Tokai Carbon Co., Ltd.) 15 parts by mass
-0.2 parts by mass of silica particles as heat resistance imparting agent,
-Platinum catalyst 0.1 mass part.

  Subsequently, the mold was heated to cure and cure the silicone rubber at a temperature of 150 ° C. for 15 minutes. The substrate on which the cured silicone rubber layer was formed on the peripheral surface was removed from the mold, and then the substrate was further heated at a temperature of 180 ° C. for 1 hour to complete the curing reaction of the silicone rubber layer. Thus, an elastic roller D-2 in which a silicone rubber elastic layer having a film thickness of 0.5 mm and a diameter of 11 mm was formed on the outer periphery of the substrate 1 was produced.

(Preparation of surface layer)
As a material of the surface layer 4, with respect to 617.9 parts by mass of the isocyanate group-terminated prepolymer A-1,
34.2 parts by mass of amino compound B-1
Carbon black (trade name, MA230; manufactured by Mitsubishi Chemical Corporation) 117.4 parts by mass, and
130.4 parts by mass of urethane resin fine particles (trade name, Art Pearl C-400; manufactured by Negami Kogyo Co., Ltd.)
Were stirred and mixed.

  Next, MEK was added so that the total solid content ratio was 30% by mass to prepare a coating material for forming a surface layer.

  Next, the rubber-free portion of the previously produced elastic roller D-2 was masked and stood vertically, and rotated at 1500 rpm, and the paint was applied while lowering the spray gun at 30 mm / s. Subsequently, the coating layer was cured and dried by heating at a temperature of 180 ° C. for 20 minutes in a hot air drying oven, whereby a surface layer having a film thickness of 8 μm was provided on the outer periphery of the elastic layer, thereby producing a toner carrier 10.

<Preparation of Toner Carriers 11-16>
A coating material for forming a surface layer was prepared in the same manner as the preparation of the toner carrier 10 except that the material shown in Table 8 below was used as the material for the surface layer 4. Then, each of the coating materials was applied to the elastic roller D-2 in the same manner as the preparation of the toner carrier 10, dried and heated to prepare toner carriers 11 to 17.

<Example 23>
A Canon printer LBP3100 was modified and used for image output evaluation. As a modification point, as shown in FIG. 4, the toner carrier 7 was modified so as to contact the electrostatic latent image carrier. The contact pressure was adjusted so that the width of the contact portion between the toner carrier and the electrostatic latent image carrier was 1.0 mm. Since there is no toner supply member, the toner on the toner carrier cannot be scraped off, which is a very strict evaluation condition for poor regulation. Further, since there is no toner supply member, the charge amount of the toner is also low, so that it is a severe condition for fogging in a high temperature and high humidity environment.

  The developing device thus modified was filled with 50 g of toner 1, and a developing device was produced using the toner carrier 10. Using the developed developing apparatus, 1500 images were output in a high temperature and high humidity environment (40 ° C./95% RH) and a low temperature and low humidity environment (15 ° C./10% RH). In addition, the image output test was performed by continuous paper passing using a horizontal line with a printing rate of 2% as an image.

  As a result, a clear image without fogging was obtained under a high temperature and high humidity environment, and a good image without fogging was obtained even under a low temperature and low humidity environment. Table 9 shows the evaluation results.

<Examples 24-29>
A developing device was produced by combining the toner and the toner carrier as shown in Table 9, and the image output of each developing device was evaluated in the same manner as in Example 23. As a result, in all developing apparatuses, good results were obtained both before and after the endurance test in the reverse fogging in the high temperature and high humidity environment and in the black post fogging in the low temperature and low humidity environment. Table 9 shows the evaluation results.

DESCRIPTION OF SYMBOLS 1 Toner carrier 2 Base body 3 Elastic layer 4 Surface layer 5 Electrostatic latent image carrier (photoreceptor)
6 Charging roller 7 Toner carrier 8 Toner supply member 9 Developing device 10 Transfer member (transfer roller)
DESCRIPTION OF SYMBOLS 11 Cleaner container 12 Cleaning blade 13 Fixing apparatus 14 Pickup roller 15 Transfer material (paper)
16 Laser generator 17 Restriction member 18 Metal plate 19 Toner 20 Stirring member 21 Magnet

Claims (10)

In a developing device for developing an electrostatic latent image formed on the surface of an electrostatic latent image carrier to form a toner image on the surface of the electrostatic latent image carrier,
The developing device is
Toner for developing the electrostatic latent image;
A toner carrier for carrying the toner, and
A regulating member for regulating the layer thickness of the toner carried on the toner carrier;
Have
The toner has toner particles and inorganic fine particles;
The toner particles are
Binder resin,
Magnetic material and
A polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group,
Containing
When the amount of carbon atoms present on the surface of the toner particles measured by X-ray photoelectron spectroscopy is A, and the amount of sulfur atoms present on the surface of the toner particles is E,
E is 0.09 atomic% or more and 0.37 atomic% or less,
E / A which is a ratio of E to A is 0.0010 or more and 0.0040 or less,
The toner carrier is
Substrate,
An elastic layer, and
Surface layer containing urethane resin,
Have
The urethane resin is
A compound represented by the following structural formula (1);
Polyisocyanate,
A developing device having a partial structure derived from the reaction of

(In structural formula (1),
n is an integer of 1 or more and 4 or less, each R ³ independently represents any one selected from the group consisting of the following (a) to (c):
(A) a hydroxyalkyl group having 2 to 8 carbon atoms,
(B) an aminoalkyl group having 2 to 8 carbon atoms,
(C) a group represented by the following structural formula (2),
R ⁴ represents an alkylene group having 2 to 4 carbon atoms. )

(In structural formula (2),
m is an integer of 2 to 3,
R ⁵ represents an alkylene group having 2 to 5 carbon atoms. ) The toner particles further contain an amorphous polyester resin, and
The toner particles have a core-shell structure having a core and a shell;
The shell
The amorphous polyester resin, and
A polymer or copolymer having the sulfonic acid group, sulfonic acid group or sulfonic acid ester group,
Containing
The developing device according to claim 1, wherein the acid value of the amorphous polyester resin is 0.1 mgKOH / g or more and 5.0 mgKOH / g or less. The amorphous polyester resin is a resin obtained by polycondensation of a polyhydric alcohol and a polycarboxylic acid,
3. The developing device according to claim 2, wherein 80 mol% or more of the polyhydric alcohol is a bisphenol A propylene oxide adduct having an average addition number of propylene oxide of 1.8 to 2.1.   The developing device according to claim 1, wherein the toner particles are toner particles manufactured in an aqueous medium. In a developing method for developing a latent electrostatic image formed on the surface of an electrostatic latent image carrier using a developing device to form a toner image on the surface of the electrostatic latent image carrier,
The developing device is
Toner for developing the electrostatic latent image;
A toner carrier for carrying the toner, and
A regulating member for regulating the layer thickness of the toner carried on the toner carrying body;
The toner has toner particles and inorganic fine particles;
The toner particles are
Binder resin,
Magnetic material and
A polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group,
Containing
When the amount of carbon atoms present on the surface of the toner particles is A and the amount of sulfur atoms present on the surface is E,
E is 0.09 atomic% or more and 0.37 atomic% or less,
E / A which is a ratio of E to A is 0.0010 or more and 0.0040 or less,
The toner carrier is
Substrate,
An elastic layer, and
Surface layer containing urethane resin,
Have
The urethane resin is
A compound represented by the following structural formula (1);
Polyisocyanate,
A developing method characterized by having a partial structure derived from the above reaction.

(In structural formula (1),
n is an integer of 1 or more and 4 or less, each R ³ independently represents any one selected from the group consisting of the following (a) to (c):
(A) a hydroxyalkyl group having 2 to 8 carbon atoms,
(B) an aminoalkyl group having 2 to 8 carbon atoms,
(C) a group represented by the following structural formula (2),
R ⁴ represents an alkylene group having 2 to 4 carbon atoms. )

(In structural formula (2),
m is an integer of 2 to 3,
R ⁵ represents an alkylene group having 2 to 5 carbon atoms. ) The toner particles further contain an amorphous polyester resin, and
The toner has a core-shell structure having a core and a shell;
The shell
The amorphous polyester resin, and
A polymer or copolymer having the sulfonic acid group, sulfonic acid group or sulfonic acid ester group,
Containing
The developing method according to claim 5, wherein the acid value of the polyester resin is 0.1 mgKOH / g or more and 5.0 mgKOH / g or less. The amorphous polyester resin is a resin obtained by polycondensation of a polyhydric alcohol and a polycarboxylic acid,
The developing method according to claim 6, wherein 80 mol% or more of the polyhydric alcohol is a bisphenol A propylene oxide adduct having an average addition number of propylene oxide of 1.8 to 2.1.   The developing method according to claim 5, wherein the toner particles are toner particles produced in an aqueous medium. Electrostatic latent image carrier,
An image exposure apparatus for forming an electrostatic latent image on the surface of the electrostatic latent image carrier; and
A developing device for developing the electrostatic latent image formed on the surface of the electrostatic latent image carrier;
In an image forming apparatus having
An image forming apparatus, wherein the developing device is the developing device according to claim 1. An image exposure process for forming an electrostatic latent image on the surface of the electrostatic latent image carrier; and
A developing step of developing the electrostatic latent image formed on the surface of the electrostatic latent image carrier;
In an image forming method having
An image forming method, wherein the developing step is performed by the developing method according to claim 5.