JP2003098724A - Toner and image forming method - Google Patents

Abstract

(57) [Summary] (with correction) [PROBLEMS] To provide a toner capable of reducing contamination of a multiplicity of charging rollers and contamination of a drum. SOLUTION: This toner is used for an image forming method including a photosensitive member, a photosensitive member charging unit, an electrostatic latent image information writing unit, a developing unit for visualizing the electrostatic latent image, a transfer unit, and a fixing unit. A charging means for arranging a developing blade for regulating the thickness of the toner layer so as to be in pressure contact with the surface of the toner carrier, uniformly applying the toner on the surface of the toner carrier, and bringing the toner carrier into contact with the photosensitive member; Is a charging roller having a conductive elastic layer, and the 10-point average surface roughness (Rz) of the charging roller is smaller than the circle-equivalent number average diameter D1 (μm) of the toner measured by the flow type particle image measuring device. The toner comprises toner particles containing a binder resin, a colorant and a release agent, and a hydrophobized inorganic fine powder;
The half-width of the SC endothermic peak is 14 ° C. or less.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, a magnetic recording method, a toner jet method, etc., and an image forming method using the toner. Is. In particular, it relates to a contact one-component toner and an image forming method thereof.

[0002]

2. Description of the Related Art There are many known electrophotographic methods. Generally, a photoconductive material is used to form an electric latent image on a photoreceptor by various means, and then an electric latent image is formed. The image is developed with toner to make it a visible image.If necessary, the toner image is transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material by heat or pressure to form a fixed image. I will get it. At this time, the toner remaining on the photoconductor without being transferred to the transfer material after the transfer is cleaned by various methods.

In recent years, a so-called contact one-component developing method has been proposed in which a semiconductive toner carrier or a toner carrier having a dielectric layer formed on the surface is used to press against a surface layer of a photoconductor to perform development. There is.

In the one-component developing method, when the photoconductor and the toner carrier are separated from each other, the lines of electric force are concentrated on the edge portion of the electrostatic latent image on the photoconductor, and the toner is developed along the lines of electric force. Therefore, the image quality is likely to deteriorate due to the edge effect in which the toner is unevenly developed at the edge portion of the image.

Although the edge effect is prevented by bringing the photoconductor and the toner carrier very close to each other, the gap between the photoconductor and the toner carrier is mechanically set, that is, the thickness of the toner layer on the toner carrier. It is difficult to set the gap smaller than that.

Therefore, the edge effect can be prevented by using the contact one-component developing method in which the toner bearing member is pressed against the photosensitive member to perform the development. However, if the toner carrier surface moving speed is the same as the photosensitive member surface moving speed, a satisfactory image cannot be obtained when the latent image on the photosensitive member is visualized. Therefore, in the contact one-component developing method, by giving a difference in the toner carrier surface moving speed with respect to the photosensitive member surface moving speed, a part of the toner on the toner carrier is removed from the latent image on the photosensitive member surface. It is developed and stripped of another portion of the toner resulting in a developed image without edge effects that is very true to the latent image.

In such a contact one-component developing method, since the surface of the photoconductor is rubbed with the toner and the toner carrier, it is used for a long period of time, especially in a severe environment such as high temperature high humidity or low temperature low humidity environment. In use, deterioration of toner, deterioration of the surface of the toner carrier, deterioration of the surface of the photosensitive member, or abrasion is remarkable, and thus this improvement method has been desired.

Further, as the charging means in the electrophotographic apparatus based on the electrophotographic method as described above, a means utilizing corona discharge has been used, but since a large amount of ozone is generated, a filter is provided. Therefore, there is a problem in that the size of the device is increased or the running cost is increased.

As a technique for solving such a problem, a charging member such as a roller or a blade is brought into contact with the surface of the photosensitive member to form a narrow space in the vicinity of the contact portion, which is interpreted by the so-called Paschen's law. A charging method has been developed in which ozone generation is suppressed as much as possible by forming such a discharge. Of these, a roller charging method using a charging roller as a charging member is particularly preferred from the viewpoint of charging stability. However, since resistance value fluctuations easily occur due to environmental fluctuations, it has been a problem to suppress contamination and deterioration of the charging roller in order to maintain image quality in continuous paper-pass printing.

Further, the current printer device is an LED,
LBP printer has become the mainstream of the market, and the direction of technology is higher resolution, namely 600dpi, 1200d.
It has become pi. Therefore, the developing system is also required to have higher definition. Copiers are also becoming more sophisticated, and as a result, they are moving toward digitalization. In the digital method, since a method of forming an electrostatic image with a laser is mainly used, the resolution is also becoming higher, and therefore, a high-resolution and high-definition developing method is required like the printer. .

For this reason, the toner particle size is being reduced,
JP-A-1-112253, JP-A-1-19115
6, JP-A-2-214156, JP-A-2-214156.
284158, JP-A-3-181952,
JP-A-4-162048 proposes a toner having a specific particle size distribution and a small particle size.

However, as the diameter of the toner is reduced, the adhesion force of the toner particles (image force, van der Waals force, etc.) to the photoconductor becomes larger than the Coulomb force applied to the toner particles by the transfer. As a result, the residual toner after transfer tends to increase, and the problems around the photosensitive drum such as fogging, drum fusion, and cleaning failure have been problems.

To solve these problems, Japanese Unexamined Patent Publication No. 2000-08
Japanese Patent Publication No. 9507 discloses a technique of adopting a simultaneous cleaning system for development and defining the polymerized toner and its deposits. Further, Japanese Unexamined Patent Publication No. 08-278673 discloses a technique of a toner containing an inorganic fine powder having a hydrophobicity regulation in a contact developing system.

However, in these prior arts, there is no detailed and clear description about the combination of the release agent and the relationship between the toner and the charging roller to exert the effects of the present invention.

[0015]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner and an image forming method which solve the above-mentioned problems even when a large number of sheets are continuously printed.

That is, an object of the present invention is to provide a toner and an image forming method capable of reducing the contamination of the charging roller and the contamination of the drum.

An object of the present invention is to provide a toner and an image forming method capable of obtaining an image with less fog under a high temperature and high humidity environment.

An object of the present invention is to provide a toner and an image forming method which do not cause drum fusion in a high temperature and high humidity environment.

An object of the present invention is to provide a toner and an image forming method capable of obtaining an image having good cleaning property and excellent image uniformity under a low temperature and low humidity environment.

[0020]

SUMMARY OF THE INVENTION The present invention is directed to a photoconductor, a charging unit for charging the surface of the photoconductor, an information writing unit for forming an electrostatic latent image on the charged photoconductor, and an electrostatic latent image. A toner used in an image forming method that includes a developing unit that supplies toner to visualize an electrostatic latent image, a transfer unit that transfers the visualized toner image to a transfer material, and a unit that fixes the toner image on the transfer material. The developing means is arranged such that a developing blade for controlling the layer thickness on the toner carrier is pressed against the surface of the toner carrier, and the toner is evenly applied to the surface of the toner carrier, and the toner carrier is applied to the photoreceptor. Are directly contacted with each other, wherein the charging means is a charging roller having a conductive elastic layer, and the toner in a number-based circle equivalent diameter-circularity scattergram measured by a flow type particle image measuring device. Equivalent number of yen The 10-point average surface roughness (Rz) of the charging roller is smaller than the average diameter D1 (μm), and the toner contains toner particles containing at least a binder resin, a colorant and a release agent. The present invention relates to a toner comprising a hydrophobized inorganic fine powder and having a half-value width at an endothermic peak of 14 ° C. or less in a differential thermal analysis (DSC) of the toner.

Further, according to the present invention, a photoconductor, a charging unit for charging the surface of the photoconductor, an information writing unit for forming an electrostatic latent image on the charged photoconductor, and a toner for supplying the electrostatic latent image with toner. In an image forming method having a developing means for visualizing an electrostatic latent image, a transfer means for transferring the visualized toner image onto a transfer material, and a means for fixing the toner image on the transfer material, at least the toner is formed. The toner is characterized by comprising toner particles containing a resin, a colorant and a release agent, and a hydrophobized inorganic fine powder, and having a half value width at the endothermic peak of differential thermal analysis (DSC) of the toner of 14 ° C. or less. The developing means arranges a developing blade for controlling the layer thickness on the toner carrier so as to be in pressure contact with the surface of the toner carrier, and evenly applies the toner to the surface of the toner carrier to directly attach the toner carrier to the photoconductor. Contact Wherein the charging means is a charging roller having a conductive elastic layer, and the number-based circle equivalent diameter measured by a flow-type particle image measuring device-the circularity equivalent number average of the toner in a circularity scattergram. Diameter D1 (μ
10-point average surface roughness (Rz) of the charging roller rather than m)
To a small image forming method.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION In a contact one-component developing method using a charging roller having a conductive elastic layer as described above,
If continuous printing is performed in a harsh environment, even if a method with a cleaning mechanism is used, the toner will slip through slightly and the toner will adhere to the photoconductor and charging roller, and eventually the functional members will become stronger. However, the image quality is deteriorated due to a decrease in the sensitivity of the photoconductor and a change in the resistance value of the charging roller.

On the other hand, as a result of intensive studies by the present inventors, in the contact one-component developing method, there is a half-value width at an endothermic peak of a toner containing a releasing agent in a differential thermal analysis (DSC). Within the range, the hydrophobic inorganic fine powder is used as an essential component of the toner, and the number-based circle equivalent diameter-circularity scattergram of the number-based circle average diameter D1 measured by a flow-type particle image measuring device is D1. (Μm) and the surface roughness (Rz) of the charging roller have been focused on and the study has been advanced.

In continuous paper feeding by a contact one-component developing method using a charging roller having a conductive elastic layer in a harsh environment, toner is slightly attached to the charging roller and damaged, thereby contaminating the surface of the charging roller. In addition to this, the toner shape is deformed or damaged, and as a result, the toner cannot be sufficiently collected by the cleaning member, and the toner remains on the photoconductor.

Further, when printing is continuously performed, the toner or the deformation of the toner, which has passed through the cleaning member, firmly adheres to the photosensitive member and the charging roller, and prevents the basic characteristics of each member from being exhibited.

The inventors of the present invention have conducted a study based on the above-mentioned point of view. As a result, in the contact one-component method, the toner containing a release agent has a half-value width of 14 ° C. or less, and a hydrophobic inorganic fine powder is used as a toner. It has been found that conventional problems can be greatly improved under the condition that the average surface roughness (Rz) of the charging roller is smaller than the average equivalent circle diameter D1 (μm) of the toner as an essential component. It was

The reason is considered as follows.

When printing is performed in a harsh environment, a small amount of toner is deformed or broken in shape as the number of printed sheets increases. The toner surface is richer in the release agent than that at the beginning of printing.

The release agent is a substance added for the effect of releasing the heating roller and the toner layer at the time of fixing an unfixed image, but on the other hand, it has a characteristic that it easily adheres to the surface of each member. I also have From this, it is assumed that the toner having a large amount of the surface release agent is likely to adhere to the photoconductor or the charging roller via the release agent. In a high-temperature and high-humidity environment, as the number of printed sheets increases, the temperature inside the machine also increases, so the above-mentioned adhesion is further accelerated.

On the other hand, reducing the full width at half maximum of the toner containing the release agent as in the present invention is synonymous with reducing the full width at half maximum of the release agent. The crystallinity of the release agent is promoted by increasing the purity and the crystallinity accordingly. By doing so, the hardness of the release agent itself is increased, and the release agent abundance ratio on the toner surface becomes
Even if the toner is damaged due to some influence and becomes a toner rich in the release agent, it is considered that the contamination of the photoconductor and the charging roller can be suppressed.

Further, by making the average surface roughness of the charging roller according to the present invention smaller than the equivalent circle number average diameter D1 (μm) of the toner in this system, a substance derived from the toner which is damaged in continuous sheet-pass printing. It greatly suppresses the entry and accumulation in the concave portion of the charging roller, and significantly reduces the contamination of the charging roller.

This suppresses the contamination of the photoconductor when the number of printed sheets is increased, further enhances the above-mentioned function and effect, and in the developing and collecting system, good fog, no fusion, and uniformity. We believe that we will make good images available.

Next, the toner of the present invention will be described.

The binder resin of the toner used when the toner of the present invention is manufactured by a pulverizing method is polystyrene;
Styrene-substituted homopolymers such as poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylic acid esters Copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, Styrene-based copolymers such as styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer; acrylic resin, methacrylic resin, polyvinyl acetate, silicone Resin, polys Le resins, polyamide resins, furan resins, epoxy resins, xylene resins.

These resins are used alone or as a mixture.

As the main component of the binder resin, a styrene copolymer which is a copolymer of styrene and another vinyl monomer is preferable from the viewpoints of developability and fixability.

Comonomers for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodite acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid. Acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, monocarboxylic acid having a double bond such as acrylamide or a substitution product thereof; maleic acid,
Dicarboxylic acids having a double bond such as butyl maleate, methyl maleate and dimethyl maleate and substituted products thereof; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; ethylene such as ethylene, propylene and butylene. Examples include olefins; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether. These vinyl monomers are used alone or in combination of two or more.

It is preferable that the styrene copolymer is crosslinked with a crosslinking agent such as divinylbenzene in order to widen the fixing temperature range of the toner and improve the offset resistance.

As the polymerizable monomer used when the toner of the present invention is produced by a polymerization method, a vinyl-based polymerizable monomer capable of radical polymerization is used. As the vinyl-based polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. As the monofunctional polymerizable monomer, styrene; α-methylstyrene, β
-Methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn -Styrene derivatives such as 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, te
rt-butyl acrylate, n-amyl acrylate,
n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate,
Acrylic polymerizable monomers such as 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,
Methacrylic polymerizable monomers such as 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid ester; vinyl acetate, vinyl propionate Vinyl esters such as vinyl butyrate, vinyl benzoate and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

As the polyfunctional polymerizable monomer, 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- (acryloxydiethoxy) 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- (methacryloxydiethoxy) phenyl) propane, 2,
2'-bis (4- (methacryloxy polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like can be mentioned.

In the present invention, the above monofunctional polymerizable monomers may be used alone or in combination of two or more kinds, or
The monofunctional polymerizable monomer and the polyfunctional polymerizable monomer described above are used in combination. The polyfunctional polymerizable monomer can also be used as a crosslinking agent.

An oil-soluble initiator and / or a water-soluble initiator is used as a polymerization initiator used in the polymerization of the above-mentioned polymerizable monomer. For example, as the oil-soluble initiator, 2,2'-azobisisobutyronitrile, 2,2 '
-Azobis-2,4-dimethylvaleronitrile, 1,
Azo compounds such as 1'-azobis (cyclohexane-1-carbonitrile) and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropylperoxycarbonate, decanoylperoxide oxide,
Lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, Examples thereof include peroxide-based initiators such as dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide and cumene hydroperoxide.

As the water-soluble initiator, ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-
Dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloride, azobis (isobutylamidine) hydrochloride, 2,2′-azobisisobutyronitrile sodium sulfonate, sulfuric acid Examples include ferrous iron or hydrogen peroxide.

In the present invention, in order to control the degree of polymerization of the polymerizable monomer, it is possible to further add and use a chain transfer agent, a polymerization inhibitor or the like.

As the crosslinking agent used in the toner of the present invention, a compound having two or more polymerizable double bonds is used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and 1,3-butanediol dimethacrylate; divinylaniline; And divinyl compounds such as divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having 3 or more vinyl groups. These are used alone or as a mixture.

As the release agent used in the toner of the present invention, candelilla wax, carnauba wax, rice wax, wood wax, plant wax such as jojoba oil,
Animal waxes such as beeswax, lanolin and whale wax, mineral waxes such as montan wax, ozokerite and ceresin, paraffin wax, microcrystalline wax, petroleum waxes such as petrolatum, polyolefin waxes, synthetic hydrocarbons such as Fischer-Tropish wax. , Amide wax, ketone wax,
Examples thereof include ester wax, higher fatty acid, higher fatty acid metal salt, and long chain alkyl alcohol. If necessary, these may be grafted, blocked, distilled, or the like.

In order to exert the above effects, carnauba wax, rice wax, montan wax, paraffin wax, microcrystalline wax, polyolefin wax, Fischer-Tropsch wax, ester wax, amide wax and ketone wax are preferable, and more preferable. Carnauba wax,
Rice wax, paraffin wax, polyolefin wax, Fischer-Tropsch wax, ester wax, amide wax, and ketone wax are desired.

Examples of ester wax, amide wax, and ketone wax are shown below, but other waxes may be used.

[0049]

[Chemical 1] (In the formula, a and b are integers from 0 to 4, and a + b is 4. R1 and R2 are organic groups having 1 to 40 carbon atoms, and the difference in carbon number between R ₁ and R ₂ is 3 or more, m and n are integers from 0 to 40, and m and n cannot be 0 at the same time)

[0050]

[Chemical 2] (In the formula, a and b are integers from 0 to 3, and a + b is 1
Through 3. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms, and the difference in carbon number between R ₁ and R ₂ is 3 or more. R ₃
Is a hydrogen atom or an organic group having 1 or more carbon atoms. However, a
When + b = 2, one of R ₃ is an organic group having 1 or more carbon atoms. k is an integer of 1 to 3. (m and n are integers from 0 to 40, and m and n cannot be 0 at the same time)

[0051]

[Chemical 3] (In the formula, R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms, and R ₁ and R ₃ may or may not be the same.
R ₂ represents an organic group having 1 to 40 carbon atoms)

[0052]

[Chemical 4] (In the formula, R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms, and R ₁ and R ₃ may or may not be the same.)

[0053]

[Chemical 5]

Or — (CH ₂ ) _n —. m is 1 to 2
An integer of 0 and n are integers of 1 to 40. )

[0055]

[Chemical 6] (In the formula, a is an integer of 0 to 4, b is an integer of 1 to 4, and a + b is 4. R ₁ is a carbon number of 1 to 40.
Is an organic group having. (m and n are integers from 0 to 40, and m and n cannot be 0 at the same time)

As the amide wax, the following formula (VI) is used.
The one formed from the compound represented by

[0057]

[Chemical 7] (In the formula, R ₁ and R ₂ are organic groups having 1 to 45 carbon atoms, R ₁ and R ₂ may or may not be the same, and R ₁ and R ₂ are unsaturated groups. May have.)

As the ketone wax, the following formula (VII)
The one formed from the compound represented by

[0059]

[Chemical 8] (In the formula, R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms.)

The full width at half maximum of the toner containing the releasing agent is A
It is measured according to STM D3418-82. It is preferably 14 ° C or lower, more preferably 7 ° C.
℃ or less is good. More preferably, the temperature is 5 ° C or lower.

Above 14 ° C., the crystallinity is not so high that the releasing agent has a soft hardness. In the contact one-component developing system of the present invention, the functional members, especially the charging roller and the photosensitive member, are not affected. Contamination occurs remarkably when continuous paper feeding is performed.

The half width of the endothermic peak here is the temperature width of the endothermic chart which is half the height of the peak from the baseline at the endothermic peak.

The endothermic peak value in the DSC endothermic curve of the release agent of the present invention is measured according to ASTM D3418-82. The release agent is extracted from the toner by an arbitrary method, and the sample is analyzed.

And more preferably 50 to 120 ° C.
A compound having a value of (60 to 100 ° C.) is more preferable, and a releasing agent having a DSC curve tangential desorption temperature of 40 ° C. or higher is particularly preferable.

When the endothermic peak value is less than 50 ° C., the self-aggregating force of the release agent is weak, so that it is difficult to form the inside or center of the toner particles, and the release agent is formed on the surface of the toner particles during the production of the toner particles. Is present more than necessary, and in the contact one-component developing system as in the present case, the charging roller and the photoconductor are easily contaminated.

Also, since the blocking resistance is poor, toner packing is likely to occur in the developing machine during continuous paper feeding.

On the other hand, when the endothermic peak exceeds 120 ° C.,
It is difficult for the release agent to ooze out instantly during fixing, and the secondary colors (red, green,
The fixing property of (blue) deteriorates. Furthermore, when the toner particles are produced by the direct polymerization method, the solubility in the polymerizable monomer composition is lowered, and the polymerizable monomer composition in the aqueous medium has a particle size of the toner particle size. In addition to the difficulty of granulation due to the release agent being deposited during the granulation of droplets, the amount of deposits on the reaction kettle also increases.

The release agent preferably has a weight average molecular weight (Mw) of 300 to 1,500.

When it is less than 300, the release agent is apt to be exposed on the surface of the toner particles, and in the contact one-component developing system of the present invention, the developing property is deteriorated and the fog in a high temperature and high humidity environment is poor. Also, the contamination of the charging roller is significant.

When it exceeds 1500, the low temperature fixing property is deteriorated and the OHT transparency and haze are deteriorated when a full color image is output. Especially 400 to 1,250
The range of is preferable.

The molecular weight of the release agent is measured by GPC under the following conditions.

(GPC measurement conditions) Apparatus: GPC-150C (manufactured by Waters) Column: GMH-MT 30 cm 2 series (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (addition of 0.1% ionol) Flow rate: 1 0.0 ml / min sample: A 0.15% sample is measured under the condition of 0.4 ml injection or more, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used for calculating the molecular weight of the sample. Further, it is calculated by performing polyethylene conversion using a conversion formula derived from the Mark-Houwink viscosity formula.

The penetration of the release agent is measured according to JIS K2235. The measurement temperature is 25 ° C. The penetration of the release agent is preferably 15 degrees or less, more preferably 8 degrees or less. More preferably, it is 4 degrees or less.

When it exceeds 15 degrees, as in the case where the full width at half maximum of the toner containing the release agent exceeds 14 ° C., in the contact one-component developing system of the present invention, the contamination of each functional member is promoted. And the developing characteristics are deteriorated.

The acid value, saponification value, hydroxyl value and iodine value of the release agent were measured by the method according to the wax analysis method described in the standard oil and fat analysis method.

The acid value is desired to be 40 or less, more preferably 20 or less, still more preferably 10 or less. The saponification value is preferably 30 to 350, more preferably 50 to 250, and further preferably 70 to 150. The hydroxyl value is 50 or less, more preferably 30 or less,
More preferably, 15 or less is desired. Iodine value is 3
0 or less, more preferably 20 or less, further preferably 1
0 or less is desired.

When the acid value exceeds 40 and the hydroxyl value exceeds 50,
In a high temperature and high humidity environment, the charging property deteriorates, resulting in poor fog and in-machine scattering.

When the iodine value is less than 30, the charging property of the toner is deteriorated, the coatability on the developing roller is deteriorated, and development streaks and the like are remarkably generated.

When the saponification value is less than 30, impurities such as unsaponifiables are present, and the functional members are contaminated particularly in a low temperature and low humidity environment, and the image uniformity is deteriorated. When it exceeds 350, the charging characteristics in a high temperature and high humidity environment are deteriorated, and fog and scattering in the machine deteriorate.

When the toner particles are produced by the melt-kneading and pulverization method, 1 part of the releasing agent is added to 100 parts by weight of the binder resin.
It is preferable to use 10 to 10 parts by mass.

When the polymerizable monomer composition is used to directly produce the toner particles in an aqueous medium, the amount of the polymerizable monomer composition is 5 to 40 parts by mass (more preferably 100 parts by mass). Is 5 to 35 parts by mass, and as a result, 5 to 40 parts by mass (more preferably 5 to 35 parts by mass) of a release agent per 100 parts by mass of a binder resin produced from a polymerizable monomer. It is better to be contained in particles.

Compared with the dry toner manufacturing method by the melt-kneading and pulverization method, in the toner manufacturing method by the polymerization method, since a large amount of the release agent is easily included in the toner particles by the polar resin, it is generally larger than the dry toner manufacturing method. It becomes possible to use a mold agent, which is particularly effective for the offset prevention effect during fixing.

Examples of the colorant used in the toner of the present invention will be given, but other colorants may be used.

As the black colorant, carbon black,
A magnetic material, which is toned in black with the following yellow / magenta / cyan colorant, is used.

As the yellow colorant, as a pigment system, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 3.7.1
0.12.13.14.15.17.13.23.24.6
0.62.74.75. 83.93.94.95.9
9.100.101.104.108.109.11.
0. 111.117.123.128.129.13
8.139.147.148.150.166.16
8.169.177.179.180.181.18
3.185.1911: 1.191.192.193.1
99 and the like are preferably used. As the dye system, for example,
C. I. solvent Yellow 33.56.
79.82.93.112.162.163, C.I.
I. disperse Yellow 42.64.20
1.211 etc. are mentioned.

As the magenta coloring agent, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8; 2, 48; 3, 48; 4, 57; 1, 81; 1, 1
22, 146, 166, 169, 177, 184, 18
5, 202, 206, 220, 221, 254, C.I.
I. Pigment Violet 19 is particularly preferable.

As cyan colorants, phthalocyanine compounds and their derivatives, anthraquinone compounds, basic dye lake compounds, etc. can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 1
5: 3, 15: 4, 60, 62, 66 and the like are particularly preferably used.

These colorants may be used alone or in combination, or in the state of solid solution. The colorant of the present invention is selected in terms of hue angle, saturation, lightness, weather resistance, OHP transparency, and dispersibility in toner. The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the resin.

The toner of the present invention may be used together with a charge control agent.

The following substances control the toner to be negatively charged. One example is given, but other than these may be used.

For example, organic metal compounds and chelate compounds are effective, and there are monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acid type metal compounds. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. Further, a urea derivative, a metal-containing salicylic acid-based compound, a metal-containing naphthoic acid-based compound, a boron compound, a quaternary ammonium salt, a calixarene, a resin-based charge control agent and the like can be mentioned.

The following substances control the toner to be positively charged. One example is given, but other than these may be used.

Nigrosine modified products of nigrosine and fatty acid metal salts, guanidine compounds, imidazole compounds, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate,
And onium salts such as phosphonium salts which are analogs thereof, lake pigments thereof, triphenylmethane dyes and lake pigments thereof (as a laker, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid) , Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids; dibutyltin oxide, dioctyltin oxide, diorganotin oxides such as dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin borate. Examples thereof include diorgano tin borates, resin type charge control agents and the like. These can be used alone or in combination of two or more.

The charge control agent is 0.01 to 20 parts by mass, more preferably 0.5 to 1 part by mass per 100 parts by mass of the binder resin.
It is recommended to use 0 part by mass.

When the toner of the present invention is a polymerized toner, a condensation resin may be added. One example is given, but other than these may be used.

Examples of the condensed resin of the present invention include polyester, polycarbonate, phenol resin, epoxy resin, polyamide and cellulose. More preferably, polyester is desired due to the variety of materials. It is preferable to use 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass per 100 parts by mass of the binder resin.

In the present invention, the hydrophobized inorganic fine powder is used as an external additive for the toner.

The hydrophobic degree of the hydrophobized inorganic fine powder is 70%.
Or more, more preferably 90% or more, and further preferably 95
% Or more is preferable.

If it is less than 70%, moisture is often adsorbed during continuous paper-passing printing in a high temperature and high humidity environment, and charging is not sufficiently imparted, resulting in many fog problems.

For the degree of hydrophobicity of the fine powder as an external additive in the present invention, the value measured by the following method is used.

The external additive may be separated by either a dry method or a wet method, but a dry method is preferable.

The dry separation method is carried out, for example, by using a toner of 40
After passing through a vibrating sieve several times with 0 mesh (opening 37 micron), the external additive is collected from the mesh.

100 ml of ion-exchanged water and 0.1 g of an external additive were put into a 200 ml separating funnel of a sealed stopper type, and the mixture was stirred at 90 rpm with a shaker (Turbra shaker mixer T2C type).
Shake for 10 minutes under the above conditions. After shaking, the mixture was allowed to stand for 10 minutes to separate the inorganic powder layer and the aqueous layer, and then the lower aqueous layer was added to 20
〜30ml is sampled, put in a 10mm cell, and the transmittance is measured at the wavelength of 500nm with reference to the blank ion-exchanged water without the fine powder. The value of the transmittance is used as the hydrophobicity of the inorganic fine powder. is there. The higher the transmittance,
The degree of hydrophobicity is high.

In the present invention, the external additive is toner particles 1
It is preferably used by mixing with 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass with respect to 100 parts by mass of the toner particles.

When the amount of the external additive added is less than 0.1 parts by mass, the fluidity imparting ability to the toner particles is not sufficient, and when it exceeds 5 parts by mass, the external additive liberated from the toner particles is used. However, the functional members are contaminated, and the image is adversely affected. Further, the fixability, especially the fixability in the halftone is significantly deteriorated.

The inorganic fine powder of the present invention comprises titanium oxide (anatase type, rutile type, non-crystalline), aluminum oxide,
Metal acid compounds such as strontium titanate, cerium oxide and magnesium oxide; nitrides such as silicon nitride; carbides such as silicon carbide; metal salts such as calcium sulfate, barium sulfate and calcium carbonate; carbon fluoride, fine powder of silicon compound ( Silica fine powder, silicone resin fine powder) and the like. Preferably, titanium oxide (anatase type, rutile type, non-crystalline), aluminum oxide,
Silicon compound fine powder, more preferably titanium oxide (anatase type, rutile type, non-crystalline), silicon compound fine powder is desired.

Examples of the method for producing titanium oxide include a method in which a titanium halogen compound or a titanium alkoxide is vapor-phase oxidized. Examples of the method for producing fine silica powder include vapor phase oxidation of a silicon halogen compound and a sol-gel method.

As a method for hydrophobizing the inorganic fine powder, either a wet method or a dry method may be used.

Examples of the hydrophobizing agent include silane coupling agents, titanium coupling agents, aluminate coupling agents, zirco aluminum coupling agents, and silicone oil.

Metal oxide compounds such as titanium oxide (anatase type, rutile type, non-crystalline), aluminum oxide, strontium titanate, cerium oxide, magnesium oxide; nitrides such as silicon nitride; carbides such as silicon carbide; calcium sulfate. , Metal salts such as barium sulfate and calcium carbonate; and silane coupling agents are particularly preferably used for those such as carbon fluoride.

General formula Rm SiYn [wherein, R represents an alkoxy group, Y represents an alkyl group,
A hydrocarbon group such as a vinyl group, a glycidoxy group, and a methacryl group is shown, m is an integer of 1 to 3, and n is an integer of 1 to 3. ] The thing represented by this is mentioned.

Among the silane coupling agents, monoalkyltoalkoxysilane coupling agents are particularly preferable. Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane and ethyl. Triethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltriethoxysilane Methoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, n-butylt Silane, include n- octyl trimethoxysilane.

Further, for hydrophobizing the silicon compound fine powder,
Silane coupling agents and silicone oils are preferred as the hydrophobizing agents. As the silane coupling agent, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyl Dimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane,
Examples thereof include dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, and 1,3-diphenyltetramethyldisiloxane.

A nitrogen-containing silane coupling agent may be used in order to impart a positive triboelectric charging property to the hydrophobized silicon compound fine powder. As the nitrogen-containing silane coupling agent, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane,
Monobutylaminopropyltrimethoxysilane, dioctylaminopropyltrimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltriethoxysilane, trimethoxysilyl-γ-propylphenylamine, trimethoxysilyl-γ -Propylbenzylamine and the like.

Examples of the silicone oil include those represented by the following formula.

[0116]

[Chemical 9] [In the formula, R represents a C1-3 alkyl group, R'represents a silicone oil-modified group such as alkyl, halogen-modified alkyl, phenyl, and modified phenyl, and R "represents C1-C1.
3 represents an alkyl group or an alkoxy group. ]

Examples thereof include dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil. The silicone oil has a viscosity at 25 ° C. of 50 to 100 mm ²
/ S (centistokes) is preferably used.

A nitrogen-containing silicone oil may be used for imparting hydrophobicity and positive triboelectric charging properties to the hydrophobized silicon compound fine powder.

As the silicone oil having a nitrogen atom in the side chain, a silicone oil having at least a partial structure represented by the following formula can be used.

[0120]

[Chemical 10] (In the formula, R ₁ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R 2 represents an alkylene group or a phenylene group, R ₃ and R ₄ represent hydrogen, an alkyl group or an aryl group, and R ₅ represents Indicates a nitrogen-containing heterocyclic group.)

The above-mentioned alkyl group, aryl group, alkylene group and phenylene group may have an organo group having a nitrogen atom, or have a substituent such as halogen within a range not impairing the charging property. May be.

As a method for treating the inorganic fine powder with silicone oil, a known technique is used.

For example, the inorganic fine powder and the silicone oil may be directly mixed by using a mixer such as a Henschel mixer, or the inorganic fine powder may be sprayed with the silicone oil. Alternatively, it may be produced by dissolving or dispersing silicone oil in an appropriate solvent, mixing with the inorganic fine powder, and then removing the solvent.

In the toner of the present invention, in addition to the inorganic powder of the present invention, the following publicly known powder may be used in combination for the purpose of improving charging stability, developability, fluidity and durability. preferable. More preferably, the volume average diameter of the toner particles is 1
It is desired that the particle size be / 2 or less.

From the viewpoint of durability, it is preferable that the additive for the purpose of improving various characteristics of the toner has a particle diameter of 1/2 or less of the volume average diameter of the toner particles.

The particle size of the additive means the average particle size of the toner particles obtained by observing the surface of the toner particles with an electron microscope. As the additives for imparting these characteristics, for example, the following ones are used. One example is given, but other than these may be used.

Fluorine-based resin powders (vinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.), metal oxides (tin oxide, zinc oxide, etc.), carbon black and the like. .

These additives are used in an amount of 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the toner particles.

These additives may be used alone or
You may use together two or more. Further, a hydrophobic treatment (oil, coupling) may be performed if necessary.

The toner manufacturing method of the present invention will be described below.

When the toner of the present invention is a pulverized toner, at least a binder resin and a colorant are kneaded and uniformly dispersed by using a pressure kneader, an extruder, a media disperser or the like, A method for producing toner particles by mechanically or by colliding with a target under a jet stream to finely pulverize to a desired toner particle size, and further through a classifying step to obtain a desired circularity using mechanical means. Or
There is a method of performing a wet or dry thermal spheroidizing treatment after the above pulverization.

When the toner of the present invention is a polymerization method,
Although not particularly limited, the Japanese Patent Publication No. 36-102
31, JP-A-59-53856, JP-A-5-
A method of directly producing a toner by using the suspension polymerization method described in JP-A 9-61842; a monomer is soluble in a monomer and is directly polymerized in the presence of a water-soluble polymerization initiator to produce toner particles. Production of toner particles by an emulsion polymerization method typified by a soap-free polymerization method can be mentioned. In addition, an interfacial polymerization method such as a microcapsule manufacturing method, an in-situ polymerization method,
The production of the coacervation method and the like is also included. Furthermore, JP-A-62-106473 and JP-A-63-1
As disclosed in Japanese Patent No. 86253, at least 1
An interface association method for aggregating at least one kind of fine particles to obtain particles having a desired particle size is also included.

The suspension polymerization method is particularly preferable because it allows toner particles having a small particle diameter to be easily obtained. Further, a seed polymerization method in which a monomer is further adsorbed on the obtained polymer particles and then the resultant is polymerized using a polymerization initiator can also be suitably used in the present invention. At this time, it is also possible to disperse or dissolve the polar compound in the adsorbed monomer.

In the case of suspension polymerization, it is usually preferable to use 300 to 3000 parts by mass of water as a dispersion medium with respect to 100 parts by mass of the monomer composition. As the dispersant used, for example, as an inorganic oxide, tricalcium phosphate,
Magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina, sodium dodecyl sulfate, etc. Is mentioned. As the organic compound, for example, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like are used. These dispersants or dispersion aids are preferably used in an amount of 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer. In order to make these dispersants finer, 0.001 to 0.1% by mass of a surfactant may be used in combination. Specifically, commercially available nonionic, anionic and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like are preferably used.

The number-based circle-equivalent diameter-circularity measured by the toner flow-type particle image measuring device of the present invention has an average circularity of 0.950 to 0.999 in the scattergram.
Is preferred. More preferable average circularity and standard deviation of circularity are 0.950 to 0.999 and preferably less than 0.040, and more preferably 0.950 to 0.9.
95, preferably 0.015 or more and less than 0.035, and more preferably 0.970 to 0.99.
5 and 0.015 to 0.035 are preferable.

When the average circularity is less than 0.950,
Deterioration of the toner shape causes remarkable deterioration of the toner transfer efficiency during continuous sheet feeding, and a large amount of transfer residual toner remains on the photoconductor, which easily causes drum fusion under high temperature and high humidity.

If the average circularity exceeds 0.999, reproducibility and yield are significantly deteriorated in terms of manufacturing, leading to an increase in cost.

When the standard deviation of circularity exceeds 0.04, the toner shape distribution is widened and uniform transfer cannot be performed, and the same phenomenon as in the case where the average circularity is less than 0.950 occurs.

The mass X (mg / g) of the oxycarboxylic acid extracted from 0.1 g of the toner with a 0.1 mol / liter sodium hydroxide aqueous solution is X = 0.10 to 2.
0.0 mg / g (based on the mass of the toner) is preferable, and 0.20 to 5.0 mg / g is more preferable.

When the amount is less than 0.10 mg / g, the background fog under high temperature and high humidity is increased, and the scattering in the machine is deteriorated accordingly. If it exceeds 20.0 mg / g, the fixability of a halftone image deteriorates. In particular, the fixability of secondary colors (red, green, blue) is poor.

The oxycarboxylic acid according to the present invention includes
Although known compounds can be used, compounds represented by the following formulas (1) and (2) are preferably used from the viewpoint of charge imparting ability.

[0142]

[Chemical 11] [In the above formula (1), (A) is selected from the following group and X ₁
Represents a hydrogen atom, a sodium atom, a potassium atom, ammonium or an aliphatic ammonium. ]

[0143]

[Chemical 12]

[0144]

[Chemical 13] [In the above formula (2), X ₂ represents a hydrogen atom, a sodium atom, a potassium atom, ammonium, or an aliphatic ammonium, and R ₄ represents a C _{1 to} C ₂₂ alkyl group, an alkenyl group, or an aryl group. , R ₅ is a hydrogen atom, C 1 to
The C ₂₂ alkyl group, alkenyl group, aryl group or alkoxy group is shown. ]

Among the oxycarboxylic acids represented by the above formulas (1) and (2), those preferably used in the present invention are oxycarboxylic acids having an aromatic ring,
Examples thereof include monoalkyl aromatic oxycarboxylic acid and dialkyl aromatic oxycarboxylic acid. In particular, alkylsalicylic acid represented by salicylic acid, ditert-butylsalicylic acid and 5-tert-octylsalicylic acid, hydroxynaphthoic acid, benzylic acid and the like are preferably used in the present invention.

[0146]

[Chemical 14]

[0147]

[Chemical 15]

[0148]

[Chemical 16]

[0149]

[Chemical 17]

[0150]

[Chemical 18]

In the present invention, from the toner, 0.1 mo
A conventionally known analysis method can be used for the amount X of oxycarboxylic acid extracted with a 1 / liter sodium hydroxide aqueous solution. A specific example will be described below.

50 ml of 0.1 mol / liter sodium hydroxide aqueous solution containing 0.04 g of Contaminone N (manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersant was prepared in separate containers, and 1 g of toner was contained in each container. Weigh and add, stir at 50 rpm using a stirrer, and disperse uniformly. After dispersion treatment for 3 hours, it was filtered using a membrane filter (pore size: 0.45 μm), and the absorption spectrum of the obtained filtrate was measured by a spectrophotometer to find the maximum value of the maximum absorption peak of oxycarboxylic acid. And the difference from the baseline. From the obtained results, the amount X of oxycarboxylic acid in the toner was calculated using a predetermined calibration curve. The absorption spectrum of oxycarboxylic acid is, for example, 28
It appears in the range of 0 to 350 nm.

The equivalent circle diameter, the circularity, and their frequency distribution of the toner in the present invention are used as a simple method for quantitatively expressing the shape of toner particles. In the present invention, the flow type particle image is used. It measured using the measuring device FPIA-1000 type (made by Toa Medical Electronics Co., Ltd.), and calculated using the following formula.

[0154]

[Equation 1]

Here, the "particle projection area" is the area of the binarized toner particle image, and the "perimeter of the particle projection image".
Is defined as the length of the contour line obtained by connecting the edge points of the toner particle image.

The circularity in the present invention is an index showing the degree of unevenness of the toner particles, and shows 1.000 when the toner particles are perfectly spherical, and the more complicated the surface shape, the more
The circularity has a small value.

In the present invention, a circle-equivalent number average diameter D1 (μ
m) and the particle size standard deviation SDd are calculated from the following equations, where di is the particle size (center value) at the dividing point i of the particle size distribution and fi is the frequency.

[0158]

[Equation 2]

[0159]

[0160]

[0161]

[Equation 3]

As a specific measuring method, 10 ml of ion-exchanged water from which impure solids and the like have been removed beforehand is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant into the container. Then, 0.02 g of a measurement sample is further added and uniformly dispersed. As a dispersing means, an ultrasonic dispersing machine UH-50 type (manufactured by SMT) equipped with a titanium alloy chip of 5φ as a vibrator is used, and dispersion treatment is performed for 5 minutes to obtain a dispersion liquid for measurement.
At that time, the dispersion liquid is appropriately cooled so that the temperature of the dispersion liquid does not exceed 40 ° C.

To measure the shape of the toner particles, a flow type particle image measuring apparatus "FPIA-1000" (manufactured by Toa Medical Electronics Co., Ltd.) was used, and the toner particle concentration at the time of measurement was 3000 to 10,000 particles / μl. Then, the concentration of the dispersion liquid is readjusted and 1,000 or more toner particles are measured. After the measurement, the equivalent circle diameter of the toner particles, the circularity frequency distribution, and the like are obtained using this data.

The toner of the present invention has an aggregation degree of 1 to 40.
%, More preferably 3 to 30%, even more preferably 5
It is preferably in the range of 25% to 25% in order to bring out the effect of the present invention. When the toner cohesion is small, the fluidity of the toner is high, and when the cohesion is large, the fluidity of the toner is low. The aggregation degree of the toner is measured by the following method.

A powder tester (manufactured by Hosokawa Micron Corp.) was used, and 400 mesh, 20
4 meshes of 0 mesh and 100 mesh so that they overlap with each other in ascending order of mesh openings, that is, 100 mesh is the highest rank.
The sieves of 00 mesh, 200 mesh, and 100 mesh are piled up in this order and set. This set 100 mesh
The sample was added on the sieve of No. 5, the input voltage to the shaking table was set to 15 V, the amplitude of the shaking table at that time was adjusted to fall within the range of 60 to 90 μm, and vibration was applied for about 15 seconds, and then,
The mass of the sample remaining on each sieve is measured, and the aggregation degree is obtained based on the following formula. The smaller the value of the aggregation degree, the higher the fluidity of the toner.

[0166]

[Equation 4]

When the toner molecular weight of the present invention is less than 10,000, as compared with the one in the optimum range, the external additive on the surface of the toner particles is likely to be buried due to the durability in continuous paper feeding, and the transferability is likely to be deteriorated. . Furthermore, the high temperature offset resistance is also poor. When the weight average molecular weight is more than 1500000, the low temperature offset is weak, and the fixability of the secondary color of thick paper is particularly weak.

The molecular weight and molecular weight distribution of the toner are measured by the following methods.

The column was stabilized in a heat chamber at 40 ° C., and the column at this temperature was charged with THF as a solvent.
(Tetrahydrofuran) at a flow rate of 1 ml per minute,
About 100 μl of the THF sample solution is injected for measurement. When measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples.
As a standard polystyrene sample for preparing a calibration curve, for example, a molecular weight of 10 by Tosoh or Showa Denko is used.
^It is suitable to use a standard polystyrene sample of at least about 10 points by using one having a weight of about ² to 10 ⁷ . An RI (refractive index) detector is used as the detector. As a column,
It is better to combine a plurality of commercially available polystyrene gel columns, for example, Shodex GP manufactured by Showa Denko KK
CKF-801, 802, 803, 804, 805
Combination of 806, 807, 800P, TSKgel G1000H (H _XL ), G2000H manufactured by Tosoh Corporation
(H _XL ), G3000H (H _XL ), G4000H
(H _XL ), G5000H (H _XL ), G6000H
(H _XL ), G7000H (H _XL ), TSKguardc
A combination of the columns is included.

The sample is manufactured as follows.

The sample is placed in tetrahydrofuran (THF), left to stand for several hours, shaken well and mixed well with THF (until the coalescence of the sample disappears), and left still for 12 hours or more. At this time, the leaving time in THF should be 24 hours or more. After that, a filter that passed a sample treatment filter (pore size 0.45 to 0.5 μm, for example, Maisho Redisk H-25-5 manufactured by Tosoh Co., Ltd., Echikro Disc 25CR Gelman Science Japan Co., Ltd.) can be used. Use as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

An image forming method suitable for the present invention will be described below.

The toner carrier in the image forming method of the present invention is not particularly limited, but a rigid roller is used as the toner carrier and the photosensitive member is a flexible member such as a belt, or a rigid member is used as the photosensitive member. It is possible to use a flexible material such as an elastic body as the toner carrier.

An elastic roller is preferably used when it is arranged in pressure contact with a rigid photoconductor.

The hardness of the elastic roller is preferably about 20 to 65 degrees (JIS A), and more preferably 30 to 60 degrees, from the viewpoint of achieving both developability and durability. As the material of the elastic roller, known materials and structures can be used. Particularly, a solid rubber elastic body such as silicone rubber, urethane rubber, NBR, or a foamed elastic body of these is preferably used. Further, a well-known multilayer structure roller having a coat layer different from the central portion on the surface can be used. Further, a known surface treatment may be applied for the purpose of imparting chargeability and transportability.

As for the surface shape of the toner carrier, it is preferable to control the surface roughness thereof in order to achieve both high image quality and high durability. As the surface roughness of the toner carrier, for example, Ra (μm) “JIS B 0601” is 0.2 to
When set to 3.0, both high image quality and high durability can be achieved. When the surface roughness Ra of the toner carrier exceeds 3.0, not only is it difficult to reduce the thickness of the developer layer on the toner carrier, but also the chargeability of the developer is not improved, so that the image quality is improved. I can't hope. When it is 3.0 or less, the developer carrying ability on the surface of the toner carrier is suppressed, the developer layer on the toner carrier is thinned, and the number of times of contact between the toner carrier and the developer is increased. Therefore, the chargeability of the developer is also improved and the image quality is synergistically improved. On the other hand, if the surface roughness Ra is less than 0.2, it becomes difficult to control the developer coating amount.

The toner on the toner carrier is regulated by a developing blade arranged so as to be in pressure contact with the surface of the toner carrier, and a toner layer is formed on the toner carrier.

It is preferable that the pressure for bringing the developing blade into pressure contact with the surface of the toner carrier to regulate the layer thickness on the toner carrier is appropriately adjusted so that the thickness of the toner coat layer is kept constant. As the material of the toner coat amount regulating member, it is preferable to select a friction charging series material suitable for charging the toner to a desired polarity, such as silicone rubber, urethane rubber, rubber elastic body such as NBR, polyethylene terephthalate. Synthetic resin elastic bodies such as, and metallic elastic bodies such as stainless steel, steel, and phosphor bronze can be used, and composites thereof, for example, those in which a resin or rubber is bonded to the sleeve abutting portion on the metallic elastic body, Alternatively, it may be coated.

Further, an organic substance or an inorganic substance may be added to the elastic regulating member, and may be melt-mixed or dispersed. For example, metal oxides, metal powders, ceramics, carbon allotropes, whiskers, inorganic fibers, dyes, pigments,
The chargeability of the toner can be controlled by adding a surfactant or the like. In particular, when the elastic body is a molded body such as rubber or resin, silica, alumina, titania, tin oxide, zirconia oxide, fine powder of metal oxide such as zinc oxide,
It is also preferable to include carbon black, a charge control agent generally used in toner, and the like.

When the conductive regulating member and the toner carrier are used in combination, it is also preferable to apply a DC electric field and / or an AC electric field between the regulating member and the toner carrier. By applying such an electric field, uniform thin layer coating and uniform chargeability are improved, and sufficient image density can be achieved and a high-quality image can be obtained.

Further, when durability is required for the elastic regulating member and the toner carrier, it is preferable that the elastic metal member be adhered with resin or rubber so that the sleeve abutting portion is abutted, or that the elastic member is coated. .

The photoconductor of the present invention includes a-Se and Cd.
A known photosensitive drum or photosensitive belt having a photoconductive insulating material layer such as s, ZnO ₂ , OPC, or a-Si is preferably used. Of these, OPC is particularly preferably used. The binder resin for the organic photosensitive layer in the OPC photoreceptor is not particularly limited, and known binder resins can be used, but from the viewpoint of toner chargeability, transferability, and filming, a polycarbonate resin or a polyarylate resin can be used. Is preferred.

The charging means of the present invention is a charging roller having a conductive elastic layer. This will be described below with reference to the drawings.

In FIG. 1, 2 is a charging member, 2a is a conductive support, 2b is an elastic layer, 2c is a resistance control layer, and 2d is a surface layer. The charging roller may have a structure of the elastic layer 2b and the surface layer 2d without the resistance control layer 2c.

The conductive support 2a used in the present invention is
Metals such as iron, copper, stainless steel, aluminum and nickel can be used. Further, these metal surfaces may be subjected to a plating treatment for the purpose of preventing rust and imparting scratch resistance, but it is necessary that the conductivity is not impaired.

In the charging roller 2, the elastic layer 2b has
Appropriate elasticity is provided to ensure good uniform adhesion of the charging roller 2 to the photoconductor 1.

The conductivity of the elastic layer 2b is adjusted by adding conductive particles such as carbon black or a conductive agent such as an alkali metal salt and an ammonium salt to an elastic material such as rubber. Elasticity is adjusted by the addition of process oils and plasticizers. Specific examples of the elastic material of the elastic layer 2b include natural rubber, ethylene propylene diene methylene rubber (EPDM), and styrene-butadiene rubber (S).
BR), silicone rubber, urethane rubber, epichlorohydrin rubber, isoprene rubber (IR), butadiene rubber (BR), nitrile-butadiene rubber (NBR) and chloroprene rubber (CR), and further polyamide resin, polyurethane resin, Resins such as silicone resin and fluororesin are also included. Moreover, you may use the foam of the said elastic material for the elastic layer 2b.

The electric resistance of the elastic layer is 1 × 10 ³ to 1
Preferably it has a conductivity in the range of × ¹⁰ 10 [Ωcm]. Further, the film thickness depends on the diameter of the conductive support and is not particularly limited.

The surface layer 2d is often provided in order to prevent bleed-out of the plasticizer or the like in the elastic layer 2b to the surface of the charging roller, and to maintain the smoothness and smoothness of the surface of the charging roller. The surface layer 2d is provided by coating or coating a tube.

When the surface layer 2d is provided by coating, specific materials include polyamide resins, polyurethane resins, acrylic resins, fluororesins and silicone resins, as well as epichlorohydrin rubber, urethane rubber,
Examples thereof include chloroprene rubber and acrylonitrile rubber. As a coating method, a dip coating method, a roll coating method, a spray coating method and the like are preferable.

When the surface layer 2d is provided by covering a tube, specific materials include nylon 12, PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin), PVDF (polyvinylidene fluoride). , FEP (tetrafluoroethylene-6 fluoropropylene copolymer resin), and further thermoplastic elastomers such as polystyrene type, polyolefin type, polyvinyl chloride type, polyurethane type, polyester type and polyamide type.

The tube may be a heat-shrinkable tube or a non-heat-shrinkable tube. Surface layer 2d
In order to have appropriate conductivity, conductive particles such as carbon black and carbon graphite and conductive agents such as conductive metal oxides such as conductive titanium oxide, conductive zinc oxide and conductive tin oxide should be used. Used.

The electric resistance of the surface layer is 1 × 10 ⁶ to 1
It is preferably in the range of × 10 ¹⁴ [Ωcm]. The film thickness is preferably 2 to 500 μm.
More preferably, it is 2 to 250 μm.

The resistance control layer 2c is often provided to control the resistance of the charging member. Specific examples of the material for the resistance control layer 2c include resins such as polyamide resin, polyurethane resin, fluororesin and silicone resin, as well as epichlorohydrin rubber, urethane rubber, chloroprene rubber and acrylonitrile rubber. Resistance control layer 2c
Also, for the purpose of adjusting the resistance, conductive particles such as carbon black and carbon graphite, conductive metal oxides such as conductive titanium oxide, conductive zinc oxide and conductive tin oxide, or alkali metal salts and ammonium salts, etc. The conductive agent can be dispersed.

The resistance control layer 2c is also provided by coating or coating the tube.

The electric resistance of the resistance control layer is 1 × 10 ^6.
It is preferably in the range of 1 × 10 ¹⁰ [Ωcm].
Further, the film thickness is preferably 10 to 1000 μm. More preferably, it is 10 to 750 μm.

The volume resistivity of the present invention is measured by JI
It was carried out according to SK 6911.

The Asker C hardness of the roller is preferably 25 to 75 degrees. More preferably, it is 30 to 55 degrees. The hardness was measured by using an Asker C rubber hardness meter (manufactured by Kobunshi Keiki Co., Ltd.), and the numerical value was obtained by averaging five points. The measurement is performed with a load of 4.9 N (500 g) on one side.

Next, the image forming method of the present invention will be specifically described below with reference to the accompanying drawings.

In FIG. 2, 140 is a developing device and 100
Is a photoconductor, 127 is a transfer target such as paper, 114 is a transfer member, 126 is a fixing pressure roller, 128 is a fixing heating roller, and 117 is a primary charging member that comes into contact with the photoconductor 100 for direct charging. Show.

A bias power source 131 is connected to the primary charging member 117 so as to uniformly charge the surface of the photoconductor 100.

The developing device 140 contains the toner 142, and is provided with the toner carrier 104 which comes into contact with the photosensitive member 100 and rotates in the direction of the arrow. Further, the developing blade 143 for toner amount regulation and charge imparting is attached to the toner carrier 104 and the toner carrier 104 is attached.
A coating roller 141 that rotates in the direction of the arrow is also provided in order to apply a charge to the toner by friction with. A developing bias power source 133 is connected to the toner carrier 104.
The bias power source 132 is also connected to the coating roller 141, and a voltage is set to the negative side of the developing bias when the negative charging toner is used, and to the positive side of the developing bias when the positive charging toner is used. To be done.

A transfer bias power source 134 having a polarity opposite to that of the photosensitive member 100 is connected to the transfer member 114.

Here, the photoconductor 100 and the toner carrier 10
The length of the contact portion 4 in the rotation direction, that is, the so-called developing nip width, is preferably 0.2 mm or more and 8.0 mm or less from the viewpoint of image density and mechanical stress on the toner.

The toner coating amount is controlled by the developing blade 143, which is in contact with the toner carrier 104 via the toner layer.

In FIG. 2, the primary charging member 117 uniformly charges the photoconductor 100 rotating in the arrow direction. The primary charging member used here is a charging roller having a central core bar 117b and a conductive elastic layer 117a forming the outer periphery thereof as a basic configuration. The charging roller 117 is brought into contact with the one surface of the photoconductor with a pressing force, and is driven to rotate as the photoconductor 100 rotates.

After the primary charging step, an exposure 123 from the light emitting element 121 forms an electrostatic latent image on the photosensitive member 100 according to the information signal. The electrostatic latent image on the photoconductor 100 is visualized by the toner at the position where it is in contact with the toner carrier 104.

Next, the visible image is transferred onto the transfer target 127 by the transfer member 114, and the transfer toner 129 is transferred to the transfer target 127 together with the heating roller 128 and the pressure roller 126.
It is passed through and fixed to obtain a permanent image. As the heating / pressurizing fixing means, other than the heating roller system which basically has a heating roller having a heating element such as a halogen heater shown here and an elastic pressing roller pressed against the heating roller with a pressing force. A method of heating and fixing with a heater through a film is also used.

On the other hand, the untransferred toner 124 remaining on the photosensitive member 100 without being transferred is the cleaning blade 120.
It is cleaned by the cleaning means 120 having a and collected in the cleaning container.

The toner and image forming method of the present invention can also be used in full color image formation. The image forming method shown in FIG. 3 will be described as an example of the full-color image forming method.

The full-color image forming method is not limited to the configuration shown in FIG. 3, but a full-color image forming method in which color toners are directly superposed on a transfer material and multiple development is performed, particularly in-line A full-color image forming method in which color developing devices are arranged to perform sequential development can also be preferably used in the present invention.

In the apparatus system shown in FIG. 3, the developing devices 4-1, 4-2, 4-3, and 4-4 each have a developer containing cyan toner, a developer containing magenta toner,
A developer having a yellow toner and a developer having a black toner are introduced, and the electrostatic charge image formed on the photoconductor 1 is developed by the contact one-component developing method, and toner images of respective colors are formed on the photoconductor 1. The photoreceptor 1 is a photosensitive drum or photosensitive belt having a photoconductive insulating material layer. Photoconductor 1
Is rotated in the direction of the arrow by a driving device (not shown).

The charging roller 2 is basically composed of a cored bar 2b at the center and a surface layer 2a forming the outer periphery thereof. The charging roller 2 is pressed against the surface of the photoconductor 1 with a pressing force and is rotated by the rotation of the photoconductor 1.

The toner image on the photosensitive member has a voltage (for example, ±
It is transferred to the intermediate transfer member 5 to which 0.1 to ± 5 kV) is applied. The surface of the photoconductor after the transfer is cleaned by a cleaning unit 9 having a cleaning blade 8.

The intermediate transfer member 5 is a pipe-shaped conductive core metal 5.
b and an elastic layer 5a having a medium resistance formed on the outer peripheral surface thereof. The core metal 5b may be a plastic pipe coated with conductive plating.

The elastic layer 5a of medium resistance is made of silicone rubber, fluorine rubber, chloroprene rubber, urethane rubber,
EPDM (ethylene propylene diene terpolymer)
Conductivity-imparting materials such as carbon black, zinc oxide, tin oxide, and silicon carbide are mixed and dispersed in elastic materials such as to adjust the electric resistance value (volume resistivity) to a medium resistance of 10 ⁵ to 10 ¹¹ Ω · cm. A solid or foamed fleshy layer.

The intermediate transfer member 5 is disposed in parallel with the photosensitive member 1 so as to be in contact with the lower surface of the photosensitive member 1, and rotates in the counterclockwise direction indicated by an arrow at the same peripheral speed as the photosensitive member 1. To do.

The toner image of the first color formed and carried on the surface of the photoconductor 71 is transferred by the applied transfer bias to the intermediate transfer body 5 while passing through the transfer nip portion where the photoconductor 1 and the intermediate transfer body 5 are in contact with each other. The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer body 5 by the electric field formed in the nip region.

If necessary, the detachable cleaning means 10 cleans the surface of the intermediate transfer member 5 after the toner image is transferred to the transfer material.

When there is a toner image on the intermediate transfer body, the cleaning means 10 is separated from the surface of the intermediate transfer body so as not to disturb the toner image.

A transfer means is disposed in parallel with the intermediate transfer body 5 so as to be in contact with the lower surface of the intermediate transfer body 5, and the transfer means 7 is, for example, a transfer roller or a transfer belt. Rotates clockwise at the same peripheral speed as the arrow. The transfer means 7 may be arranged so as to be in direct contact with the intermediate transfer body 5, or a belt or the like may be arranged so as to be in contact between the intermediate transfer body 5 and the transfer means 7.

In the case of the transfer roller, the core metal 7b at the center and the surface layer 7a having the outer periphery thereof are used as a basic structure.

The transfer means 7 is rotated at a constant speed or a peripheral speed different from that of the intermediate transfer member 5. The transfer material 6 is the intermediate transfer member 5.
And the transfer means 7 and the transfer means 7 at the same time.
The toner image on the intermediate transfer member 5 is transferred to the surface side of the transfer material 6 by applying a bias having a polarity opposite to that of the triboelectric charge of the toner from the transfer bias means.

As the material of the transfer rotary member, the same material as that of the charging roller can be used, and a preferable contact process condition is a roller contact pressure of 4.9 to 490 N.
/ M (5 to 500 g / cm), DC voltage is ± 0.2 to
± 10 kV.

Next, the transfer material 6 is conveyed to a fixing device H having a heating roller having a heating element such as a halogen heater incorporated therein and an elastic pressure roller pressed against the heating roller with a pressing force, as a basic structure, and heated. The toner image is heated and pressed and fixed on the transfer material by passing between the roller and the pressure roller. A method of fixing with a heater through a film may be used.

In the case of evaluation of only a single color, four same toners are set in each developer and continuous paper feed printing is performed.

FIG. 4 shows an example of the developing means of the present invention.

Development can be carried out using a one-component system contact developing type developing means provided with the developing device 31. Specifically, while being applied with a direct current or an alternating electric field to the toner carrier 37 by the power source 36, the toner is supplied from the coating roller 32,
Development is performed in a state where the toner 34 whose coating amount is regulated by the developing blade 33 is in contact with the photoconductor 35. When using an alternating electric field, triangular wave, rectangular wave, sine wave, Dut
It is possible to select and use a waveform with a changed y-ratio or a waveform with periodic alternating off, but in the present invention, a DC electric field with a small voltage load on the photosensitive member is preferably used, and the applied voltage is a photosensitive voltage. It is set to an appropriate value between the dark potential on the body (potential immediately after the charging step) and the bright potential (potential after the exposure step).

[0229]

EXAMPLES The present invention will be explained more concretely by showing examples below, but this does not limit the present invention in any way.

Manufacturing Method of Charging Roller : ( Manufacturing Method of Charging Roller No. 1) 100 parts by mass of styrene-butadiene rubber (SBR) 30 parts by mass of carbon black 5.5 parts by mass of zinc oxide 2 parts by mass or more of fatty acid 10 of the ingredients in a closed type mixer adjusted to 60 ° C
After kneading for 10 minutes, 20 parts by weight of naphthenic oil was added to 100 parts by weight of SBR, and the mixture was kneaded for 20 minutes with a closed mixer cooled to 20 ° C. to prepare a raw material compound. In addition, raw material rubber styrene-butadiene rubber (SB
R) 0.5 parts by mass of sulfur as a vulcanizing agent, 1 part by mass of thiazole type and 1 part by mass of thiuram type as a vulcanization accelerator to 100 parts by mass of a vulcanizing agent were added to the raw material compound, and the mixture was cooled to 20 ° C. in a two-roll machine And kneaded for 10 minutes. Using this compound, a roller-like elastic layer 2b was vulcanized by transfer molding around a stainless conductive support 2a having a diameter of 6 mm and a length of 320 mm.

The surface roughness of the charging roller was determined by polishing the roller surface at this point. The 10-point average surface roughness of the elastic layer roller after polishing was Rz = 11.0 μm.

Further, as a material for the resistance control layer 2c, 100 parts by mass of epichlorohydrin rubber and 30 parts by mass of titanium oxide were dispersed and dissolved in a solvent of toluene to prepare a coating material for the resistance control layer. This paint was applied on the elastic layer 2b by a dipping method to form a resistance control layer 2c having a film thickness of 700 μm.

Further, a surface layer 2d was formed on the formed resistance control layer 2c as follows. As a material for the surface layer 2d, 100 parts by mass of polyurethane resin and 90 parts by mass of titanium oxide were dispersed and dissolved in a solvent of methyl ethyl ketone to prepare a coating material for the surface layer. This coating material is applied onto the resistance control layer 2c by a dipping method to form a surface layer 2d having a film thickness of 10 μm. Got 1. The 10-point average surface roughness (Rz) was 1.2 μm.

(Manufacturing Method of Charging Roller No. 2) Charging Roller No. 2 Rz of the elastic layer roller 2b after polishing is set to 14.8 μm by using a process rougher than the polishing of No. 1 and the charging roller NO. In the same manner as in the manufacturing method of No. 1, finally, the charging roller No. 1 having a surface roughness (Rz) of 5.0 μm was used. Got 2.

(Manufacturing Method of Charging Roller No. 3) Charging Roller No. 3 Rz of 2b of the elastic layer roller after polishing is set to 20.4 μm by using a process rougher than the polishing of No. 2 and the charging roller NO. In the same manner as in the manufacturing method of No. 1, finally, the charging roller No. 1 having a surface roughness (Rz) of 7.8 μm was used. Got 3.

Toner Manufacturing Method: ( Manufacturing Method of Black Toner No. 1) High Speed Stirring Device T
In a 2 liter four-necked flask equipped with a K-homomixer, 910 parts by mass of ion-exchanged water, 2 parts by mass of polyvinyl alcohol, and 1 part by mass of sodium dodecyl sulfate were added to adjust the rotation speed to 10,000 revolutions / minute, The dispersion medium system was heated to 60 ° C.

On the other hand, the dispersoid system includes: styrene monomer 60 parts by mass, 2-ethylhexyl acrylate monomer 40 parts by mass, grafted carbon black pigment (carbon content 50%) 10 parts by mass, urea derivative 0. 7 parts by mass / 0.5 parts by mass of the oxycarboxylic acid (2-A) / 10 parts by mass of a saturated polyester resin (polycondensation product of propylene oxide-modified bisphenol A and phthalic acid) The above mixture was mixed with a media type disperser 2 After being dispersed for 25 hours, 25 parts by mass of a low softening point substance (paraffin wax DSC peak 60 ° C.) was added, and the internal temperature was adjusted to 60 ° C. and kept for 30 minutes.

Then, the dispersion containing 3 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) which is a polymerization initiator was added to the above dispersion medium while maintaining 12,000 rpm. Granulated for 8 minutes. After that, the stirrer was changed from the high-speed stirrer to the propeller stirrer, and the polymerization was performed at 150 rpm for 12 hours. After the polymerization was completed, the slurry was cooled, washed with water and dried to obtain black particles.

To 100 parts by mass of the obtained black particles, 1.5 parts by mass of silica fine powder having a hydrophobicity of 97% was added and uniformly adhered by a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain black toner NO. Got 1.

The obtained black toner NO. The circle-equivalent number average diameter of ₁ was D ₁ 5.7 μm. Details are shown in Table 1.

(Production Method of Black Toner No. 2) Black Toner No. 2 was prepared except that the granulation time of the dispersoid in the dispersion medium was 14 minutes. Black toner NO. Got 2. The obtained toner had an equivalent circle number average diameter of D _{1 of} 5.5 μm. Details are shown in Table 1.

(Production Method of Black Toner No. 3) Low Softening Point Substance (Ester Wax DSC Peak 75 ° C.)
Black toner NO. Black toner NO. Got 3. The obtained toner had a circle-equivalent number average diameter of D ₁ 5.9 μm. Details are shown in Table 1.

(Production Method of Black Toner No. 4) Black Toner No. 4 was prepared except that silica fine powder having a hydrophobicity of 97% was 1.0 part by mass. Black toner NO. Got 4. The circle-equivalent number average diameter of the obtained toner was D ₁ 5.7 μm. Details are shown in Table 1.

(Manufacturing Method of Black Toner No. 5) Black Toner No. 5 except that silica fine powder having a hydrophobicity of 85% is 1.5 parts by mass. Black toner NO. Got 5. The circle-equivalent number average diameter of the obtained toner was D ₁ 5.7 μm. Details are shown in Table 1.

(Production Method of Black Toner No. 6) Low Softening Point Substance (Paraffin Wax DSC Peak 70
Black toner NO. Black toner NO. Got 6. The obtained toner had a circle-equivalent number average diameter of D ₁ 5.9 μm. Details are shown in Table 1.

(Production Method of Black Toner No. 7) Low Softening Point Substance (Carnauba Wax DSC Peak 60 ° C.)
Black toner NO. 2 except that 0.4 parts by mass of silica fine powder having a hydrophobicity of 97% is used. Black toner NO. Got 7. The circle-equivalent number average diameter of the obtained toner was D ₁ 6.0 μm. Details are shown in Table 1.

(Manufacturing Method of Black Toner No. 8) Black Toner No. 8 except that silica fine powder having a hydrophobicity of 3% is 1.5 parts by mass. Black toner NO. Got 8. The circle-equivalent number average diameter of the obtained toner was D ₁ 5.7 μm. Details are shown in Table 1.

(Production Method of Black Toner No. 9) Low Softening Point Substance (Carnauba Wax DSC Peak 62)
.Degree. C.), except that the fine silica powder having a hydrophobicity of 3% is 1.5 parts by mass. Black toner NO. Got 9. The obtained toner had a circle-equivalent number average diameter of D ₁ 5.9 μm. See Table 1 for details
Shown in.

(Production Method of Yellow Toner No. 1) Black Toner No. 1 In the same manner as the yellow toner No. 1 except that the colorant in the production method of No. 1 was changed to a benzimidazolone pigment. Got 1. The obtained toner had an equivalent circle number average diameter of D _{1 of} 5.8 μm. Details are shown in Table 1.

(Production Method of Yellow Toner No. 2) Low Softening Point Substance (Paraffin Wax DSC Peak 70)
C.)), the yellow toner NO. Yellow toner NO. Got 2. The obtained toner had a circle-equivalent number average diameter of D ₁ 5.9 μm.
Details are shown in Table 1.

(Production Method of Yellow Toner No. 3) Low Softening Point Substance (Carnauba Wax DSC Peak 60 ° C.)
Yellow toner NO. Yellow toner NO. Got 3. The circle-equivalent number average diameter of the obtained toner was D ₁ 6.0 μm. Details are shown in Table 1.

(Production Method of Yellow Toner No. 4) Low Softening Point Substance (Carnauba Wax DSC Peak 62)
C.), and the amount of silica fine powder having a hydrophobicity of 3% is 1.5 parts by mass, except that the yellow toner NO. Yellow toner NO. Got 4. The obtained toner had a circle-equivalent number average diameter of D ₁ 5.9 μm. Details are shown in Table 1.

(Manufacturing Method of Magenta Toner No. 1) Black Toner No. 1 Magenta Toner N except that the quinacridone pigment was used instead of the colorant used in the production method 1.
O. Got 1. The circle-equivalent number average diameter of the obtained toner is D
Was _{1 5.7μm.} Details are shown in Table 1.

(Production Method of Magenta Toner No. 2) Low Softening Point Substance (Paraffin Wax DSC Peak 70
Magenta toner NO. In the same manner as the manufacturing method of No. 1, magenta toner No. Got 2. The obtained toner had a circle-equivalent number average diameter of D ₁ 5.9 μm.
Details are shown in Table 1.

(Production Method of Magenta Toner No. 3) Low Softening Point Substance (Carnauba Wax DSC Peak 60 ° C.)
Magenta toner NO. In the same manner as the manufacturing method of No. 1, magenta toner No. Got 3. The circle-equivalent number average diameter of the obtained toner was D ₁ 6.0 μm. Details are shown in Table 1.

(Production Method of Magenta Toner No. 4) Low Softening Point Substance (Carnauba Wax DSC Peak 62)
.Degree. C.), and magenta toner NO. In the same manner as the manufacturing method of No. 1, magenta toner No. Got 4. The obtained toner had a circle-equivalent number average diameter of D ₁ 5.9 μm. Details are shown in Table 1.

(Manufacturing Method of Cyan Toner No. 1) Black Toner No. 1 Cyan Toner N except that the colorant used in the production method 1 is changed to a copper phthalocyanine pigment.
O. Got 1. The circle-equivalent number average diameter of the obtained toner is D
Was _{1 5.9μm.} Details are shown in Table 1.

(Production Method for Cyan Toner No. 2) Low Softening Point Substance (Paraffin Wax DSC Peak 70 ° C.)
Cyan toner NO. Cyan toner NO. Got 2. The obtained toner had a circle-equivalent number average diameter of D ₁ 5.9 μm. Details are shown in Table 1.

(Production Method for Cyan Toner No. 3) Cyan Toner No. 3 except that a low softening point substance (Carnauba wax DSC peak 60 ° C.) is used. Cyan toner NO. Got 3. The circle-equivalent number average diameter of the obtained toner was D ₁ 6.0 μm. See Table 1 for details
Shown in.

(Production Method for Cyan Toner No. 4) Low Softness
Chemical substance (carnauba wax DSC peak 62 ° C),
Other than 1.5 parts by mass of fine silica powder having a hydrophobicity of 3%
Cyan toner NO. Shear in the same manner as in the manufacturing method of 1.
Toner No. Got 4. Equivalent number of toner particles obtained
Average diameter is D ₁It was 5.9 μm. Details are shown in Table 1.

<Embodiment 1> The black toner NO. Set 1
In a high temperature and high humidity environment (30 ° C./80%), using a laser beam printer of A3 size configured as shown in FIG. 3, a solid image (F of toner loading 0.55 to 0.75 mg / cm ²
F HEX output) and two white solid images (00 HEX output image) were output.

After that, 300 images with an image area ratio of 5% are obtained.
0 sheets were continuously printed, and 30 sheets each of the solid image and the white solid image were output.

Fog, toner scattering in the machine, and fusing of the photosensitive drum were confirmed by using the initial 30th image sample and the first image sample after 3000 continuous image outputs. The results are shown in Table 2.

In a low temperature and low humidity environment (10 ° C./15%)
However, the black toner NO. Four sets of No. 1 were set in each developing machine, and two halftone images having a toner carrying amount of 0.20 to 0.40 mg / cm ² were output using the laser beam printer.

After that, 300 images with an image area ratio of 5% are obtained.
0 sheets are printed continuously, and the above halftone image is 3
0 sheets were output.

Using the initial 30th image sample and the first image sample after 3000 continuous image outputs, the cleaning property and the image uniformity were confirmed. The results are shown in Table 2.
Described in.

The image evaluation methods shown in Table 2 are as follows.

(1) Fogging The measurement of fogging is conducted by the REFLECTOMETER MOD.
It measured using EL TC-6DS (made by Tokyo Denshoku Co., Ltd.).
The black / magenta toner image was calculated using the green filter, the yellow toner image was calculated using the blue filter, and the cyan toner image was calculated using the amber filter. The smaller the fog value, the better. Fog (reflectance;%) = (reflectance of standard paper;%)-(reflectance of sample;%) A: 0.8% or less B: 0.8% or more and 1.2% or less C: 1. 2% to 1.6% or less D: 1.6% to 2.0% or less E: 2.0% or more

(2) Drum Fusing Drum fusing was evaluated by observing the surface of the obtained image and the photoreceptor. The evaluation was A, B, C, D. A: There is no fusion on the image and the surface of the photoconductor is clean. B: There is no fusion on the image, but a slight fusion is seen on the surface of the photoconductor. C: Five fusions on the image. Less than the level, and the fused substance can be clearly recognized on the surface of the photoconductor D: 5 or more fused substances are present on the image, and many fused substances can be recognized on the surface of the photoconductor

(3) Cleaning The cleaning was evaluated based on the images obtained after continuous printing in a low temperature and low humidity environment and the state of the cleaning blade shown in FIG. The evaluation was A, B, C, D. A: The image has no defective cleaning, and there is no trace of toner slipping on the back of the cleaning blade. B: The image has no cleaning failure, but there is a trace of toner slipping through on the back of the cleaning blade. C: The image has no cleaning failure, but the back of the cleaning blade is considerably soiled due to the toner slipping through. D: The image has been cleaned, and the back of the cleaning blade is considerably dirty due to the toner slipping through.

(4) Image uniformity Image uniformity was judged from the images obtained after continuous printing in a low temperature and low humidity environment. The evaluation was A, B, C, D. A: The uniformity of the halftone image is very good, and there is no stain on the charging roller. Level B: The uniformity of the halftone image is good, but there is some stain on the charging roller, and some ghost images are also visible. The image density difference between the ghost portion and the non-ghost portion is less than 0.01. Level C: The uniformity of the halftone image is not very good, the charging roller is stained, and the ghost image is slightly visible. The image density difference between the ghost portion and the non-ghost portion is 0.01 or more and less than 0.03. Level D: The uniformity of the halftone image is poor, and the charging roller is also heavily soiled. The ghost image is clearly generated, and the image density difference between the ghost part and the non-ghost part is 0.03 or more.

<Examples 2 to 17, Comparative Examples 1 to 6> Table 1 shows combinations of toners and charging rollers of Examples 2 to 17 and Comparative Examples 1 to 6. The experimental method and evaluation means are to be learned from Example 1. The results are shown in Table 2.

[0273]

[Table 1]

[0274]

[Table 2]

[0275]

According to the present invention having the above-described structure, it is possible to provide a toner and an image forming method which, even when a large number of sheets are continuously printed, have little fog in a high temperature and high humidity environment and do not cause drum fusion. it can.

Further, it is possible to provide a toner and an image forming method capable of obtaining an image having good cleaning and good image uniformity in a low temperature and low humidity environment.

[Brief description of drawings]

FIG. 1 is a schematic view of a charging roller suitable for the present invention.

FIG. 2 is a schematic diagram of a one-component image forming apparatus suitable for the present invention.

FIG. 3 is a schematic diagram of a full-color image forming apparatus using an intermediate transfer member, which is suitable for the present invention.

FIG. 4 is a schematic explanatory view of a developing device suitable for the present invention.

[Explanation of symbols]

1 photoconductor 2 charging member 100 photoconductor 104 toner carrier 117 charging member 120 cleaning means

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 15/01 G03G 9/08 346 15/02 101 321 15/20 102 361 F term (reference) 2H005 AA01 AA06 AA08 AA15 AA21 CA14 CB07 DA02 EA03 EA05 EA06 EA10 FA07 FB02 2H030 AD01 BB02 BB23 BB42 BB63 2H033 AA09 BA58 BB01 BB28 2H200 FA01 FA08 GA16 JA18 GA34 B44 H12B45 B28 HBJB28 H45 B12 B45 B12 B45 B12 B25 B12 B45 B12 B45 B12 B45 B12 B25 B12 B45 B12 B22 B25 B12 B25 B12 B25 B12 B25 B12 B25 B12 B25 B12 B25 B12 B25 B25 B12 B25 B12 B25 B12 B25 B12 B25 HB2B25 B12 B25 B12 B25 B12 B25 B12 B25 HB2B25 B12 B25 B12 B25 B12 B25 B12 B25 B12 B25 B12 B25 B12 B25 B12 B25 B12 B25 B12 B25 B25 B12 B25 B12 B25 B12 B45 HB02 JC15 JC16 JC18 LA24 LB02 LB09 LB13 LC02 LC03 LC04 LC08 LC10 MA03 MA04 MA08 MA14 MA20 MB04 MC02 MC06 NA02 NA09

Claims (58)

[Claims] 1. A photosensitive member, a charging unit for charging the surface of the photosensitive member, an information writing unit for forming an electrostatic latent image on the charged photosensitive member, and an electrostatic latent image for supplying toner to the electrostatic latent image. A toner used in an image forming method having a developing means for visualizing a toner, a transfer means for transferring the visualized toner image to a transfer material, and a means for fixing the toner image on the transfer material, the developing means comprising: A developing blade for controlling the layer thickness on the toner carrier is arranged so as to be in pressure contact with the surface of the toner carrier, the toner is evenly applied to the surface of the toner carrier, and the toner carrier is brought into direct contact with the photoconductor. The charging means is a charging roller having a conductive elastic layer, and the number-based circle-equivalent diameter-circularity scattergram of the toner has a circle-equivalent number average diameter D1 ( than μm) The charging roller has a small 10-point average surface roughness (Rz), and the toner is composed of at least toner particles containing a binder resin, a colorant, and a release agent, and a hydrophobic inorganic fine powder. A toner having a full width at half maximum at an endothermic peak in differential thermal analysis measurement (DSC) of 14 ° C or less. 2. An average circularity in a number-based circle-equivalent diameter-circularity scattergram measured by a flow-type particle image measuring device for the toner is 0.950 to 0.999. 1. The toner according to 1. 3. The toner according to claim 1, wherein the toner has an average circularity of 0.950 to 0.999 and a circularity standard deviation of less than 0.040. 4. The toner according to claim 1, wherein the toner has an average circularity of 0.950 to 0.995 and a circularity standard deviation of 0.015 or more and less than 0.035.
The toner according to. 5. The toner has an average circularity of 0.970 to 0.995 and a circularity standard deviation of 0.015 or more and 0.0.
The toner according to claim 1 or 2, which is less than 35. 6. The toner according to claim 1, wherein the toner has an aggregation degree of 1 to 40%. 7. The toner according to claim 1, wherein the toner has an aggregation degree of 3 to 30%. 8. The mass X (mg / g) of oxycarboxylic acid extracted from 1 g of the toner with a 0.1 mol / liter sodium hydroxide aqueous solution is X = 0.10 to 20.0 mg / g (toner). The toner according to any one of claims 1 to 7, characterized in that 9. The mass X (mg / g) of oxycarboxylic acid extracted from 0.1 g of the toner with a 0.1 mol / liter sodium hydroxide aqueous solution is X = 0.20 to 5.0 mg / g (toner The toner according to any one of claims 1 to 7, characterized in that 10. Tetrahydrofuran (TH) of the toner
The weight average molecular weight of the soluble component of F) in gel permeation chromatography (GPC) is 10,000 to
It is 1500000, It is characterized by the above-mentioned.
And the image forming method. 11. Tetrahydrofuran (TH) of the toner
The weight average molecular weight of the soluble component of F) in gel permeation chromatography (GPC) is 50,000-
It is 1,000,000, It is characterized by the above-mentioned.
The toner according to any one of 1. 12. The toner according to claim 1, wherein the inorganic fine powder is treated with a hydrophobicity of 70% or more. 13. The toner according to claim 1, wherein the inorganic fine powder is treated with a hydrophobicity of 90% or more. 14. The release temperature of a tangential line of an endothermic curve of the release agent is 40 ° C. or higher.
4. The toner according to any one of 3 above. 15. The toner according to claim 1, wherein the half-value width at the endothermic peak of the toner is 7 ° C. or less. 16. The toner according to claim 1, wherein the release agent has an endothermic peak value in a DSC endothermic curve of 50 ° C. to 120 ° C. 17. The toner according to claim 1, wherein an endothermic peak value in a DSC endothermic curve of the release agent is 60 ° C. to 100 ° C. 18. The release agent has a weight average molecular weight (Mw) of 300 to 1,500.
18. The toner according to any one of 1 to 17. 19. The release agent has a weight average molecular weight (Mw) of 400 to 1,250.
18. The toner according to any one of 1 to 17. 20. The ten-point average surface roughness (Rz) of the charging roller is 5 μm or less.
20. The toner according to any one of 19 to 19. 21. The ten-point average surface roughness (Rz) of the charging roller is 3 μm or less.
20. The toner according to any one of 19 to 19. 22. The toner according to claim 1, wherein the inorganic fine powder is titanium oxide, aluminum oxide and a silicon compound. 23. The primary particle size of the inorganic fine powder is 3 to 5.
23. The toner according to claim 1, wherein the toner has a thickness of 00 nm. 24. The toner according to claim 1, wherein the releasing agent is contained in an amount of 1 to 40 parts by mass based on 100 parts by mass of the binder resin. 25. The toner according to claim 1, wherein the releasing agent is contained in an amount of 5 to 35 parts by mass with respect to 100 parts by mass of the binder resin. 26. The toner according to claim 1, wherein the toner is a non-magnetic single-component toner. 27. The toner according to claim 1, wherein the fixing unit is oilless fixing. 28. The toner according to claim 1, wherein the image forming method has a cleaning mechanism. 29. The toner according to claim 1, wherein the image forming method is a full color image forming method. 30. A photoconductor, charging means for charging the surface of the photoconductor, information writing means for forming an electrostatic latent image on the charged photoconductor, and electrostatic latent image by supplying toner to the electrostatic latent image. In the image forming method, the image forming method includes a developing unit that visualizes the toner, a transfer unit that transfers the visualized toner image to a transfer material, and a unit that fixes the toner image on the transfer material. Characterized by comprising toner particles containing a developing agent and a releasing agent and a hydrophobized inorganic fine powder, and having a half-value width at the endothermic peak of differential thermal analysis (DSC) of the toner of 14 ° C. or less. However, a developing blade that regulates the layer thickness on the toner carrier is arranged so as to be in pressure contact with the surface of the toner carrier, and the toner is evenly applied to the surface of the toner carrier, and the toner carrier is brought into direct contact with the photoreceptor. As a feature The charging means is a charging roller having a conductive elastic layer, and the toner has a circle-equivalent number average diameter D1 (μm) in number-based circle-equivalent diameter-circularity scattergram measured by a flow-type particle image measuring device. The image forming method is characterized in that the 10-point average surface roughness (Rz) of the charging roller is smaller than that of (1). 31. The average circularity in a number-based circle equivalent diameter-circularity scattergram measured by a flow type particle image measuring device of the toner is 0.950 to 0.999. 30. The image forming method according to item 30. 32. The image forming method according to claim 30, wherein the toner has an average circularity of 0.950 to 0.999 and a circularity standard deviation of less than 0.040. 33. The toner according to claim 30, wherein the toner has an average circularity of 0.950 to 0.995 and a circularity standard deviation of 0.015 or more and less than 0.035. Image forming method. 34. The toner has an average circularity of 0.970 to 0.995 and a circularity standard deviation of 0.015 or more.
It is less than 035, 30 or 31 characterized by the above-mentioned.
The image forming method described in 1 .. 35. The image forming method according to claim 30, wherein the aggregation degree of the toner is 1 to 40%. 36. The image forming method according to claim 30, wherein the aggregation degree of the toner is 3 to 30%. 37. The mass X (mg / g) of oxycarboxylic acid extracted from 0.1 g of the toner with a 0.1 mol / liter sodium hydroxide aqueous solution is X = 0.10.
37 to 20.0 mg / g (based on the mass of the toner). 37. The image forming method according to claim 30, wherein 38. The mass X (mg / g) of oxycarboxylic acid extracted from 0.1 g of the toner with a 0.1 mol / liter sodium hydroxide aqueous solution is X = 0.20.
37 to 5.0 mg / g (based on the mass of the toner). 37. The image forming method according to claim 30, wherein 39. Tetrahydrofuran (TH
The weight average molecular weight of the soluble component of F) in gel permeation chromatography (GPC) is 10,000 to
39. The image forming method and the image forming method according to claim 30, wherein the image forming method is 1500000. 40. Tetrahydrofuran (TH
The weight average molecular weight of the soluble component of F) in gel permeation chromatography (GPC) is 50,000-
39. The image forming method according to claim 30, wherein the image forming method is 1,000,000. 41. The inorganic fine powder is treated with a hydrophobicity of 70% or more, 30 to 40.
The image forming method according to any one of 1. 42. The inorganic fine powder is treated with a degree of hydrophobicity of 90% or more, 30 to 40.
The image forming method according to any one of 1. 43. The image forming method according to claim 30, wherein a tangential desorption temperature of an endothermic curve of the release agent is 40 ° C. or higher. 44. The half value width at the endothermic peak of the toner is 7 ° C. or less.
The image forming method according to any one of 1. 45. The image forming method according to claim 30, wherein the releasing agent has an endothermic peak value in a DSC endothermic curve of 50 ° C. to 120 ° C. 46. The image forming method according to claim 30, wherein the endothermic peak value in the DSC endothermic curve of the release agent is 60 ° C. to 100 ° C. 47. The weight average molecular weight (Mw) of the release agent is 300 to 1,500.
The image forming method according to any one of 0 to 46. 48. The release agent has a weight average molecular weight (Mw) of 400 to 1,250.
The image forming method according to any one of 0 to 46. 49. The image forming method according to claim 30, wherein the 10-point average surface roughness (Rz) of the charging roller is 5 μm or less. 50. The image forming method according to claim 30, wherein the 10-point average surface roughness (Rz) of the charging roller is 3 μm or less. 51. The image forming method according to claim 30, wherein the inorganic fine powder is titanium oxide, aluminum oxide or a silicon compound. 52. The primary particle size of the inorganic fine powder is 3 to 5.
52. The image forming method according to claim 30, wherein the image forming method is 00 nm. 53. The image forming method according to claim 30, wherein the releasing agent is contained in an amount of 1 to 40 parts by mass based on 100 parts by mass of the binder resin. 54. The image forming method according to claim 30, wherein the release agent is contained in an amount of 5 to 35 parts by mass based on 100 parts by mass of the binder resin. 55. The image forming method according to claim 30, wherein the toner is a non-magnetic one-component toner. 56. The image forming method according to claim 30, wherein the fixing unit is oilless fixing. 57. The image forming method according to claim 30, further comprising a cleaning mechanism. 58. The image forming method according to claim 30, wherein the image forming method is a full-color image forming method.