JP2003076193A - Fixing method and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fixing method and toner which provide images of high quality for a long period, neither spoil fixation performance and offsetting resistance nor form a defective image accompanying fixing device contamination, and can shorten the warming-up time of a fixing roller. SOLUTION: The fixing device which has at least a fixing roller with a heating means and a pressure roller pressed against the fixing roller is used; when a toner image is heated and fixed on a recording material by passing the recording material having the toner image between rollers of the fixing device at a process speed of 100 to 250 mm/sec, a fixing roller of 0.05 to 4.0 μm in surface roughness, 1.0×10<7> to 1.0×10<4> Ω in surface resistance, and 60 to 95% in the area presence ratio of gaps in section is used as the fixing roller and toner of 65 to 120 deg. in contact angle to water is used as the toner for forming the toner image.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for heating and pressurizing and fixing a visible image formed by a toner for developing an electrostatic charge image used in electrophotography, electrostatic recording, magnetic recording and the like. .

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, U.S. Pat. No. 2,297,691 and JP-B-42-23910 are known.
Publication (US Pat. No. 3,666,363) and Japanese Patent Publication No. 43-24748 (US Pat. No. 4,074)
Although a large number of methods are known, as described in No. 1,361), etc., a photoconductive substance is generally used and an electric latent image is formed on a photoconductor by various means. ,
Then, the latent image is developed with toner to form a visible image, and the toner image is transferred to a transfer material (recording material) such as paper, if necessary, and then fixed by heating, pressure or the like to obtain a copy. Is. Conventionally, a fixing roller as a heating member has been widely used as a fixing device in such an image forming apparatus.

FIG. 2 is a sectional view of a schematic structure showing an example of a fixing roller type fixing device. In the figure, reference numeral 1 denotes a fixing roller (heating roller, heat roller), which has a heating means such as a halogen heater 3 inside and is heated at the time of fixing. 4 is below the fixing roller 1,
A pressure roller as a pressure member that is arranged in parallel with the fixing roller and is pressed against the lower surface of the fixing roller with a predetermined pressing force by a biasing means such as a spring. By introducing a recording material (unfixed toner image) having a toner image as a heated material into the pressure contact nip portion (N) formed between the fixing roller 1 and the pressure roller 4 and passing the recording material, The toner image on the recording material having the toner image is fixed as a fixed image on the recording material surface by heating by the fixing roller 1 and pressure by the pressure roller 4 in the pressure contact nip portion.

On the other hand, in recent years, there has been a demand for fixing at a low temperature for the purpose of energy saving and shortening of waiting time. For example, JP-A-7-140708 and JP-A-7-181.
In Japanese Patent Laid-Open No. 730 and Japanese Patent Laid-Open No. 8-305080, although the maximum molecular weight of the resin used in the toner is specified, good fixing characteristics cannot be satisfied, and a fixing roller, a pressure roller, etc. The fixing member is likely to be contaminated, and it is difficult to use the fixing device for a long time. Especially, the toner image sticks to the fixing roller,
A so-called offset phenomenon easily occurs. Further, this phenomenon may appear as a phenomenon in which the toner is transferred to a pressure roller or other member inside the fixing device and the contaminants are transferred to a transfer material to be subsequently fixed, or the image is disturbed.

Conventionally, in order to solve the offset phenomenon, as a proposal from the toner, for example, Japanese Patent Publication No. 51-23.
No. 354 proposes a toner composed of a vinyl polymer which is appropriately cross-linked by adding a cross-linking agent and a molecular weight modifier, and Japanese Patent Publication No. 55-6805 discloses an α, β-unsaturated ethylenic monomer. A toner having a wide molecular weight distribution so that the ratio of the weight average molecular weight to the number average molecular weight of a monomer is 3.5 to 40 has been proposed. Further, in a vinyl-based polymer, a blend-based toner in which Tg, molecular weight, gel content and the like are specified has been proposed.

Although the toners proposed by these proposals have a higher offset temperature than toners made of a single resin having a narrow molecular weight distribution, their durability is not sufficiently affected. Furthermore, when offset measures are taken by these means, the amount of heat required for fixing increases remarkably, and it is necessary to raise the temperature of the fixing roller, which causes problems such as increase in power consumption and temperature rise inside the machine. Tends to become.

Further, in terms of energy saving, various studies have been conducted in order to shorten the warming-up time of the fixing roller after turning on the power of the main body. However, it is also true that there are various problems. In the method of proceeding by examining the material of the fixing roller in order to shorten the warming-up time of the fixing roller, (1) there is a problem of thermal deformation of the fixing roller, which causes deterioration in fixing property and offset resistance. However, (2) the degree of cooling of the fixing roller during continuous sheet feeding becomes remarkable, and the fixing property and the offset resistance are deteriorated due to the cooling degree.

By the way, recently, the performance required of the image forming apparatus has been widespread. In addition to images of characters, thin lines, and thick lines, excellent image quality is required for solid images and halftone images included in photographs and graphics. In these cases, it is necessary that the fixing device does not deteriorate the image, and further improvement in performance is required.

A problem that occurs when these images are repeatedly output is the above-mentioned offset. This phenomenon remarkably appears especially in a graphic image having many halftones and solid portions. This is because the toner on the transfer material is not sufficiently melted, or the melted toner does not adhere sufficiently to the transfer material. To solve this problem, applying a releasing oil to the surface of the fixing roller has been studied, but a satisfactory one has not been obtained yet.

In recent years, a wide variety of recording materials have been used. For example, the type of paper used as a recording material is not only different in the amount of weighing, but also in the difference in material, in particular, the type and amount of filler contained. Among these recording materials, there are various kinds of recording materials such as those that easily adhere to the constituent members inside the fixing device and those that are easily released. With conventional methods, it is difficult to avoid the adverse effects of these recording material-derived contaminants,
These contaminants derived from the recording material and the toner, which is the developer, are agglomerated and adhered to the fixing roller, which peels off on the recording material to contaminate the recording material and improve the quality of copying and printing. There was something to lose.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high quality image for a long period of time and fix a large number of various transfer materials without impairing the fixing performance and the offset resistance performance. Also in the above, it is to propose a fixing method and a toner used in this method, in which a defective image due to contamination of the fixing device does not occur.

Another object of the present invention is to provide a fixing method capable of shortening the warm-up time of the fixing roller.

[0013]

SUMMARY OF THE INVENTION The present invention uses a fixing device having at least a fixing roller having a heating means and a pressure roller in pressure contact with the fixing roller, and a recording material having a toner image between the rollers of the fixing device. Is a fixing method in which the toner image is heated and fixed on the recording material by passing the toner at a process speed of 100 to 250 mm / sec, and the surface roughness of the fixing roller is 0.05 to 4.0 μm. Is 1.0 × 10 ^{7 to} 1.0 × 10 ¹⁴
Ω, the area existence ratio of voids in the cross section of the fixing roller is 60 to 95%, and the toner forming the toner image has a contact angle with water of 65 to 120 °.

Further, the present invention uses a fixing device having at least a fixing roller having a heating means and a pressure roller in pressure contact with the fixing roller, and processes a recording material having a toner image between the rollers of the fixing device at a process speed of 100 to 100. When the toner image is heated and fixed on the recording material by passing it at 250 mm / sec, the fixing roller has a surface roughness of 0.05 to 4.0 μm and a surface resistance of 1.0 ×.
From 10 ⁷ to 1.0 × 10 ¹⁴ Omega, and a toner area existence ratio of voids in the cross-section is used in the fixing method using the fixing roller is 60 to 95%, the contact angle to water of 65 to Providing a toner that is 120 °.

The fixing roller used in the present invention has a surface roughness of 0.15 to 3.0 μm, a surface resistance of 1.0 × 10 ^{9 to} 1.0 × 10 ¹² Ω, and a cross section. It is more preferable that the area abundance ratio of voids is 75 to 85%.

The toner of the present invention has a contact angle with water of 80 to 110 °, contains a polyester resin as a binder resin, and has a toluene insoluble content of 5 to 50% by mass, and further 10 to 10. 35% by mass, Mw / M, which is the ratio of the weight average molecular weight to the number average molecular weight, where Mw is the weight average molecular weight and Mn is the weight average molecular weight in the molecular weight distribution measurement by GPC.
n is 10 to 2000, more preferably 20 to 1600, and contains wax, which has an endothermic peak in DSC measurement of 60 to 150 ° C., further 75 to 1
More preferably, the wax is present at 40 ° C.

According to the present invention, the warming-up time of the fixing roller can be shortened, and at the same time, good image fixability and good offset resistance can be obtained, and a high-quality image can be provided for a long period of time. Is possible.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a fixing device having at least a fixing roller having a heating means and a pressure roller in pressure contact with the fixing roller is used. First, the fixing device used in the present invention will be described.

FIG. 2 is a schematic explanatory view showing an example of a fixing device applicable to the present invention. In the figure, 1 is a fixing roller (heating roller), which has a heater as a heating means inside. The pressure roller 4 is a roller arranged so as to face the fixing roller 1. In this embodiment, the pressure roller 4 is arranged below the fixing roller 1 in parallel with the fixing roller 1 and is made of a resin elastic body or a spring. The biasing means presses the lower surface of the fixing roller 1 with a predetermined pressing force.

A recording material (unfixed toner image) having a toner image as a material to be heated is introduced into a pressure contact nip portion N formed between the fixing roller 1 and the pressure roller 4 and conveyed therethrough. As a result, the toner image on the recording material having the toner image is fixed on the surface of the recording material as a fixed image by heat and pressure by heat from the fixing roller 1 and pressure of the roller pairs 1 and 4.

As the fixing roller, a fixing roller having a conventionally known structure can be used. One example thereof is
A cored bar made of aluminum, iron or the like in a cylindrical shape, and PFA, P formed on the surface of the cored bar and covering the surface of the cored bar.
A configuration having a releasable resin layer such as TFE can be mentioned.
A heating means such as a halogen heater is arranged inside the cylindrical core metal, and a voltage is applied to the halogen heater. The method of manufacturing the fixing roller used in the present invention is not particularly limited, and the fixing roller can be manufactured by a conventionally known method.

In the fixing device used in the present invention,
In addition to the fixing roller and the pressure roller, various conventionally known means and devices can be appropriately used. For example, in the present embodiment, a temperature detecting element for detecting the temperature of the fixing roller, for example, a thermistor is brought into contact with the fixing roller, and the thermistor is connected to the control means. The control means controls the electric power supplied to the halogen heater based on the output signal of the thermistor to maintain the temperature of the outer peripheral surface of the fixing roller within a predetermined range.

On the other hand, the pressure roller is arranged such that the fixing roller and the rotation axis are parallel to each other. A structure having a core metal such as stainless steel or iron and an elastic layer covering the core metal is generally used for the pressure roller, and the pressure roller having such a structure is also applied to the present invention. it can. The elastic layer is formed of silicone rubber, fluororubber, or the like, which has excellent heat resistance and releasability. It should be noted that the pressure roller urges, for example, one or both of the fixing roller and the pressure roller (only the pressure roller in the present embodiment) toward the facing roller by the urging means described above. By adopting the configuration described above, it is arranged so as to be in pressure contact with the fixing roller.

If necessary, the fixing device used in the present invention may be provided with a member for cleaning the fixing roller and the pressure roller. The member for cleaning the fixing roller and the pressure roller is not particularly limited, and any cleaning member can be used as long as the purpose is to remove the toner and other contaminants on the fixing roller and the pressure roller. It can also be used as a member.
Examples of the member for cleaning the fixing roller include a cleaning wave for contacting the fixing roller, and an example of the member for cleaning the pressure roller includes a cleaning roller for contacting the pressure roller.

The fixing roller used in the present invention has a surface roughness of 0.05 to 4.0 μm, more preferably 0.15 μm to 3.0 μm.

When the surface roughness of the fixing roller is in the above range, the balance between the frictional state between the paper passing through the fixing device and the fixing roller and the balance of the pressure applied to the paper passing through the fixing device are further improved. Therefore, the image quality after fixing is further improved.

The fixing roller used in the present invention has a surface resistance
Resistance is 1.0 × 10⁷Through 1.0 x 10¹⁴Stipulated in Ω
The surface resistance of the fixing roller is more preferably 1.0 ×
10 ⁹Through 1.0 x 10¹²It is in the range of Ω.

When the surface resistance of the fixing roller is in the above range, deterioration of image quality after fixing and an increase in charge amount of the fixing roller can be suppressed, and image quality can be further improved.

In the present invention, the means for achieving the above-mentioned surface roughness and surface resistance is not particularly limited and can be achieved by a conventionally known method. The surface roughness and the surface resistance are achieved, for example, by a method such as a polishing step or a blasting method if the surface roughness is obtained, and if the surface resistance is obtained by a method such as dispersing a conductive substance in a resin layer covering the core metal. It is preferable. As an example of such a means for achieving this, conductive particles such as carbon black may be added to a releasing resin (for example, PTF) at the time of manufacturing the fixing roller.
E) and the method of coating at the same time.

The fixing roller used in the present invention has an area existence ratio of voids of 60 to 95 in the cross section of the fixing roller.
Stipulated in%. In the present invention, the area presence ratio of the voids in the cross section of the fixing roller means the ratio of the cavity in the cross section of the fixing roller. As shown in FIG. 1, the inner diameter of the cored bar in the central part of the fixing roller is D, When the outer diameter of the fixing roller is L, it is calculated by the following formula (1).

## EQU1 ## Area existence ratio of voids in cross section of fixing roller = [π (D / 2) ² / π (L / 2) ² ] × 100 (1)

In the present invention, by setting the area existence ratio of the voids in the cross section of the fixing roller to 60 to 95%, it becomes possible to control the balance between the heating of the fixing roller by the fixing heater and the heat radiation from the fixing roller. As a result, the warming-up time of the fixing roller can be shortened, and at the same time, the fixing property during continuous sheet feeding can be improved.

More preferably, the area existence ratio of the voids in the cross section of the fixing roller is in the range of 75 to 85, and in such a range, the warm-up time of the fixing roller is shortened and the temperature is lowered during continuous sheet feeding. Further, it is possible to make the configuration satisfying with good balance. As is clear from FIG. 1 and the above formula (1), the area existence ratio can be adjusted by the inner diameter and thickness of the core metal used and the thickness of the resin layer.

The toner used in the present invention has a contact angle to water of 65 to 120 °, preferably 80 to 110 °.

As the toner of the present invention, a toner having a commonly adopted structure can be used. Examples of such toner include toner particles containing a binder resin, a colorant, and, if necessary, other additives such as a charge control agent and wax, and inorganic fine powder and the like which are blended as necessary. A toner having an additive and carrier particles such as a magnetic carrier may be used.
In the present invention, by using a polyester resin as the binder resin, the contact angle of the toner with water is 65 to 1
It can be controlled at 20 °. Further, in the present invention, it is also a preferable mode to employ a toner composition in which a styrene-acrylic resin is mixed with a polyester resin.

When the contact angle of the toner with respect to water is within this range, the contact between the toner and the fixing roller can be further improved while effectively preventing the offset.

The contact angle of the toner with water is 65 to 12
As an example of means for controlling at 0 °, adjusting the blending ratio of these blending components depending on the polarities of various materials to be blended in the toner. The specific method is shown below.

When a polyester resin having a relatively high polarity is used, the contact angle of the toner with water tends to be low. Therefore, by using a hydrocarbon type wax component as the wax component, It can be adjusted within a preferable contact angle range.

When a styrene resin having a relatively low polarity is used, the contact angle of the toner with water tends to be high. Therefore, by using a wax component having a polarity, the toner of the present invention It can be adjusted within a preferable contact angle range.

It is also preferable to use a polyester resin and a styrene resin in combination, and in this case as well, a wax is added to adjust the contact angle to a preferable range.

In the present invention, the toluene insoluble content of the toner is preferably 5 to 50% by mass, more preferably 10 to 35% by mass.

Within the above range, the toner can have a better balance of viscosity and elasticity, and a better balance of fixability and offset resistance can be achieved.

In the present invention, when the weight average molecular weight is Mw and the number average molecular weight is Mn in the molecular weight distribution measurement of the toner by GPC, Mw / Mn, which is the ratio of the weight average molecular weight to the number average molecular weight, is It is preferably 10 to 2000, and more preferably 20 to 1600.

Within the above range, the toner can have a better balance between viscosity and elasticity, and a better balance between fixability and offset resistance can be achieved.

In the present invention, the toluene insoluble content of the toner is 5 to 50% by mass, and the ratio (Mw / Mw) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in the molecular weight distribution measurement of the toner by GPC. Mn) is 10 to 2
By setting the viscosity to 000, the balance between the viscosity and the elasticity of the toner can be further improved, and as a result, the better balance between the fixing property and the offset resistance can be achieved.

In the present invention, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) in the measurement of the molecular weight distribution of the toner by GPC with the toluene insoluble content of the toner being 5 to 50 mass%. 10 to 20
There is no particular limitation on the means for achieving the value of 00, and it is sufficient that the method is achieved by a conventionally known method. As an example of the means for achieving the value, for example, regarding the constituent material of the toner, considering the compounding amount thereof, with respect to toluene, There is a method of adjusting the solubility by examining the solubility and appropriately selecting the constituent material based on the result. Further, a method of controlling the kneading conditions at the time of toner production may be mentioned.

In the present invention, the wax contained in the toner is preferably a wax having an endothermic peak at 60 to 150 ° C. in DSC (differential scanning calorimetry) measurement, more preferably an endothermic peak of 75. To 140 ° C.

The waxes described above are preferable in order to balance good fixing property and anti-offset property.

In the present invention, a more preferable toner composition is a toner composition using a mixture of a polyester resin and a wax having an endothermic peak in DSC measurement of 123 to 150 ° C., or a styrene-acrylic resin. And a polyester resin and a wax having an endothermic peak at 60 to 100 ° C. in DSC measurement.

In the present invention, the above-mentioned toner is used for fixing the toner image on the recording material using the fixing device having the above-mentioned fixing roller. Among them, the above-mentioned toner has a contact angle with water of 65. Through 120 °
And contains a polyester resin as a binder resin,
The toluene insoluble content is 5 to 50% by mass, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 10 to 2 in the molecular weight distribution measurement by GPC.
000 is a toner containing a wax and having an endothermic peak in the DSC measurement of 60 to 150 ° C., which is a toner having a conventional problem. It was found that the problem of contamination of the recording material due to the contamination of the above can be solved, and more preferable results can be obtained in order to obtain a high-quality image having fine line reproducibility, resolution, halftone image quality, and separation nail marks for a long period of time. It was

The reason for this is that with the above configuration, heat and pressure are applied more uniformly on the recording material (unfixed image) having the toner image passing through the fixing device, while The phenomenon that the repulsive force of the toner with respect to the fixing roller is increased and the slipperiness of the toner with respect to the fixing roller is improved appears, and the toner on the recording material (unfixed image) having the toner image that has passed through the fixing roller is not It is presumed that the cause is that the toner preferentially adheres to the paper, and that when the toner is fixed on the paper, the anchoring effect of the toner on the paper acts more uniformly.

The above-mentioned effect is obtained at a process speed of 100.
To 250 mm / sec can be obtained. That is, the effect of the present invention can be obtained by forming an image (fixing a toner image) at a process speed within the above range using the fixing roller and toner described above.

In the image forming apparatus, since the fixing speed generally tends to control the process speed, it is important to use the fixing device which can realize the above process speed. In order to achieve the above process speed in the fixing device, it is important to use appropriate means, members, and constituent materials in terms of the heating capacity of the heating means used, the heat conductivity of the fixing roller, the layer thickness of the fixing roller, and the like. . Further, it is important to use a means or the like that can achieve the above process speed as other means or the like in the image forming apparatus other than the fixing device.

With respect to the toner used in the present invention, various constituent materials applicable in the present invention will be described in more detail below.

In the present invention, the polyester resin used as the binder resin of the toner is not particularly limited, and conventionally known polyester resins can be used. As the monomer constituting the polyester resin,
Conventionally known dihydric or higher alcohol components and divalent or higher acid components described below can be used, but the present invention is not limited thereto.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, dipropylene glycol,
Triethylene glycol, 1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
Pentaerythritol diallyl ether, trimethylene glycol, 2-ethyl-1,3-hexanediol,
Examples thereof include hydrogenated bisphenol A and diols such as bisphenol derivatives represented by the following formula (1).

[0056]

[Chemical 1] (In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2
It is -10. )

As the acid component, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid or acid anhydrides thereof, dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or these And aromatic dicarboxylic acids such as phthalic acid and terephthalic acid.

Further, trihydric or higher alcohols include glycerin, sorbit, sorbitan and the like, and trihydric and higher acids include trimellitic acid, pyromellitic acid and the like and acid anhydrides thereof.

The method for producing the polyester resin used in the present invention is not particularly limited, and a conventionally known production method can be applied.

In the present invention, a styrene-acrylic resin may be mixed with a polyester resin as a binder resin for the toner. In the present invention, the styrene-acrylic resin is not particularly limited, and a conventionally known styrene-acrylic resin can be used. As the monomer constituting the styrene-acrylic resin, the following conventionally known substances can be used, but the present invention is not limited thereto.

Examples of the above-mentioned monomer include styrene, o
-Methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chloro. styrene,
3,4-dichlorostyrene, m-nitrostyrene, o-
Styrene derivatives such as nitrostyrene and p-nitrostyrene; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate. , Stearyl methacrylate, phenyl methacrylate and other α-
Methylene aliphatic monocarboxylic acid esters; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate , Acrylic acid 2-
Acrylic esters such as chloroethyl and phenyl acrylate; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; acrolein; acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride, fumaric acid, Examples thereof include carboxyl group-containing vinyl monomers such as maleic acid and their monoesters such as methyl, ethyl, butyl and 2-ethylhexyl.

In the present invention, a combination of a styrene monomer, methacrylic or an acrylic monomer and a carboxyl group-containing monomer is preferable.

As the binder resin for the toner, in addition to the styrene-acrylic resin as the binder resin, a styrene-vinyl methyl ether copolymer, a styrene-butadiene copolymer, a styrene-vinyl methyl ketone copolymer are used. , Styrene-styrene copolymers of styrene and other vinyl monomers such as styrene-acrylonitrile-indene copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid, Phenolic resins, aliphatic or alicyclic hydrocarbon resins, petroleum resins, chlorinated paraffins, etc. can be mixed and used.

In the present invention, a charge control agent may be incorporated, if desired, and a conventionally known charge control agent is used. Charge control agents known in the art today include the following.

For example, organic metal complexes and chelate compounds are effective, and there are monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid type metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides and esters; and phenol derivatives such as bisphenol.

In the present invention, it is preferable to use an organometallic compound as the charge control agent, and particularly, one containing an organic compound rich in vaporization and sublimation as a ligand or counterion is useful. As such an organometallic compound, an azo metal complex compound is preferably used from the viewpoint of charging property. As the azo-based metal complex compound, JP-B-41-20
No. 153, No. 42-27596, and No. 44-6.
There are metal complexes of azo dyes described in JP-A-397, 45-26478 and the like. Especially dispersive
From the viewpoint of chargeability, the azo metal complex compound represented by the following general formula (2) is preferable, and among them, the azo metal complex compound having a central metal of iron is preferable. More preferably, an azo metal complex compound represented by the following general formula (3) is used.

[0067]

[Chemical 2] [In the formula, M represents a coordination center metal selected from the group consisting of Cr, Co, Ni, Mn, Fe, Ti and Al. Ar represents an aryl group which may have a substituent selected from the group consisting of a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms. Show. X,
X ′, Y and Y ′ represent —O—, —CO—, —NH— or —NR— (R is an alkyl group having 1 to 4 carbon atoms).
A ⁺ represents hydrogen, sodium ion, potassium ion, ammonium ion or aliphatic ammonium ion. ]

[0068]

[Chemical 3] Wherein, X ₁ and X ₂ are a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, X ₁
And X ₂ may be the same or different. m and m'represent an integer of 1 to 3. R ₁ and R ₃ are hydrogen atoms,
C1 to C18 alkyl, alkenyl, sulfonamide, mesyl, sulfonic acid, carboxyester, hydroxy, C1 to C18 alkoxy, acetylamino,
A benzoylamino group or a halogen atom, R ₁ and R ₃
May be the same or different. n and n'are 1
3 to 3 are shown. R ₂ and R ₄ represent a hydrogen atom or a nitro group. A ⁺ represents a cation ion selected from the group consisting of ammonium ion, hydrogen ion, sodium ion, potassium ion and mixed ions thereof. ]

The content of the azo metal complex compound is preferably 0.5 to 5 parts by mass, and particularly preferably 0.2 to 3 parts by mass, relative to 100 parts by mass of the binder resin. If the content of the azo metal complex compound in the toner is too large, the fluidity of the toner is deteriorated and fogging is likely to occur, while if it is too small, it is difficult to obtain a sufficient charge amount.

In the present invention, wax is added for the purpose of improving the offset resistance at the time of heat roll fixing and controlling the contact angle of the toner. The wax used in the present invention has an endothermic peak of 6 in DSC measurement.
Examples of waxes present at 0 to 150 ° C. include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax.

As the aliphatic hydrocarbon wax, for example, a low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or by a Ziegler catalyst under low pressure, an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer, A wax such as a synthetic hydrocarbon obtained from a distillation residue of a hydrocarbon obtained by the Arge method from a synthesis gas composed of carbon monoxide / hydrogen, or obtained by hydrogenating these can be used. Further, it is possible to use a product obtained by fractionating the hydrocarbon wax by using a press sweating method, a solvent method, vacuum distillation, or a fractional crystallization method.

An example of the aliphatic hydrocarbon wax is a DSC curve measured by a differential scanning calorimeter, which shows an endothermic onset temperature of 50 to 110 with respect to the endothermic peak at the time of temperature increase and the exothermic peak at the time of temperature decrease. Aliphatic hydrocarbon wax having an endothermic peak in the temperature range of 70 to 130 ° C. and a maximum exothermic peak at the time of lowering the peak temperature of the endothermic peak ± 9 ° C. Can be mentioned.

The hydrocarbon as a base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often two or more multi-component system), for example, the gintol method, the hydrocol method ( A fluidized catalyst bed is used), or an Arge process (using a fixed catalyst bed) that produces a large amount of waxy hydrocarbons is used to polymerize hydrocarbons having up to several hundred carbon atoms and alkylenes such as ethylene with a Ziegler catalyst. Hydrocarbons can be used. Also,
A wax synthesized by a method that does not depend on the polymerization of alkylene can be used.

Further, as the wax used in the present invention, an oxide of an aliphatic hydrocarbon wax such as an oxidized polyethylene wax, or a block copolymer thereof, a structure having an ester bond such as carnauba wax or montanic acid ester wax. The waxes mentioned above and those obtained by partially or completely deoxidizing esters such as deoxidized carnauba wax can be used.

Further, saturated straight-chain fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as blancinic acid, eleostearic acid and valinaric acid;
Saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol and melysyl alcohol; polyhydric alcohols such as sorbitol, linoleic acid amides,
Fatty acid amides such as oleic acid amide and lauric acid amide, saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylene Unsaturated fatty acid amides such as bisoleic acid amide, N, N'-dioleyl adipamide, N, N'-dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, N'-distearyl isophthalic acid Aromatic bisamides such as amides; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally referred to as metallic soap); aliphatic hydrocarbon waxes such as styrene and acrylic acid. Graft waxes grafted with vinyl monomers; partial esterification products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils, etc. You can

Further, examples of the wax-like substance used in the present invention include aliphatic alcohol wax and alkyl monocarboxylic acid wax. The aliphatic alcohol wax is represented by the following general formula (4). The alkyl monocarboxylic acid wax is represented by the following general formula (5).

[0077]

CH ₃ (CH ₂ ) _X CH ₂ OH (4) (In the formula, X represents an average value and is 20 to 250)

CH ₃ (CH ₂ ) _Y CH ₂ COOH (5) (wherein Y represents an average value and is 20 to 250)

The waxy substance used in the present invention may be added to the binder resin in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the binder resin. If the amount of wax added is too small, it will be difficult to adjust the contact angle with water, and if the amount of wax added is too large, the fluidity and durability of the toner will deteriorate.

The toner used in the present invention may contain a magnetic material, and examples of such a magnetic material include magnetite, ferrite and iron oxide. In addition, metals such as iron, cobalt and nickel, or aluminum, cobalt, and
Magnetic materials such as alloys of metals such as copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof may be appropriately used.

The magnetic material that can be contained is not particularly limited, but the average particle size is 0.1 to 2 μm.
m, preferably about 0.1 to 0.5 μm, and the amount contained in the toner is preferably about 20 to 200 parts by mass with respect to 100 parts by mass of the binder resin component. If necessary, a surface treatment agent such as a coupling agent may be used to make the surface hydrophobic.

Further, as the colorant which may be used in the toner used in the present invention, various colorants may be used depending on the color of the toner, and any suitable pigment or dye may be mentioned. Toner colorants are well known, and for example, pigments such as carbon black, aniline black, acetylene black, naphthol yellow, Hansa yellow,
Examples include rhodamine lake, alizanin lake, red iron oxide, phthalocyanine blue, induslen blue, and the like.

These can be used in an amount necessary and sufficient for maintaining the optical density of the fixed image, and can be 0. 1 to 20 parts by mass, preferably 2 to 1
The addition amount of 0 parts by mass is good. Further, a dye can be further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, methine dyes, etc., and the addition amount of 0.1 to 20 parts by mass, preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of the binder resin. Good.

In the toner of the present invention, the charging stability,
In order to improve developability, fluidity and durability, it is preferable to add an inorganic fine powder externally, and it is preferable to add silica fine powder as such an inorganic fine powder.

The silica fine powder used in the present invention is BE.
Specific surface area due to nitrogen adsorption measured by T method is 30 m ² / g
Those above (especially 50 to 400 m ² / g) give good results. It is preferable to use 0.01 to 8 parts by mass, preferably 0.1 to 5 parts by mass of fine silica powder with respect to 100 parts by mass of the toner.

Further, the silica fine powder used in the present invention may contain silicone varnish, various modified silicone varnishes, and various modified silicone varnishes for the purpose of hydrophobizing and controlling the charging property.
It is also preferable that the surface is treated with a treatment agent such as silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having a functional group, and other organosilicon compounds.

Further, as other additives, for example, lubricants such as Teflon (registered trademark), zinc stearate, polyvinylidene fluoride and the like can be used. Further, a polishing agent such as cerium oxide, silicon carbide, or strontium titanate can be used, and among them, strontium titanate is preferable. Alternatively, for example, a fluidity-imparting agent such as titanium oxide or aluminum oxide is used, and among them, a hydrophobic agent is particularly preferable. An appropriate amount of anti-caking agent, a conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide, tin oxide, or white and black fine particles having opposite polarities can be used as a developing property improver.

The toner of the present invention can be mixed with a carrier and used as a two-component developer composed of the toner and the carrier. As the carrier, all known carriers can be used. For example, powders having magnetism such as iron powder, ferrite powder and nickel powder, non-magnetic powders such as glass beads, etc. Examples include those treated with a resin, a vinyl resin, a silicone resin, or the like.

The toner according to the present invention is not particularly limited in its production method as long as it has the above-mentioned physical properties, but it can be produced by utilizing a so-called pulverization method.
That is, a binder resin, a pigment or dye as a colorant, a charge control agent, and other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and then a heat kneader such as a heating roll, a kneader or an extruder. Melt, knead, and knead using to dissolve or disperse the pigments or dyes in the resin to make them compatible with each other, cool and solidify, then pulverize and classify, and further add desired additives as needed. The toner according to the present invention can be obtained by sufficiently mixing with a mixer such as a mixer.

Preferred methods for measuring physical properties according to the present invention are shown below. In the examples described below, the results of measurement based on the following measuring method are shown.

(1) Method for measuring the surface roughness of the fixing roller Under normal conditions of normal temperature and normal humidity (23.5 ° C., 60%),
It is measured using a surface roughness meter SE3500 manufactured by Kosaka Laboratory. As a measurement condition, using a 2CR filter, C
UT OFF length 0.08mm, measurement length 2.5m
m, DriveSpeed is measured under the condition of 0.1 mm / sec.

(2) Method for measuring the surface resistance of the fixing roller Under normal conditions of normal temperature and normal humidity (23.5 ° C., 60%),
It is measured using Mitsubishi Yuka High Resistance Resistor Hiresta IP. As the measurement conditions, an IIA probe is used as the probe, and the applied voltage is 10 V and the application time is 10 seconds.

(3) Method for measuring contact angle of toner with water The toner is press-molded into pellets and dried at room temperature and normal humidity (2
Under an environmental condition (3.5 ° C., 60%), a contact angle with water is measured using a contact angle meter CX-A type manufactured by Kyowa Interface Science Co., Ltd.

(4) Method for Measuring Toluene Insoluble Content of Toner 1 g of the toner is weighed and put in a cylindrical filter paper (for example, No. 86R size (28 × 100 mm) manufactured by Toyo Filter Paper Co., Ltd.) and put on a Soxhlet extractor. 200 ml of toluene as a solvent
Extract for about 20 hours. At this time, extraction is performed using an oil bath whose temperature is controlled at about 160 ° C. at a reflux rate such that the extraction cycle of toluene is once every about 4 to 5 minutes. After the extraction, the cylindrical filter paper is taken out, dried and vacuum dried at 60 ° C. for 24 hours, and the cylindrical filter paper after the extraction is weighed to obtain the mass of toluene-insoluble matter in the toner.

The ratio of the toluene insoluble content of the toner is expressed by the following equation (where W ₁ g is the weight of the toner before extraction placed in the cylindrical filter paper and W ₂ g is the toluene insoluble content on the cylindrical filter paper after the extraction is completed). Calculated from 2).

[Equation 2] Toluene insoluble content of toner (mass%) = (W ₂ / W ₁ ) × 100 (2)

An example of the Soxhlet extraction device is shown in FIG. 3, and the extraction mechanism will be briefly described. The toluene 12 contained in the container 11 is heated by the heater 18 and vaporized, and the vaporized toluene is guided to the cooler 15 through the pipe 17. The cooler 15 is constantly cooled by the cooling water 16. Toluene cooled and liquefied by the cooler 15 accumulates in the storage part having the cylindrical filter paper 13, and when the liquid level of the toluene becomes higher than that of the middle pipe 14, the toluene is stored in the container 11 from the storage part.
Is discharged to. The toner contained in the cylindrical filter paper 13 is extracted by circulating toluene. And container 1
In 1, toner-soluble components of the toner are retained.

(5) Method for measuring molecular weight distribution by GPC The molecular weight distribution by GPC (gel permeation chromatography) is measured under the following conditions. That is, 40
The column is stabilized in a heat chamber at 0 ° C., and THF (tetrahydrofuran) as a solvent is flown through the column at this temperature at a flow rate of 1 ml / min.

After toluene was evaporated to dryness from the toluene-soluble portion of the toner obtained when the ratio of the toluene-insoluble portion of the toner was measured in the above (4), it was dissolved in THF and left standing overnight, Filter with a 2 μm filter and use the filtrate as a sample. The measurement is performed by injecting 50 to 200 μl of a THF sample solution of the toluene-soluble portion of the toner adjusted to a sample concentration of 0.05 to 0.6% by mass.

In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared using several kinds of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical
Co. Made or manufactured by Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 ×
10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ ,
5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.
It is suitable to use 6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

The column is 10 ^{3 to} 2 × 10 ^6.
It is advisable to combine a plurality of commercially available polystyrene gel columns in order to accurately measure the molecular weight region of
ters μ-styragel 500, 10
Combination of 3, 104, 105 and s made by Showa Denko KK
hodex KA-801, 802, 803, 804,
A combination of 805, 806 and 807 is preferable.

(6) DSC measuring method ASTM D3418-8 using a differential scanning calorimeter (DSC measuring device), DSC-7 (manufactured by Perkin Elmer).
Measure according to 2. A measurement sample is accurately weighed in an amount of 2 to 10 mg, preferably 5 mg. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and a temperature rising rate is 10 ° C / m in a measurement temperature range of 30 to 200 ° C.
The measurement is performed at room temperature and normal humidity. During this temperature raising process, an endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. is obtained.

[0101]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.

<Fixing Roller Manufacturing Example 1> Outer Diameter of Central Part 3
100 parts by mass of PTFE and 5 parts by mass of carbon black were applied by a spray gun onto an aluminum cored bar having an inner diameter of 9.95 mm and an inner diameter of 36 mm in the central part, and baked and cooled in a furnace in an atmosphere of about 380 ° C. After that, the above-mentioned PTFE
Was sprayed with a spray gun, baked in a furnace at an atmosphere of about 380 ° C., then cooled, and the surface was polished so that the outer diameter of the central part was 4
0.0 mm, the inner diameter of the central portion is 36 mm, the surface roughness is 2.5 μm, the surface resistance is 5.0 × 10 ⁹ Ω, and the area existence ratio of voids in the cross section of the fixing roller is 8
A fixing roller 1 having a ratio of 1.0% was obtained.

<Fixing Roller Manufacturing Example 2> Outer Diameter of Central Part 3
100 parts by mass of PTFE and 5 parts by mass of carbon black were applied by a spray gun onto an aluminum cored bar having an inner diameter of 9.95 mm and an inner diameter of 36 mm in the central part, and baked and cooled in a furnace in an atmosphere of about 380 ° C. After that, the above-mentioned PTFE
Was sprayed with a spray gun, baked in a furnace at an atmosphere of about 380 ° C., then cooled, and the surface was polished so that the outer diameter of the central part was 4
0.0 mm, the inner diameter of the central part is 36 mm, the surface roughness is 0.1 μm, the surface resistance is 1.0 × 10 ⁸ Ω, and the area existence ratio of voids in the cross section of the fixing roller is ⁸ mm.
A fixing roller 2 having a ratio of 1.0% was obtained.

<Fixing Roller Manufacturing Example 3> Outer Diameter of Central Part 3
100 parts by mass of PTFE and 5 parts by mass of carbon black were applied by a spray gun onto an aluminum cored bar having an inner diameter of 9.95 mm and an inner diameter of 36 mm in the central part, followed by firing and cooling in a furnace at an atmosphere of about 380 ° C. After that, the above-mentioned PTFE
Was sprayed with a spray gun, baked in a furnace at an atmosphere of about 380 ° C., then cooled, and the surface was polished so that the outer diameter of the central part was 4
0.0 mm, the inner diameter of the central portion is 36 mm, the surface roughness is 3.5 μm, the surface resistance is 1.0 × 10 ¹³ Ω, and the area existence ratio of voids in the cross section of the fixing roller is 8
A fixing roller 3 having a ratio of 1.0% was obtained.

<Fixing Roller Manufacturing Example 4> Outer Diameter of Central Part 3
100 parts by mass of PTFE and 5 parts by mass of carbon black were applied by a spray gun on an aluminum cored bar having an inner diameter of 9.95 mm and an inner diameter of 34 mm at the central part, and baked and cooled in a furnace at an atmosphere of about 380 ° C. After that, the above-mentioned PTFE
Was sprayed with a spray gun, baked in a furnace at an atmosphere of about 380 ° C., then cooled, and the surface was polished so that the outer diameter of the central part was 4
0.0 mm, the inner diameter of the central part is 34 mm, the surface roughness is 2.3 μm, the surface resistance is 8.0 × 10 ⁹ Ω, and the area existence ratio of voids in the cross section of the fixing roller is 7
A fixing roller 4 having a rate of 2.25% was obtained.

<Fixing Roller Manufacturing Example 5> Outer Diameter of Central Part 3
100 parts by mass of PTFE and 5 parts by mass of carbon black were applied by a spray gun onto an aluminum cored bar having an inner diameter of 9.95 mm and an inner diameter of 38 mm in the central part, followed by firing and cooling in a furnace at an atmosphere of about 380 ° C. After that, the above-mentioned PTFE
Was sprayed with a spray gun, baked in a furnace at an atmosphere of about 380 ° C., then cooled, and the surface was polished so that the outer diameter of the central part was 4
0.0 mm, the inner diameter of the central part is 38 mm, the surface roughness is 2.6 μm, the surface resistance is 1.0 × 10 ¹⁰ Ω, and the area existence ratio of voids in the cross section of the fixing roller is 9
The fixing roller 5 having 0.25% is obtained.

<Fixing Roller Manufacturing Example 6> Outer Diameter of Central Part 3
100 parts by mass of PTFE and 5 parts by mass of carbon black were applied by a spray gun onto an aluminum core metal having an inner diameter of 9.95 mm and an inner diameter of 30 mm at the center, and after firing in an atmosphere of about 380 ° C., it was cooled. After that, the above-mentioned PTFE
Was sprayed with a spray gun, baked in a furnace at an atmosphere of about 380 ° C., then cooled, and the surface was polished so that the outer diameter of the central part was 4
The inner diameter of the central portion is 30 mm, the surface roughness is 2.7 μm, the surface resistance is 1.0 × 10 ¹⁰ Ω, and the area existence ratio of voids in the cross section of the fixing roller is 56.2.
A fixing roller 6 of 5% was obtained.

<Fixing Roller Manufacturing Example 7> Outer Diameter of Central Part 3
100 parts by mass of PTFE and 5 parts by mass of carbon black were applied by a spray gun on an aluminum cored bar having an inner diameter of 9.95 mm and an inner diameter of 39.1 mm in the central part, followed by firing and cooling in a furnace at an atmosphere of about 380 ° C. Then, further PT
FE is applied with a spray gun, baked in a furnace of an atmosphere of about 380 ° C., then cooled, and the surface is polished so that the outer diameter of the central portion is 40.0 mm and the inner diameter of the central portion is 39.1 mm,
Surface roughness is 2.4 μm and surface resistance is 7.0 × 10.
^A fixing roller 7 having a resistance of ⁹ Ω and an area existence ratio of voids in the cross section of the fixing roller of 95.55% was obtained.

<Fixing Roller Manufacturing Example 8> Outer Diameter of Central Part 3
9.95 mm, PTFE 100 parts by mass and carbon black 25 on an aluminum core metal having an inner diameter of 36 mm at the center
Parts by mass were applied with a spray gun, and baked and cooled in a furnace having an atmosphere of about 380 ° C. Then, further PTF
E was applied by a spray gun, baked in a furnace of about 380 ° C., then cooled, and the surface was polished to have a center outer diameter of 40.0 mm and a center inner diameter of 36 mm. Is 0.02 μm and the surface resistance is 1.0 × 10 ⁶ Ω
Thus, a fixing roller 8 having a void area presence ratio of 81.0% in the cross section of the fixing roller was obtained.

<Fixing Roller Manufacturing Example 9> Outer Diameter of Central Part 3
100 parts by mass of PTFE and 1 part by mass of carbon black were applied onto an aluminum cored bar having an inner diameter of 9.95 mm and an inner diameter of 36 mm at the center by a spray gun, followed by firing and cooling in a furnace at an atmosphere of about 380 ° C. After that, the above-mentioned PTFE
Was sprayed with a spray gun, baked in a furnace at an atmosphere of about 380 ° C., then cooled, and the surface was polished so that the outer diameter of the central part was 4
0.0 mm, the inner diameter of the central portion is 36 mm, the surface roughness is 4.5 μm, the surface resistance is 1.0 × 10 ¹⁵ Ω, and the area existence ratio of voids in the cross section of the fixing roller is 8
A fixing roller 9 of 1.0% was obtained.

A list of manufacturing examples of the fixing roller is as follows.

[0112]

[Table 1]

[0113] <Toner Production Example 1> ・ Binder resin   Polyester resin (ethylene glycol-bisphenol A-trimerit Acid-polyester resin consisting of terephthalic acid) 100 parts by mass 2 parts by mass of charge control agent (metal complex type monoazo type compound represented by the following formula)

[Chemical 6] Carbon black 4 parts by mass Wax (polypropylene wax having endothermic peak at 136 ° C. in DSC measurement) 3 parts by mass

After thoroughly mixing the above materials with a blender,
The mixture was kneaded by a twin-screw kneading extruder set to 130 ° C.
The obtained kneaded product was cooled, coarsely pulverized by a cutter mill and then finely pulverized by a fine pulverizer using a jet stream, and the finely pulverized powder obtained was classified to have a volume average particle diameter of 7.55 μm.
A toner classification product A was obtained. To 100 parts by mass of the obtained black fine powder toner classified product A, 0.6 parts by mass of negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner A. It was The contact angle of toner A with water is 102 °, the toluene insoluble content of toner A is 16% by mass, and the molecular weight distribution of toner A is measured by GPC. The weight average molecular weight (Mw) and the number average are Molecular weight (Mn)
The ratio (Mw / Mn) was 30. After that, toner A and silicone resin coated carrier (300/350 m
and two-component type developer A to obtain a two-component developer A.

<Toner Production Example 2> Kneading condition is 100 ° C.
A volume average particle size of 7.4 was obtained in the same manner as in Production Example 1 except that the kneading was carried out by the twin-screw kneading extruder set to 1.
A toner classification product B of 5 μm was obtained. To 100 parts by mass of the obtained black fine powder toner-classified product B, negatively charged hydrophobic dry colloidal silica (BET specific surface area of 300 m ² / g) was added.
Toner B was obtained by adding 6 parts by mass and mixing with a Henschel mixer. The contact angle of toner B with water is 72 °, the toluene insoluble content of toner B is 8% by mass, and the molecular weight distribution of toner B is measured by GPC. The weight average molecular weight (Mw) and the number average are Molecular weight (M
The ratio (n /) (Mw / Mn) was 15. Then, toner B and a silicone resin coated carrier (300/35
0 mesh) to give a two-component developer B.

<Toner Production Example 3> Kneading conditions are set to 160 ° C.
A volume average particle size of 7.6 was obtained in the same manner as in Production Example 1 except that the kneading was carried out by the twin-screw kneading extruder set to.
A toner classification product C of 4 μm was obtained. To 100 parts by mass of the obtained black fine powder toner classified product C was added negatively charged hydrophobic dry colloidal silica (BET specific surface area of 300 m ² / g) of 0.
6 parts by mass were added and mixed with a Henschel mixer to obtain a toner C. The contact angle of toner C with water was 116 °, the toluene-insoluble content of toner C was 45% by mass, and the molecular weight distribution of toner C was measured by GPC. The weight average molecular weight (Mw) and number average were measured. The ratio (Mw / Mn) to the molecular weight (Mn) was 1950. After that, the toner C and the silicone resin coated carrier (30
0/350 mesh) to give a two-component developer C.

<Production Example 4 of Toner> The same as Production Example 1 except that the wax was changed to 3 parts by mass of polypropylene wax having an endothermic peak in DSC measurement of 144 ° C. Using the same material and in the same manner as in Production Example 1, the volume average particle size was 7.41.
A toner classified product D having a size of μm was obtained.

The obtained black fine powder toner classified product D10
In 0 parts by mass, negatively charged hydrophobic dry colloidal silica (B
0.6 parts by mass of ET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner D. Toner D
Has a contact angle of 107 ° with water, and the toluene insoluble content of Toner D was measured to be 18% by mass. The molecular weight distribution of Toner D was measured by GPC. The weight average molecular weight (Mw) and the number average molecular weight ( Mn) ratio (Mw)
/ Mn) was 35. Then, Toner D and a silicone resin coated carrier (300/350 mesh) were mixed to prepare a two-component developer D.

<Manufacturing Example 5 of Toner> Binder resin is prepared in the same manner as in Manufacturing Example 1. 1) Polyester resin (polyester resin consisting of ethylene glycol-bisphenol A-trimellitic acid-terephthalic acid) 90 parts by mass. ) Styrene-acrylic resin (styrene-acrylic resin consisting of styrene-2 ethylhexyl acrylate) is changed to 10 parts by mass, and wax is changed to 3 parts by mass of carnauba wax having an endothermic peak in DSC measurement of 83 ° C. Except that the same materials as in Production Example 1 were used and in the same manner as in Production Example 1 with a volume average particle size of 7.48.
A toner classification product E having a size of μm was obtained.

The obtained black fine powder toner classified product E10
In 0 parts by mass, negatively charged hydrophobic dry colloidal silica (B
0.6 parts by mass of ET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner E. Toner E
Has a contact angle with water of 82 °, and the toluene-insoluble content of Toner E was measured to be 33% by mass.
When the molecular weight distribution was measured by GPC, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw /
Mn) was 1170. Thereafter, Toner E and a silicone resin coated carrier (300/350 mesh) were mixed to prepare a two-component developer E.

<Manufacturing Example 6 of Toner> Binder resin is prepared in accordance with Manufacturing Example 5: 1) Polyester resin (polyester resin consisting of ethylene glycol-bisphenol A-trimellitic acid-terephthalic acid) 80 parts by mass. ) Styrene-acrylic resin (styrene-acrylic resin consisting of styrene-2 ethylhexyl acrylate) Except for changing to 20 parts by mass, the same material as in Production Example 5 was used, and the same method as in Production Example 1 was used. Volume average particle size 7.52
A toner classified product F having a size of μm was obtained.

The obtained black fine powder toner classified product F10
In 0 parts by mass, negatively charged hydrophobic dry colloidal silica (B
0.6 parts by mass of ET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner F. Toner F
Has a contact angle of 95 ° with water, and the toluene insoluble content of Toner F was measured to be 27% by mass.
When the molecular weight distribution was measured by GPC, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw /
Mn) was 1050. Then, Toner F and a silicone resin coated carrier (300/350 mesh) were mixed to prepare a two-component developer F.

<Manufacturing Example 7 of Toner> Binder resin is prepared in accordance with Manufacturing Example 5: 1) Polyester resin (polyester resin consisting of ethylene glycol-bisphenol A-trimellitic acid-terephthalic acid) 70 parts by mass. ) Styrene-acrylic resin (styrene-acrylic resin composed of styrene-2 ethylhexyl acrylate) The same material as in Production Example 5 was used and the same method as in Production Example 1 was used except that the amount was changed to 30 parts by mass. Volume average particle size 7.41
A toner classification product G having a size of μm was obtained.

The obtained black fine powder toner classified product G10
In 0 parts by mass, negatively charged hydrophobic dry colloidal silica (B
0.6 parts by mass of ET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner G. Toner G
Has a contact angle with water of 104 °, and the amount of toluene-insoluble matter in Toner G was measured to be 22% by mass. When the molecular weight distribution of Toner G was measured by GPC, the weight average molecular weight (Mw) and the number average molecular weight ( Mn) ratio (Mw)
/ Mn) was 930. Then, Toner G and a silicone resin coated carrier (300/350 mesh) were mixed to prepare a two-component developer G.

<Production Example 8 of Toner> The same as Production Example 6, except that the wax is changed to 3 parts by mass of carnauba wax having an endothermic peak in DSC measurement of 70 ° C. Using the same material and in the same manner as in Production Example 1, the volume average particle size was 7.52.
A toner classification product H having a size of μm was obtained.

Toner classification product H10 of the obtained black fine powder
In 0 parts by mass, negatively charged hydrophobic dry colloidal silica (B
0.6 parts by mass of ET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner H. Toner H
Has a contact angle with water of 87 °, and the toluene-insoluble content of Toner H was measured to be 31% by mass.
When the molecular weight distribution was measured by GPC, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw /
Mn) was 1250. Then, Toner H and a silicone resin-coated carrier (300/350 mesh) were mixed to prepare a two-component developer H.

<Production Example 9 of Toner> The same material as in Production Example 1 except that 3 parts by mass of polypropylene wax having an endothermic peak in DSC measurement of 136 ° C. is not used. In the same manner as in Production Example 1 except that the kneading was performed using a twin-screw kneading extruder having kneading conditions set to 80 ° C.
A toner classified product I having a volume average particle diameter of 7.47 μm was obtained.

The obtained black fine powder toner classified product I10
In 0 parts by mass, negatively charged hydrophobic dry colloidal silica (B
ET specific surface area 300 m ^{2 /} g) 0.05 part by mass,
Toner I was obtained by mixing with a Henschel mixer. The contact angle of the toner I with water was 61 °, and the toluene insoluble content of the toner I was measured to be 3% by mass.
When the molecular weight distribution was measured by GPC, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw /
Mn) was 5. Thereafter, Toner I and a silicone resin coated carrier (300/350 mesh) were mixed to prepare a two-component developer I.

<Production Example 10 of Toner> The same materials as in Production Example 1 were used except that the charge control agent was changed to 2 parts by mass of a chromium complex of ditertiarybutylsalicylic acid complex in Production Example 1. In the same manner as in 1, the volume average particle diameter is 7.51.
A toner classification product J having a size of μm was obtained.

Toner classification product J10 of the obtained black fine powder
In 0 parts by mass, negatively charged hydrophobic dry colloidal silica (B
Toner J was obtained by adding 1.0 part by mass of ET specific surface area 300 m ^{2 /} g) and mixing with a Henschel mixer. Toner J
Has a contact angle of 125 ° with water, and the toluene-insoluble content of Toner J is measured to be 55% by mass. The molecular weight distribution of Toner J is measured by GPC. The weight-average molecular weight (Mw) and number-average molecular weight ( Mn) ratio (Mw)
/ Mn) was 2100. After that, Toner J and silicone resin coated carrier (300/350 mesh)
To prepare a two-component developer J.

<Production Example 11 of Toner> The same as Production Example 1 except that the wax is changed to 3 parts by weight of carnauba wax having an endothermic peak in DSC measurement of 55 ° C. Using the same material and in the same manner as in Production Example 1, the volume average particle size was 7.58.
A toner classification product K having a size of μm was obtained.

Toner classification product K10 of the obtained black fine powder
In 0 parts by mass, negatively charged hydrophobic dry colloidal silica (B
0.6 parts by mass of ET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner K. Toner K
Has a contact angle of 60 ° with water, and the toluene-insoluble content of Toner K was measured to be 18% by mass.
When the molecular weight distribution was measured by GPC, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw /
Mn) was 35. Thereafter, Toner K and a silicone resin-coated carrier (300/350 mesh) were mixed to prepare a two-component developer K.

<Toner Production Example 12> The same as Production Example 1 except that the wax is changed to 3 parts by mass of polypropylene wax having an endothermic peak in DSC measurement of 156 ° C. Using the same material and in the same manner as in Production Example 1, the volume average particle size was 7.51.
A toner classification product L having a size of μm was obtained.

Toner classification product L10 of the obtained black fine powder
In 0 parts by mass, negatively charged hydrophobic dry colloidal silica (B
0.6 parts by mass of ET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner L. Toner L
Has a contact angle of 128 ° with water, and the toner insoluble content of Toner L was measured to be 21% by mass. The molecular weight distribution of Toner L was measured by GPC. The weight average molecular weight (Mw) and number average molecular weight ( Mn) ratio (Mw)
/ Mn) was 33. Then, the toner L and a silicone resin coated carrier (300/350 mesh) were mixed to obtain a two-component developer L.

<Manufacturing Example 13 of Toner> In comparison with Manufacturing Example 1, the binder resin was changed to 100 parts by mass of styrene-acrylic resin (styrene-acrylic resin consisting of styrene-2 ethylhexyl acrylate). Using the same material as in Production Example 1 and in the same manner as in Production Example 1 gave a volume average particle size of 7.46.
A toner classification product M having a size of μm was obtained.

The obtained black fine powder toner classified product M10
In 0 parts by mass, negatively charged hydrophobic dry colloidal silica (B
0.6 parts by mass of ET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner M. Toner M
Has a contact angle of 131 ° with water, and has a toluene insoluble content of Toner M of 22% by mass. When the molecular weight distribution of Toner M is measured by GPC, the weight average molecular weight (Mw) and the number average molecular weight ( Mn) ratio (Mw)
/ Mn) was 1400. After that, toner M and silicone resin coated carrier (300/350 mesh)
To obtain a two-component developer M.

<Embodiment 1> In this embodiment, a commercially available copying machine Canon GP-405 (process speed 210 mm
/ Sec) is modified so that a two-component developer can be used, and a copying machine in which the fixing roller of GP-405 is replaced with the fixing roller 1 manufactured in the fixing roller manufacturing example 1 is used as an image forming apparatus. did. Then, the two-component developer A is applied to the image forming apparatus to apply normal temperature and normal humidity (23.5 ° C., 6
Under the environmental condition of 0%), 20,000 sheets of printed images were evaluated for durability. The durability evaluation items and measurement procedure are shown below.

1) Measurement of warming-up time of fixing roller 2) Evaluation method of fixing property 3) Evaluation method of anti-offset property 4) Occurrence of paper jam around fixing device 5) By paper passing (image output durability) Contamination of the recording material due to contamination of the fixing roller 6) Fine line reproducibility 7) Resolution 8) Halftone image quality 9) Nail mark measurement method on a solid black image The above evaluation and measurement were performed by the following procedure.

1) Measurement of warming-up time of the fixing roller After printing at room temperature and normal humidity (23.5 ° C., 60%), the copying machine used for evaluation of durability was left overnight with the power outlet unplugged. Immediately after turning on the power outlet, turn on the main switch of the main body of the copying machine used for image evaluation and durability evaluation.
Then, measure the time until the main body of the copier becomes operable. It is determined that the shorter the warm-up time of the fixing roller, the better the warm-up time of the fixing roller. The evaluation criteria of the warm-up time of the fixing roller are as shown in the following table.

[0140]

[Table 2]

2) Evaluation Method of Fixing Property The fixing property is evaluated by the image forming durability evaluation by leaving the copying machine used for the image forming durability evaluation in a low temperature and low humidity environment (15 ° C., 10%) overnight. The copying machine and the fixing device therein were completely adapted to the environment of low temperature and low humidity, and 200 copies of the copied image were continuously taken, and the 200th copy of the copied image was used for the evaluation of the fixing property. The fixing property was evaluated by rubbing the image with sillbon paper 5 times in a reciprocating manner under a load of about 100 g, and peeling of the image was evaluated by a reduction rate (%) of reflection density. Therefore, as the value of the reduction rate of the reflection density after rubbing (image density reduction rate) is larger, the rate of peeling of the image due to rubbing is higher, and the toner fixability is worse. The evaluation criteria for fixability are as shown in the following table.

[0142]

[Table 3]

3) Evaluation method of anti-offset property The anti-offset property is based on whether the toner once taken in the cleaning wave during continuous copying is transferred to the fixing roller and contaminates the copy. did. The evaluation method was as follows: In the low temperature and low humidity environment (15 ° C., 10%) of the copying machine used for the image development durability evaluation, 200 consecutive copy images were taken, and then the copy images were taken at 30 second intervals. 3 each
It was taken up to a minute and it was examined whether image contamination occurred. When image contamination occurred, the evaluation of offset resistance was rated as ×, and when image contamination did not occur, evaluation of offset resistance was rated as ○.

4) Occurrence of Paper Jam Around the Fixing Device During Image Display Endurance If a paper jam occurs around the fixing device, it is determined that there is a paper jam around the fixing device. When the paper jam of No. 1 did not occur, it was evaluated that the paper jam around the fixing device did not occur.

5) Contamination of recording material due to contamination of the fixing roller due to paper passing (image output durability) A solid white copy image is formed using A4 paper after the image output durability is completed, and a solid white copy image (recording material) is formed. ) The stain adhering to the top was measured as reflectance using a reflection densitometer TC-6MC manufactured by Tokyo Denshoku. Absolute difference between the reflectance of dirt adhering to the solid white copy image (recording material) after passing through the fixing device and the reflectance between the paper (recording material) passed through the copying machine and the paper of the same lot (recording material). The value was evaluated as the amount of image smearing on the white background portion of the recording material. The evaluation value of the contamination of the recording material due to the contamination of the fixing roller due to the paper passing (image output durability) is such that the value of the difference in reflectance becomes larger as the degree of contamination of the white background portion of the recording material increases.
It is as shown in the following table.

[0146]

[Table 4]

6) Fine line reproducibility Fine line reproducibility was measured by the following method after image formation and durability. That is, an image obtained by copying an original of a fine line having a width of 100 μm accurately under appropriate copying conditions is used as a measurement sample, and a Luzex 450 particle analyzer is used as a measuring device. Take a measurement. At this time, since the measurement position of the line width has unevenness in the width direction of the thin line image of the toner, the average line width of the unevenness is used as the measurement point. From this, the fine line reproducibility value (%) is calculated by the following formula (3).

[Equation 3]

Here, the closer the fine line reproducibility value is to 100%, the more faithful the copied image is due to the line width of the original.
Therefore, the closer the fine line reproducibility value is to 100%, the higher the image quality. The evaluation standard of fine line reproducibility was based on the absolute value of the value (%)-100 (%) of the fine line reproducibility of the copied image. The evaluation criteria for fine line reproducibility are as shown in the following table.

[0149]

[Table 5]

7) Resolving power The resolving power of the copied image was evaluated by the following method after completion of image formation and durability. A pattern composed of five thin lines having the same line width and spacing, and 2.8, 3.2, 3.
6, 4.0, 4.5, 5.0, 5.6, 6.3, 7.
Create an original image that looks like there are 1, 8.0, 9.0, 10.0 lines. The original document having these 12 types of line images is copied under appropriate copying conditions and the image is observed with a magnifying glass. The number of images (lines / mm) in which fine lines are clearly separated is used as an evaluation means. I was there. here,
The larger the number of images (lines / mm) in which fine lines are clearly separated, the better the level of blurring of the line image of the copied image, the higher the resolution, and the higher the image quality. The evaluation criteria of resolution are as shown in the following table.

[0151]

[Table 6]

8) Halftone image quality Halftone image quality is as follows. After completion of image output, an image obtained by copying a 0.3 halftone full-face solid document on A4 paper is used to obtain 10 arbitrary images using a Macbeth reflection densitometer. The density was measured, and the difference between the maximum value and the minimum value of the obtained image density was used as the evaluation standard. The halftone image quality here means the halftone density uniformity of the halftone image obtained by copying. Poor halftone density uniformity (poor halftone image quality)
Means that the halftone image obtained by copying has unevenness in light and shade, and there is a large variation in halftone image density. The evaluation standard of halftone image quality is
It is as shown in the following table.

[0153]

[Table 7]

9) Method for measuring nail marks on a solid black image. Under normal conditions of normal temperature and normal humidity (23.5 ° C., 60%), images were printed and the copying machine used for durability evaluation was left overnight with the power outlet unplugged. Immediately after turning on the power outlet, turn on the main switch of the main body of the copying machine used for the image evaluation and durability evaluation.
Immediately after the main body becomes operable, five A3 solid black images are continuously taken and the length of the fixing nail mark generated at the leading end on the fifth A3 solid black image is measured. It is indicated that the longer the length of the fixing nail mark generated at the tip of the fifth A3 solid black image, the worse the nail mark level in the solid black image. The evaluation criteria for the level of nail marks in a solid black image are shown below.

[0155]

[Table 8]

The conditions of durability evaluation and the results of durability evaluation in this example are shown in Tables 9 and 10.

<Embodiment 2> In this embodiment, except that the process speed is changed to 240 mm / sec,
The same evaluation as in Example 1 was performed. The conditions of the durability evaluation and the results of the durability evaluation in this example are shown in Tables 9 and 10.

<Embodiment 3> In this embodiment, except that the process speed is changed to 120 mm / sec,
The same evaluation as in Example 1 was performed. The conditions of the durability evaluation and the results of the durability evaluation in this example are shown in Tables 9 and 10.

<Embodiment 4> In this embodiment, the fixing roller 1 is used.
The same evaluation as in Example 1 was carried out except that the fixing roller 2 was used instead of. The conditions of the durability evaluation and the results of the durability evaluation in this example are shown in Tables 9 and 10.

<Embodiment 5> In this embodiment, the fixing roller 1 is used.
The same evaluation as in Example 1 was carried out except that the fixing roller 3 was used instead of. The conditions of the durability evaluation and the results of the durability evaluation in this example are shown in Tables 9 and 10.

<Embodiment 6> In this embodiment, the fixing roller 1 is used.
The same evaluation as in Example 1 was carried out except that the fixing roller 4 was used instead of. The conditions of the durability evaluation and the results of the durability evaluation in this example are shown in Tables 9 and 10.

<Embodiment 7> In this embodiment, the fixing roller 1 is used.
The same evaluation as in Example 1 was performed except that the fixing roller 5 was used instead of the fixing roller 5. The conditions of the durability evaluation and the results of the durability evaluation in this example are shown in Tables 9 and 10.

<Embodiment 8> In this embodiment, except that the two-component developer B is used instead of the two-component developer A,
The same evaluation as in Example 1 was performed. The conditions of the durability evaluation and the results of the durability evaluation in this example are shown in Tables 9 and 10.

<Embodiment 9> In this embodiment, except that the two-component developer C is applied instead of the two-component developer A,
The same evaluation as in Example 1 was performed. The conditions of the durability evaluation and the results of the durability evaluation in this example are shown in Tables 9 and 10.

Example 10 In this example, the same evaluation as in Example 1 was performed except that the two-component developer D was used instead of the two-component developer A. The conditions of the durability evaluation and the results of the durability evaluation in this example are shown in Tables 9 and 10.

<Example 11> In this example, the same evaluation as in Example 1 was performed except that the two-component developer E was used instead of the two-component developer A. The conditions of the durability evaluation and the results of the durability evaluation in this example are shown in Tables 9 and 10.

<Example 12> In this example, the same evaluation as in Example 1 was performed except that the two-component developer F was used instead of the two-component developer A. The conditions of the durability evaluation and the results of the durability evaluation in this example are shown in Tables 9 and 10.

<Example 13> In this example, the same evaluations as in Example 1 were performed except that the two-component developer G was used instead of the two-component developer A. The conditions of the durability evaluation and the results of the durability evaluation in this example are shown in Tables 9 and 10.

Example 14 In this example, the same evaluation as in Example 1 was performed except that the two-component developer H was used instead of the two-component developer A. The conditions of the durability evaluation and the results of the durability evaluation in this example are shown in Tables 9 and 10.

<Comparative Example 1> In this comparative example, the same evaluation as in Example 1 was performed except that the process speed was changed to 80 mm / sec. The conditions of the durability evaluation and the results of the durability evaluation in this comparative example are shown in Tables 9 and 10.

Comparative Example 2 In this comparative example, except that the process speed is changed to 300 mm / sec,
The same evaluation as in Example 1 was performed. The conditions of the durability evaluation and the results of the durability evaluation in this comparative example are shown in Tables 9 and 10.

Comparative Example 3 In this comparative example, the fixing roller 1 is used.
The same evaluation as in Example 1 was performed except that the fixing roller 8 was used instead of the fixing roller 8. The conditions of the durability evaluation and the results of the durability evaluation in this comparative example are shown in Tables 9 and 10.

Comparative Example 4 In this comparative example, the fixing roller 1
The same evaluation as in Example 1 was carried out except that the fixing roller 9 was used instead of. The conditions of the durability evaluation and the results of the durability evaluation in this comparative example are shown in Tables 9 and 10.

<Comparative Example 5> In this comparative example, the fixing roller 1 is used.
The same evaluation as in Example 1 was carried out except that the fixing roller 6 was used instead of. The conditions of the durability evaluation and the results of the durability evaluation in this comparative example are shown in Tables 9 and 10.

Comparative Example 6 In this comparative example, the fixing roller 1 is used.
The same evaluation as in Example 1 was carried out except that the fixing roller 7 was used instead of. The conditions of the durability evaluation and the results of the durability evaluation in this comparative example are shown in Tables 9 and 10.

Comparative Example 7 In this comparative example, except that the two-component developer I is used instead of the two-component developer A,
The same evaluation as in Example 1 was performed. The conditions of the durability evaluation and the results of the durability evaluation in this comparative example are shown in Tables 9 and 10.

Comparative Example 8 In this comparative example, except that the two-component developer J is applied instead of the two-component developer A,
The same evaluation as in Example 1 was performed. The conditions of the durability evaluation and the results of the durability evaluation in this comparative example are shown in Tables 9 and 10.

Comparative Example 9 In this comparative example, the two-component developer K is used instead of the two-component developer A,
The same evaluation as in Example 1 was performed. The conditions of the durability evaluation and the results of the durability evaluation in this comparative example are shown in Tables 9 and 10.

Comparative Example 10 In this comparative example, the same evaluation as in Example 1 was performed except that the two-component developer L was used instead of the two-component developer A. The conditions of the durability evaluation and the results of the durability evaluation in this comparative example are shown in Tables 9 and 10.

Comparative Example 11 In this comparative example, the same evaluation as in Example 1 was carried out except that the two-component developer M was used instead of the two-component developer A. The conditions of the durability evaluation and the results of the durability evaluation in this comparative example are shown in Tables 9 and 10.

[0181]

[Table 9]

[0182]

[Table 10]

[0183]

According to the present invention, a fixing device having at least a fixing roller having a heating means and a pressure roller in pressure contact with the fixing roller is used, and a recording material having a toner image is provided between the rollers of the fixing device. Process speed 1
When the toner image is heated and fixed on the recording material by passing the toner image at a speed of 00 to 250 mm / sec, the fixing roller has a surface roughness of 0.05 to 4.0 μm and a surface resistance of 1.
A fixing roller having a cross-sectional area ratio of voids of 60 to 95% is used, and a toner forming a toner image has a contact angle with water of 65 to 10 × 10 ^{7 to} 1.0 × 10 ¹⁴ Ω. Since the toner of 120 ° is used, a high quality image is provided for a long period of time, and the fixing device is contaminated even after fixing a large number of transfer materials without impairing the fixing performance and the anti-offset performance. It is possible to provide a fixing method and a toner used in this method, in which a defective image due to the above does not occur, and the warming-up time of the fixing roller can be shortened.

In the present invention, when the surface roughness of the fixing roller is 0.15 to 3.0 μm, the balance between the frictional state between the recording material and the fixing member and the pressure applied to the recording material becomes better. , More effective in improving the image quality after fixing.

Further, in the present invention, when the surface resistance of the fixing roller is 1.0 × 10 ^{9 to} 1.0 × 10 ¹² Ω, the deterioration of the image quality after fixing and the increase of the charge of the fixing roller are suppressed, and the fixing roller after fixing is suppressed. It is more effective in improving the image quality.

Further, in the present invention, when the contact angle of the toner with water is 80 to 110 °, it is more effective in preventing the offset and sufficiently fixing the toner image.

Further, in the present invention, when the area existence ratio of the voids in the cross section of the fixing roller is 75 to 85%, the warm-up time of the fixing roller is shortened, and the temperature decrease of the fixing roller during continuous sheet feeding is prevented. Is more effective in doing.

In the present invention, it is more effective for the toner to contain the polyester resin as the binder resin in adjusting the contact angle of the toner with water.

Further, in the present invention, when the toluene insoluble content of the toner is 5 to 50% by mass, more preferably 10 to 35% by mass, the balance between the viscosity and the elasticity of the toner is improved, and the fixability and offset resistance are improved. It is more effective in achieving both.

In the present invention, in the measurement of the molecular weight distribution of the toner by GPC, when the weight average molecular weight is Mw and the number average molecular weight is Mn, Mw / Mn, which is the ratio of the weight average molecular weight to the number average molecular weight, is 10 to. 200
When it is 0, more preferably 20 to 1600, it is more effective in satisfying both the fixability and the offset resistance, as in the case of the toluene-insoluble matter described above.

Further, in the present invention, the toner contains a wax, and when the wax has a heat absorption peak in the DSC measurement of 60 to 150 ° C., more preferably 75 to 140 ° C., the fixing property and the offset resistance are It is more effective in achieving both sex.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a cross-sectional view of a central portion of a fixing roller used in the present invention.

FIG. 2 is a diagram showing an example of a fixing device used in the present invention.

FIG. 3 is a diagram showing an example of a Soxhlet extraction apparatus used for measurement of toluene insoluble matter.

[Explanation of symbols]

1 fixing roller 2 Fixing roller surface layer 3 heating means 4 pressure roller 5 core metal 11 containers 12 Toluene 13 Cylindrical filter paper 14 Middle tube 15 Cooler 16 cooling water 17 tubes 18 Heater (hot water) N Nip part P recording material

Claims (21)

[Claims] 1. A fixing device having at least a fixing roller having a heating means and a pressure roller in pressure contact with the fixing roller is used, and a recording material having a toner image is provided between the rollers of the fixing device at a process speed of 100 to 250 m.
A fixing method in which the toner image is heated and fixed on the recording material by passing it at m / sec, wherein the surface roughness of the fixing roller is 0.05 to 4.0 μm, and the surface resistance of the fixing roller is 1.0 x 10 ^{7 to} 1.0
× 10 ¹⁴ Ω, and the area existence ratio of voids in the cross section of the fixing roller was 6
The fixing method is characterized in that the toner forming the toner image has a contact angle with water of 65 to 120 °. 2. The fixing method according to claim 1, wherein the surface roughness of the fixing roller is 0.15 to 3.0 μm. 3. The surface resistance of the fixing roller is 1.0 × 1.
3. The fixing method according to claim 1, wherein the fixing method is ^{09 to} 1.0 × 10 ¹² Ω. 4. The fixing method according to claim 1, wherein a contact angle of the toner with water is 80 to 110 °. 5. The fixing method according to claim 1, wherein an area existence ratio of voids in a cross section of the fixing roller is 75 to 85%. 6. The fixing method according to claim 1, wherein the toner contains a polyester resin as a binder resin. 7. The toluene insoluble content of the toner is 5 to 5
The fixing method according to claim 6, wherein the fixing amount is 0% by mass. 8. The fixing method according to claim 6, wherein the toluene insoluble content of the toner is 10 to 35% by mass. 9. In the molecular weight distribution measurement of the toner by GPC, when the weight average molecular weight is Mw and the number average molecular weight is Mn, Mw / Mn, which is the ratio of the weight average molecular weight to the number average molecular weight, is 10 to 2000. The fixing method according to claim 1, wherein the fixing method is present. 10. In the molecular weight distribution measurement of the toner by GPC, when the weight average molecular weight is Mw and the number average molecular weight is Mn, Mw / Mn which is a ratio of the weight average molecular weight to the number average molecular weight is 20 to 1600. The fixing method according to claim 1, wherein the fixing method is present. 11. The toner contains wax, and the wax has an endothermic peak of 60 to 150 in DSC measurement.
A wax which is present at 0 ° C.
11. The fixing method according to any one of items 1 to 10. 12. The toner contains a wax, and the wax has an endothermic peak of 75 to 140 in DSC measurement.
A wax which is present at 0 ° C.
12. The fixing method according to any one of items 1 to 11. 13. A fixing device having at least a fixing roller having a heating means and a pressure roller in pressure contact with the fixing roller is used, and a recording material having a toner image between the rollers of the fixing device is processed at a process speed of 100 to 250.
When the toner image is heated and fixed on the recording material, the fixing roller has a surface roughness of 0.05 to 4.0 μm and a surface resistance of 1.0 × 10 ^{7 to} 10 μm. a 1.0 × 10 ¹⁴ Ω, and a toner area existence ratio of voids in the cross-section is used in the fixing method using the fixing roller is 60 to 95%, a contact angle of 65 to 120 ° against water Toner characterized by being present. 14. The contact angle of the toner with water is 80.
14. The toner according to claim 13, wherein the toner is at an angle of 110 to 110 degrees. 15. The toner according to claim 13, wherein the toner contains a polyester resin as a binder resin. 16. The toner insoluble matter in the toner is in the range of 5 to 50% by mass.
The toner according to any one of 1. 17. The toner insoluble content of the toner is 10 to 35% by mass.
6. The toner according to any one of 6 above. 18. In the molecular weight distribution measurement of the toner by GPC, when the weight average molecular weight is Mw and the number average molecular weight is Mn, Mw / Mn, which is the ratio of the weight average molecular weight to the number average molecular weight, is 10 to 2000. The toner according to any one of claims 13 to 17, wherein the toner is present. 19. In the measurement of the molecular weight distribution of the toner by GPC, when the weight average molecular weight is Mw and the number average molecular weight is Mn, Mw / Mn, which is the ratio of the weight average molecular weight to the number average molecular weight, is 20 to 1600. The toner according to any one of claims 13 to 18, wherein the toner is present. 20. The toner contains wax, and the wax has an endothermic peak of 60 to 150 in DSC measurement.
A wax which is present at 0 ° C.
20. The toner according to any one of 3 to 19. 21. The toner contains a wax, and the wax has an endothermic peak of 75 to 140 in a DSC measurement.
A wax which is present at 0 ° C.
21. The toner according to any one of 3 to 20.