JP3267509B2 - Image forming method and heat fixing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat fixing method using an electrostatic image developing toner suitable for heat fixing used in electrophotography, electrostatic recording and magnetic recording, and an image forming method.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
It is known in a number of ways, as described in Japanese Patent Publication No. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is developed using toner, and if necessary, using direct or indirect means. After transferring a toner image onto a recording material such as paper, the toner image is fixed by heating, pressure, heating and pressurizing, or solvent vapor to obtain a copy.
Then, the toner remaining on the photosensitive member without being transferred to the recording material is cleaned by various methods, and the above-described steps are repeated.

Further, a method of forming a general full-color image will be described. The photoreceptor on the photoreceptor drum is uniformly charged by the primary charger, image exposure is performed by laser light modulated by the magenta image signal of the original, an electrostatic latent image is formed on the photoreceptor drum, and magenta toner is retained. Developing the electrostatic latent image by a magenta developing device,
A magenta toner image is formed. Next, the magenta toner image developed on the photosensitive drum by the transfer charger is transferred to the conveyed transfer material using direct or indirect means.

On the other hand, the photosensitive drum after the development of the electrostatic latent image is neutralized by a static eliminator, cleaned by a cleaning unit, and charged again by a primary charger. A cyan toner image is formed and the cyan toner image is transferred to a transfer material on which the magenta toner image has been transferred. Further, the same procedure is performed sequentially for the yellow toner image and the black toner image, and
The color toner image is transferred to a transfer material. A full-color image is formed by fixing the transfer material having the four color toner images by the action of heat and pressure by a fixing roller.

[0005] In recent years, such devices have begun to be used not only as office work copiers for copying original manuscripts, but also as printers as personal computer outputs or personal copies for individuals.

[0006] In addition to such fields represented by laser beam printers, the development of plain paper faxes using a basic engine has been rapidly developing.

[0007] Therefore, smaller, lighter and faster,
Higher image quality and higher reliability are being demanded, and machines are being configured with simpler elements in various respects. As a result, the performance required of the toner has become higher, and if the performance of the toner cannot be improved, a better machine cannot be realized. In recent years, demands for color copying have rapidly increased along with various copying needs, and further higher image quality and higher resolution are desired in order to more faithfully copy an original color image. From these viewpoints, the toner used in the color image forming method needs to have good meltability and color mixing when heat is applied, and has a low softening point, a low melt viscosity, and a high sharpness. It is preferable to use a toner having a melt property.

That is, by using the toner having the high sharp melt property, the color reproduction range of a copy can be widened and a color copy faithful to the original image can be obtained.

However, the color toner having such a high sharp melt property generally has a high affinity with the fixing roller, and tends to be easily offset to the fixing roller during fixing.

Particularly, in the case of a fixing device in a color image forming apparatus, since a magenta toner, a cyan toner, a yellow toner, and a black toner are formed on a transfer material, a plurality of toner layers are formed. It tends to occur.

Conventionally, for the purpose of preventing toner from adhering to the surface of a fixing roller, for example, the roller surface is formed of a material having excellent releasability with respect to toner such as silicone rubber or fluororesin. In order to prevent this, the roller surface is coated with a thin film of a highly releasable liquid such as silicone oil or fluorine oil.

Although this method is extremely effective in preventing the offset of the toner, it has a problem that the fixing device is complicated because a device for supplying the liquid for preventing the offset is required. Needless to say, this oil application causes peeling between the layers constituting the fixing roller, resulting in a disadvantage that the life of the fixing roller is shortened. Further, as a transfer material for fixing a toner image using these fixing devices, various papers, coated papers, and plastic films are generally used. In particular, the necessity of using a transparency film using an overhead projector as a transfer material for presentations has recently been required. Particularly in the case of transparency films, unlike paper, the oil absorption capacity is low, so the currently obtained copied transparency films are inevitably greasy due to oil application, and the quality of the obtained images remains a major problem. . Further, there is a great possibility that oil such as silicone oil evaporates due to heat, thereby contaminating the inside of the machine and causing a problem of processing collected oil.

Therefore, a method of adding a release agent such as low molecular weight polyethylene or low molecular weight polypropylene to the toner, from the viewpoint of supplying the anti-offset liquid during heating from the toner instead of using the silicone oil supply device. Has been proposed. However, if such an additive is added in a large amount in order to obtain a sufficient effect, filming on the photoreceptor and contamination of the surface of the toner carrier such as a carrier or a sleeve are deteriorated, and the image is deteriorated, which is a practical problem. Become. Accordingly, a device that supplies a small amount of release oil to the toner while adding a small amount of release agent to the toner to such an extent that the image is not deteriorated, or a device using a member such as a web that takes up the offset toner or a cleaning device, or cleaning. A cleaning device using a pad is also used in combination.

However, particularly in the field of full color, in the conventional means for containing a release agent in a toner, when a transparency film is used as a transfer material, high crystallization of the release agent and a difference in refractive index from the resin are caused. This causes a problem that the transparency and haze of the image after fixing are slightly reduced.

It is known that a wax is contained in a toner as a release agent. This technology is, for example,
No. 2-3304, JP-B-52-3305 and JP-A-57-52574.

JP-A-3-50559 and JP-A-2-50559
JP-A-79860, JP-A-1-109359, JP-A-62-14166, JP-A-61-27355
No. 4, JP-A-61-94062, JP-A-61-94062
-138259, JP-A-60-252361, JP-A-60-252360 and JP-A-60-252.
Japanese Patent No. 217366 discloses a technique for containing waxes.

Waxes are used to improve the toner's anti-offset properties at low and high temperatures and to improve the fixability at low temperatures. However, there is a problem that the developing property is deteriorated when exposed to heat as in the case of the temperature rise, or the wax is migrated to the toner surface when the toner is left for a long time, so that the developing property is deteriorated.

None of the conventional toners satisfies all of these aspects, causing some problems. For example, high-temperature offset and developability are excellent but low-temperature fixability is not sufficient; low-temperature offset and low-temperature fixability are excellent, but blocking resistance is slightly inferior, and developability decreases when the temperature in the machine is increased. There were adverse effects; inadequate offset resistance at low and high temperatures; and extremely poor OHP transparency.

Particularly with respect to the transparency of OHP, a proposal is made to add a crystallization nucleating agent to the wax in order to reduce the crystallization of the wax itself (JP-A-4-149559 and JP-A-4-107467); Proposal of using a material having a low degree of crystallinity (Japanese Patent Application Nos. Hei 3-091108 and Hei 3-242397) A substance having good compatibility with a binder and a lower melt viscosity than the binder is used in the binder. To improve the surface smoothness of the toner layer after fixing (Japanese Patent Application No. 3-21265).
No. 2 gazette).

One release agent having relatively good transparency and low-temperature fixing performance is montan wax, which is a mineral wax.

The following structural formula is used as the montan wax.

[0022]

[Outside 1] (Wherein, R represents a hydrocarbon group having 28 to 32 carbon atoms,
(wherein n represents an integer) having a molecular weight of about 800, which is disclosed in JP-A-1-185660, JP-A-1-185661, JP-A-1-185662, and JP-A-1-185666. JP-A-1-23
No. 8672 proposes this. However, none of these is fully satisfactory in terms of transparency and haze (cloudiness) of OHP.

On the other hand, in order to inhibit the crystallinity of the release agent itself, Japanese Patent Application No. 5-11851 discloses the use of an ester wax in which the structural symmetry of the release agent itself is broken.
7, Japanese Patent Application No. 5-126180, Japanese Patent Application No. 5-126180.
No. 126181, and fairly good results have been obtained.

However, even in recent full-color fixing devices, high durability and high reliability have been demanded, and the improvement of the binder resin and release agent of the toner alone without the improvement of the fixing device has led to the reduction of the image area from a high image area to a low image. It is difficult to stably realize an image forming method applicable to an area image and even a full-color OHP over a long period of time, and further improvement is desired.

Japanese Patent Application Laid-Open No. 4-35657 (corresponding to US Pat. No. 5,391,450) discloses that a heating member which is in pressure contact with a toner image is formed of a fluorine-containing substance, and a non-polar Mw of 500 to 1500 is formed in the toner. It has been shown to contain wax. However, the non-polar wax such as paraffin wax described here has poor compatibility with the binder resin of the toner (small SP value), and tends to cause a decrease in transmittance in full-color transparency. Was not what you get.

JP-A-6-123994 (corresponding to European Patent Publication No. 0587540) discloses that a wax having Mw / Mn of 1.5 or less is contained in order to achieve both blocking resistance and fixability. I have. However,
What is described here is the content of the magnetic toner. As in the present invention, the SP value of the wax contained in the color toner, which is an important factor of the transparency in full-color transparency, is indicated, and the toner is used. The value of the contact angle between the image and the heating member pressed against the image is not shown.

[0027]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method which solves the above-mentioned problems.

It is an object of the present invention to provide a heating method and an image forming method which are excellent in low-temperature fixability to a recording material and anti-offset properties over a long period of time.

It is a further object of the present invention to provide a heat fixing method and an image forming method capable of fixing without applying a large amount of oil or without applying any oil.

It is a further object of the present invention to provide a heat fixing method and an image forming method capable of obtaining a high quality full color OHP having excellent transparency.

[0031]

The above object is achieved by the following constitution of the present invention.

That is, the present invention provides a latent image forming step of forming an electrostatic latent image on a latent image holding member,
A developing step of developing the electrostatic latent image with color toner, a transferring step of transferring the toner image to a recording material, and a heat fixing device having a heating member for pressing the toner image transferred to the recording material against the toner image In the image forming method having a fixing step of fixing to the recording material according to, the color toner has at least a binder resin, a colorant and a wax,
The wax has a weight average molecular weight / number average molecular weight (Mw / Mn) of 1.45 or less in a molecular weight distribution measured by GPC, and 8.4 to 10.5.
When the contact angle between the wax and the heating member at 100 ° C. is A and the contact angle between the wax and the heating member at 200 ° C. is B, the contact angles A and B relates to an image forming method characterized by satisfying the following relationship: 60 ° ≦ A ≦ 80 ° 10 ° ≧ BA−3 °

Further, the present invention relates to a heat fixing method for fixing a toner image formed by a color toner on a recording material to the recording material by a heat fixing device having a heating member for pressing the toner image against the toner image. , At least a binder resin, a colorant and a wax, wherein the wax has a molecular weight distribution measured by GPC,
Weight average molecular weight of 1.45 or less / number average molecular weight (Mw /
Mn), and has a solubility parameter of 8.4 to 10.5, and the contact angle between the wax and the heating member at 100 ° C. is A, Assuming that the contact angle at 200 ° C. is B, the contact angles A and B satisfy the following relationship: 60 ° ≦ A ≦ 80 ° 10 ° ≧ B−A ≧ 3 ° .

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive studies, the present inventors have found that as a wax to be contained in a toner, a weight average molecular weight (Mw) / number average in a molecular weight distribution measured by gel permeation chromatography (GPC). By using a wax having a molecular weight (Mn) of 1.45 or less and a solubility parameter of 8.4 to 10.5, the toner has excellent fluidity, and a uniform fixed image without gloss unevenness can be obtained. The heating member of the fixing device is hardly contaminated or deteriorated in storage stability, and has excellent fixing properties and light transmittance of a fixed image. The contact angle A between the wax and the heating member of the fixing device at 100 ° C. is 60 °.
When the angle is within the range of about 80 °, the wettability of the wax with respect to the heating member of the fixing device becomes appropriate. Therefore, when the toner is melted to form a full-color OHP having excellent transparency, a part or all of the wax is moderate. In addition to being able to form a full-color OHP without causing toner offset and exhibiting good low-temperature fixability, the difference between the contact angle A at 100 ° C. and the contact angle B at 200 ° C. It has been found that when the angle is in the range of 3 ° to 10 °, good offset resistance can be maintained and the life of the press-contact member can be extended.

Further, a winding type member cleaning pad such as a web which comes into contact with the surface of the heating member,
Since the cleaning member such as the cleaning roller does not consider the wettability of the toner, the toner residue that slightly adheres to the surface of the heating member may not be sufficiently removed. However, the cleaning member contacts the pressing member. 100 ° C. between the cleaning member and the wax contained in the toner
When the contact angle C is in the range of 0 ° to 60 °, the wax which has been finely dispersed or dissolved in the binder easily adheres to the cleaning member in the unfixed toner. It has been found that the offset toner can be removed in particular.

In the present invention, the contact angle was measured by forming a thin piece (about 5 mm thick) of the surface layer material of the press-contact member, and measuring the contact angle by a drop method using a CA-X type manufactured by Kyowa Interface Science.

In the present invention, when the contact angle between the wax contained in the toner and the heating member of the fixing device at 100 ° C. is A, and the contact angle at 200 ° C. is B, the contact angles A and B have the following relationship: ° ≦ A ≦ 80 ° 10 ° ≧ BA−3 °, and preferably, the following relationship 60 ° ≦ A ≦ 72 ° 9 ° ≧ BA ≧ 4 °. .

If the contact angle A is less than 60 °, the wax which has been finely dispersed in the unfixed toner or compatible with the binder is re-agglomerated, and the color reproducibility is reduced, or the transmittance of full-color OHP is reduced. Or If the contact angle A is larger than 80 °, it will not be possible to homogenize on the heating member, and as a result, uneven fixing and partial offset will occur, resulting in image defects.

When the contact angle BA is less than 3 °, the compatibility of the wax with the binder resin of the toner is reduced, so that the fixing area becomes narrower and the transparency of the full-color OHP is improved. When the value of the contact angle BA is larger than 10 °,
When a recording material having a large heat capacity such as cardboard or transparency is used, the temperature change of the heating member surface layer is large.As a result, the wettability of the wax to the pressure contact member changes, and a uniform glossy image is obtained. Will be gone.

If the contact angle C is larger than 60 °, the wettability of the cleaning member with respect to the toner is not sufficient, so that the toner residue adhered to the surface of the heating member cannot be effectively removed from the offset toner. .

The wax contained in the toner used in the present invention has a weight average molecular weight (Mw) / number average molecular weight (Mw) of 1.45 or less, preferably 1 in molecular weight distribution by GPC using a double column. .30 or less is more preferable in terms of uniformity of a fixed image, good transferability of toner, and prevention of contamination of a contact charging unit for charging by contacting the photoreceptor.

When the value of Mw / Mn of the wax exceeds 1.45, the fluidity of the toner decreases,
Gloss unevenness of a fixed image is apt to occur, and further, the transferability of the toner is deteriorated and the contact charging member is likely to be contaminated.

In the present invention, the molecular weight distribution of the wax is measured by GPC using a double column under the following conditions.

(GPC measurement conditions) Apparatus: GPC-150C (manufactured by Waters) Column: GMH-HT 30 cm double (manufactured by Tosoh Corporation) Temperature: 135 ° C Solvent: o-dichlorobenzene (0.1% ionol added) Flow rate: 1.0 ml / min Sample: Inject 0.4 ml of 0.15% sample

The molecular weight of the sample is measured and the molecular weight of the sample is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. In addition, Mark-Hou
The molecular weight is calculated by converting to polyethylene using a conversion formula derived from the win viscosity formula.

The solubility parameter (SP value) of the wax used in the present invention is preferably in the range of 8.4 to 10.5, more preferably 8.5 to 10.0. S
When a wax having a P value of less than 8.4 is used, the compatibility with the binder resin to be used is poor, so that it is difficult to obtain good dispersion in the binder resin. Sufficient permeability of the sheet cannot be obtained. When a wax having an SP value of more than 10.5 is used, the toner tends to be blocked when the toner is stored for a long period of time, and the compatibility between the binder resin and the wax is too good. Thus, it is difficult to form a sufficient release layer between the toner binder resin layer and the toner, and an offset phenomenon is easily caused.

[0047] In the present invention, the solubility parameter (SP) value of wax scan utilized the additive property of atomic groups Fed
ors method (Polym. Eng. Sci., 14).
(2) 147 (1974)).

In order to obtain a sufficiently transparent OHP image with a low heat capacity of the fixing device, it is important to reduce the crystallinity of the wax contained in the toner. There are some undissolved toner grain boundaries that did not dissolve even after normal fixing,
Due to the irregular reflection of light, the crystallinity of the wax layer may reduce the effective light transmission, resulting in a reduction in haze. Furthermore, even if the components mixed in the toner are sufficiently dissolved at the time of fixing, if the difference in the refractive index between the melted toner layer and the wax layer formed between the fixing members is large, this also causes irregular reflection of light. It is not preferable because it causes.

An increase in the irregular reflection of light leads to a decrease in the brightness of the projected image and a decrease in the sharpness of the color. In particular, when a reflective overhead projector is used, this problem is further increased than when a transmissive overhead projector is used.

That is, in order to lower the crystallinity of the wax, it is important to lower the crystallinity of the wax alone. Furthermore, in order to prevent unmelted toner grain boundaries from being present in the toner fixing layer, it is necessary to adjust the glass transition temperature (Tg) of the binder resin and the melting point (mp) of the wax as much as possible. Particularly, a material having a small enthalpy of fusion (ΔH), which is the latent heat of wax, is particularly preferable. Further, it is preferable to appropriately adjust the difference in solubility parameter (SP) between the binder resin and the wax in order for the molten wax layer to quickly move between the binder resin layer and the fixing member to form an anti-offset layer.

From the above viewpoint, preferred examples of the present invention will be described in detail below.

In the present invention, polyester resins, styrene-acrylic resins, epoxy resins, or styrene-butadiene resins are preferably used as binder resins for toners. Those having similar rates are preferred.

As a method of measuring the refractive index, a vertical (20 to 3)
A solid sample having a size of 0) × width (8) × thickness (3 to 10) was prepared, and then a small amount of bromonaphthalene was applied to the prism surface in order to improve the adhesion to the prism surface. A method of placing a solid sample on a sample and measuring the refractive index is exemplified.
As a measuring device, for example, Atago's Appe refractometer 2
T.

The difference in the refractive index between the binder resin and the wax is 0.18 or less at a temperature of 25 ° C., more preferably 0.18 or less.
A value of 10 or less is particularly effective. If the difference in refractive index exceeds 0.18, the transparency of the OHP image is likely to be reduced, and a halftone projected image is not preferable because the brightness becomes low.

The melting point of the wax used in the present invention is 3
The temperature is preferably from 0 to 150 ° C, more preferably from 50 to 120 ° C. The melting point of the wax is 3
When the temperature is lower than 0 ° C., the blocking resistance of the toner, the suppression of sleeve contamination at the time of copying a large number of sheets, and the prevention of contamination of the photoreceptor are likely to deteriorate. If the melting point of the wax exceeds 150 ° C., excessive energy is required for uniform mixing with the binder resin in the production of the toner by the pulverization method, and the homogenization of the binder resin in the production of the toner by the polymerization method is also required. In addition, since the size of the apparatus is increased due to the increase in viscosity or the amount of compatibility is limited, it is not preferable because it becomes difficult to contain a large amount.

In the present invention, the melting point of the wax is AS
The temperature was defined as a temperature of a main peak value in an endothermic curve measured according to TM D3418-8.

The measurement according to ASTM D3418-8 is performed by using, for example, DSC-7 manufactured by PerkinElmer. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. An aluminum pan was used as a sample, an empty pan was set as a control, and the temperature was raised at a rate of 10 ° C / min. At a temperature in the range of 20 to 200 ° C.

The melt viscosity at 100 ° C. of the wax used in the present invention is preferably 1 to 50 mpa · s, more preferably 3 to 30 mpa · s.
A wax compound having ec is particularly preferred.

The melt viscosity of the wax is 1 mpa · sec.
If it is lower, when the toner layer is thinly coated on the sleeve by a toner layer thickness regulating member that regulates the toner layer thickness by an elastic force such as an elastic blade in a one-component developing method, the sleeve is contaminated by mechanical shearing force. When the toner is developed using the carrier in the two-component developing method, the toner tends to be damaged due to the shear force between the toner and the carrier, and the external additive is easily buried or the toner is crushed. When the melt viscosity of the wax exceeds 50 mPas · sec, when producing the toner using the polymerization method, the viscosity of the dispersoid is too high, and it is easy to obtain a toner having a fine particle diameter having a uniform particle diameter. And the toner tends to have a wide particle size distribution.

In the present invention, the melt viscosity of the wax can be measured by a method using a cone plate type rotor (PK-1) with VT-500 manufactured by HAAKE.

The Vickers hardness of the wax used in the present invention is preferably in the range of 0.3 to 5.0, and more preferably 0.5 to 3.0.

A toner containing a wax having a Vickers hardness lower than 0.3 is liable to be crushed at a cleaning portion of a copying machine in copying a large number of sheets, easily causing toner fusion on the drum surface, and consequently causing black streaks on an image. In addition to the above, in addition to the above, when multiple image samples are stored while being superposed, toner is transferred to the surface, so-called show-through tends to occur, which is not preferable. A toner containing a wax having a Vickers hardness of more than 5.0 requires a fixing device to be used at the time of heat fixing and requires a strong pressing force. When fixing is performed using the fixing device of (1), the offset resistance tends to decrease, which is not preferable.

In the present invention, the hardness of the wax is measured, for example, by using a Shimadzu Dynamic Ultra Micro Hardness Tester (DUH-2).
00). The measurement conditions were as follows. After displacing 10 μm at a load speed of 9.67 mg / sec under a load of 0.5 g using a Vickers indenter, holding for 15 seconds, and analyzing the dents on the sample, the Vickers hardness was determined. As a sample, a sample previously melted using a mold having a diameter of 20 mmφ is molded into a column having a thickness of 5 mm.

The crystallinity of the wax used in the present invention is preferably 10 to 50%, more preferably 20 to 35%.

When the crystallinity of the wax is less than 10%, the toner storage stability and fluidity are liable to deteriorate. When the crystallinity of the wax exceeds 50%, the transparency of the OHP image tends to deteriorate.

In the present invention, the excess of the crystal of the wax is measured by the following formula from the area ratio between the amorphous scattering peak and the crystal scattering peak without using a calibration curve.

[0067]

[Outside 2]

As a measuring device, for example, Rotorflex RU300 (Cu target, point focus, output 50 KV / 250 mA) manufactured by Rigaku Corporation can be mentioned. The measurement method used the transmission method-rotation method, and the measurement angle was 2θ.
= 5 to 35 °.

As described above, the wax used in the present invention has a suitable affinity for the binder resin, a high hydrophobicity and a low melting point in order to exhibit good low-temperature fixability and offset resistance. Those having low crystallinity are preferred.

Further, the wax used in the present invention is:
The molecular weight distribution measured by GPC has two or more peaks or one or more peaks and one or more shoulders, and in the molecular weight distribution, weight average molecular weight (Mw)
Is 200 to 2000, and the number average molecular weight (Mn) is 150
It is preferably from 2000 to 2000. It has been found that the above-mentioned molecular weight distribution may be achieved with either a single wax or a plurality of waxes, and as a result, crystallinity can be inhibited and transparency can be further improved. The method of blending two or more waxes is not particularly limited,
For example, a media disperser (ball mill, sand mill, attritor,
It is also possible to perform melt blending using an apex mill, a coball mill, or a handy mill, or to dissolve a wax to be blended in a polymerizable monomer and blend with a media type disperser. At this time, a pigment, a charge control agent, and a polymerization initiator may be used as additives.

The weight average molecular weight (Mw) of the wax is 20
0 to 2000, number average molecular weight (Mn) is 150 to 2
000 is preferred. More preferably, Mw is 2
00 to 1500, more preferably 300 to 100
0 Mn is 200 to 1500, more preferably 250
It is preferably from 1000 to 1,000. Mw of wax is 20
If it is less than 0 and Mn is less than 150, the blocking resistance of the toner decreases. Mw of wax is 2000, M
When n exceeds 2,000, the crystallinity of the wax itself is developed, and the transparency is reduced.

The wax is used in an amount of 1 to 40 parts by weight, preferably 2 to 30 parts by weight, based on 100 parts by weight of the binder resin of the toner.

In a pulverized toner production method in which a mixture having a binder resin, a colorant and a wax is melt-kneaded, cooled, pulverized and then classified to obtain toner particles, the amount of wax added is as follows.
It is preferable to use 1 to 10 parts by weight, more preferably 2 to 7 parts by weight, based on 100 parts by weight of the binder resin.

In a polymerized toner production method in which toner particles are directly obtained by superposing a mixture containing a polymerizable monomer, a colorant and a wax, the amount of the wax added depends on the amount of the polymerizable monomer or the polymerizable polymer. 2 to 40 parts by weight, more preferably 5 to 30 parts by weight, more preferably 10 to 10 parts by weight, based on 100 parts by weight of the resin synthesized by polymerization of the reactive monomer
It is preferred to use 20 parts by weight.

In the polymerized toner production method as compared with the pulverized toner production method, the wax used is lower in polarity than the binder resin, and the polymerization method in an aqueous medium makes it easy to encapsulate a large amount of wax inside the toner particles. In comparison, a large amount of wax can be used, which is particularly effective for the effect of preventing offset during fixing.

If the amount of the wax is less than the lower limit, the effect of preventing offset tends to decrease, and if the amount exceeds the upper limit, the anti-blocking effect is reduced and the anti-offset effect is liable to be adversely affected. In particular, in the case of a polymerization toner production method, a toner having a wide particle size distribution tends to be produced.

Examples of the wax that can be used in the present invention include paraffin wax, polyolefin wax, modified products thereof (eg, oxides and grafted products), higher fatty acids, metal salts thereof, and amide waxes. And ester-based waxes.

Higher quality full color OHP among them
Ester wax is particularly preferred in that an image can be obtained.

As the method for producing the ester wax preferably used in the present invention, for example, a synthesis method by an oxidation reaction, a synthesis from a carboxylic acid and a derivative thereof, and an ester group introduction reaction represented by a Michael addition reaction are used.
A particularly preferable method for producing the wax used in the present invention is a method using a dehydration condensation reaction of a carboxylic acid compound and an alcohol compound represented by the following formula (1) or a compound represented by the following formula (2) because of the variety of raw materials and ease of reaction. The reaction of a halide represented by) with an alcohol compound is particularly preferred.

[0080]

[Outside 3] In the formula, R ₁ and R _{2 each} represent an organic group such as an alkyl group, an alkenyl group, an aralkyl group and an aromatic group, and n represents an integer of 1 to 4. The organic group has 1 to 50 carbon atoms, preferably 2 to 2 carbon atoms.
More preferably, it is 4 to 30, more preferably 45, and more preferably linear.

In order to transfer the above-mentioned ester equilibrium reaction to the production system, the reaction is carried out using a large excess of alcohol or in a Dean-Stark water separator in an aromatic organic solvent capable of azeotropic distillation with water. . A method of synthesizing a polyester by adding a base as an acceptor of an acid by-produced in an aromatic organic solvent using an acid halide compound can also be used.

As the binder resin used in the toner of the present invention, the following binder resins can be used.

For example, homopolymers of styrene and its substituted substances such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene Copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Styrene such as vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer -Based copolymer; polyvinyl chloride; phenolic resin; natural modified phenolic resin; natural resin modified maleic resin; acrylic resin; methacrylic resin; polyvinyl acetate; silicone resin; polyester resin; polyurethane; polyamide resin; furan resin; A xylene resin; a polyvinyl butyral; a terpene resin; a cumarone indene resin; Preferred binders include styrene copolymers and polyester resins.

Examples of the comonomer for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and the like.
Double bonds such as dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide Or a substituted product thereof; for example, dicarboxylic acid having a double bond such as maleic acid, butyl maleate, methyl maleate, or dimethyl maleate and a substituted product thereof; for example, vinyl chloride, vinyl acetate, benzoic acid Vinyl esters such as vinyl acid; for example, ethylene-based olefins such as ethylene, propylene, and butylene; for example, vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; Vinyl ethyl ether, vinyl ethers such as vinyl isobutyl ether; such vinyl monomers are used alone or two or more.

In the present invention, the TH of the binder resin of the toner is
The number average molecular weight of the F-soluble component is 3,000 to 1,000,000.
00 is preferred.

The styrene-based polymer or styrene-based copolymer may be cross-linked, or may be a mixed resin of a cross-linked resin and a non-cross-linked resin.

As the crosslinking agent for the binder resin, a compound having two or more polymerizable double bonds may be mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butadiol dimethacrylate; Divinyl compounds such as, divinylaniline, divinylether, divinylsulfide, divinylsulfone; and 3
Compounds having at least two vinyl groups are used alone or as a mixture.

The amount of the cross-linking agent to be added is as follows.
0.001 to 10 parts by weight based on 00 parts by weight is preferred.

The toner of the present invention may contain a charge control agent.

The following substances control the toner to be negatively charged.

For example, organic metal compounds and chelate compounds are effective, and monoazo metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid-based metal compounds are preferably used. Further, aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, their anhydrides, their esters, their phenol derivatives such as bisphenol; urea derivatives; metal-containing salicylic acid-based compounds; Metal naphthoic acid compound; boron compound;
Quaternary ammonium salts; calixarenes; silicon compounds; styrene-acrylic acid copolymers; styrene-methacrylic acid copolymers; styrene-acrylic-sulfonic acid copolymers; and nonmetal carboxylic acid compounds.

The following substances control the toner to be positively charged.

For example, analogs of nigrosine; a modified product of a fatty acid metal salt; a guanidine compound; an imidazole compound; and a quaternary ammonium salt such as tributylbenzine ammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate. Lake pigments of onium salts such as phosphonium salts and quaternary ammonium salts or onium salts; triphenylmethane dyes and these lake pigments (for example, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid , Tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide;
Metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide and dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate and dicyclohexyltin borate.
These can be used alone or in combination of two or more. Among these, a charge control agent such as a nigrosine-based or quaternary ammonium salt is particularly preferably used from the viewpoint of good charge rising.

These charge control agents are used in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the resin component of the toner.
It is preferable to use 2 to 4 parts by weight.

As the colorant of the toner used in the present invention, carbon black, a magnetic substance, and a black colorant to which the following yellow colorant, magenta colorant or cyan colorant is used as a black colorant are used. You.

As the yellow colorant, a condensed azo compound, an isoindolinone compound, an anthraquinone compound,
An azo metal complex, a methine compound and an allylamide compound are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 9
3, 94, 95, 109, 110, 111, 128, 1,
29, 147, 168 or 180 is preferably used.

Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8; 2, 48; 3, 48; 4, 57; 1, 81; 1, 1
44, 146, 166, 169, 177, 184, 18
5, 202, 206, 220, 221 or 254 are preferably used.

As the cyan coloring agent, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds and basic dye lake compounds are used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 1
5: 3, 15: 4, 60, 62 or 66 can be particularly preferably used. These colorants can be used alone, in a mixture or in a solid solution state. In the present invention, the colorant is selected in consideration of hue angle, saturation, lightness, weather resistance, OHP transparency, and dispersibility in a toner.
In the toner used in the present invention, the amount of the colorant is preferably 1 to 20 parts by weight based on 100 parts by weight of the resin.

Further, in the present invention, the toner can be used as a magnetic toner further containing a magnetic material.
In this case, the magnetic material can also serve as a colorant.

In the present invention, examples of the magnetic material contained in the magnetic toner include iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel; and metals such as aluminum, cobalt and copper. Lead, magnesium, tin, zinc, antimony,
Alloys with metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof.

The magnetic material used in the present invention is more preferably surface-modified. When a magnetic toner is obtained by a polymerization toner production method, it is preferable to modify the surface with a surface modifier that is a substance that does not inhibit polymerization of the polymerizable monomer. Examples of such a surface modifier include silane cups. Ring agents and titanium coupling agents can be mentioned.

The ferromagnetic material as these magnetic materials has an average particle of preferably 2 μm or less, more preferably 0.1 μm or less.
It is preferably about 0.5 μm.

The amount of the magnetic material contained in the magnetic toner is preferably 10 to 2 parts by weight per 100 parts by weight of the resin component.
00 parts by weight, more preferably 20 to 100 parts by weight.

The magnetic material has a coercive force (Hc) of 20 to 300 Oersted when applied with 10 K Oersted.
It preferably has a saturation magnetization (σs) of 50 to 200 emu / g and a residual magnetization (σr) of 2 to 20 emu / g.

Additives for imparting various toner properties may have a particle size of not more than 1/5 of the volume average particle size of the toner particles from the viewpoint of durability when added to the toner or when added to the toner. preferable. The particle size of the additive means an average particle size obtained by observing the surface of the toner particles with an electron microscope. As additives for imparting these properties, for example, the following are used.

Examples of the fluidity-imparting agent include metal oxides such as silicon oxide, aluminum oxide and titanium oxide;
Carbon black; and carbon fluoride.
Each of these is preferably subjected to a hydrophobic treatment.

Examples of the abrasive include metal oxides such as strontium titanate, cerium oxide, aluminum oxide, magnesium oxide and chromium oxide; nitrides such as silicon nitride; carbides such as silicon carbide; and calcium sulfate and sulfuric acid. Metal salts such as barium and calcium carbonate are mentioned.

Examples of the lubricant include fluorine resin powders such as vinylidene fluoride and polytetrafluoroethylene, and fatty acid metal salts such as zinc stearate and calcium stearate.

As the charge controlling particles, for example, tin oxide,
Metal oxides such as titanium oxide, zinc oxide, silicon oxide and aluminum oxide; and carbon black.

These additives are preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner particles. These additives may be used alone or in combination of two or more.

Next, a method for producing the toner used in the present invention will be described. The toner used in the present invention can be manufactured using a pulverized toner manufacturing method and a polymerized toner manufacturing method.

In the present invention, a method for producing a pulverized toner includes a binder resin, a wax, a pigment as a colorant, a dye or a magnetic substance, a charge controlling agent, and other additives as necessary, such as a Henschel mixer and a ball mill. The resulting mixture is melt-kneaded using a hot kneader such as a heating roll, kneader, extruder and the like, and the metal components, pigments, dyes, and magnetic materials are mixed while the resin components are mutually compatible. The resulting kneaded material is cooled and solidified, and then pulverized and classified to obtain a toner.

Further, if necessary, the toner and the desired additives are sufficiently mixed by a mixer such as a Henschel mixer.
The toner used in the present invention can be obtained.

In the present invention, a method for producing a polymerized toner is, for example, a method for obtaining spherical toner particles by atomizing a molten mixture into air using a disk or a multi-fluid nozzle described in JP-B-56-13945; Japanese Patent Publication No. 36-
No. 10231, JP-A-59-53856 and JP-A-59-61842, in which toner particles are directly produced using a suspension polymerization method; An emulsion polymerization method typified by a dispersion polymerization method of directly producing toner particles using an aqueous organic solvent in which the resulting polymer is unnecessary or a soap-free polymerization method of directly polymerizing in the presence of a water-soluble polar polymerization initiator to produce toner particles; A method in which a primary polar emulsion polymerized particle is prepared in advance, and then a polar particle having an opposite charge is added thereto to produce a toner by a heteroaggregation method in which the particles are associated with each other.

Of these, the method of directly polymerizing a monomer composition containing at least a polymerizable monomer, a colorant and a wax to form toner particles is preferred.

However, in the dispersion polymerization method, the obtained toner shows an extremely sharp particle size distribution, but the selection of materials to be used is narrow, and the use of an organic solvent has an effect on waste solvent treatment and solvent flammability. From the viewpoint, the manufacturing apparatus is complicated and complicated. Therefore, a method of directly polymerizing a monomer composition containing at least a polymerizable monomer, a colorant and a wax in an aqueous medium to form toner particles is more preferable. However, the emulsion polymerization method represented by soap-free polymerization is effective because the particle size distribution of the toner is relatively uniform, but when the used emulsifier and the terminal of the initiator are present on the surface of the toner particles, the environmental characteristics are likely to deteriorate.

Therefore, in the present invention, a suspension polymerization method under normal pressure or under pressure, which can easily obtain a fine particle toner having a sharp particle size distribution, is particularly preferable. Further, a so-called seed polymerization method in which a monomer is further adsorbed on the obtained polymer particles and then polymerized using a polymerization initiator can also be suitably used in the present invention.

A preferred embodiment of the toner used in the present invention is a toner in which a wax is encapsulated in an outer shell resin layer by a tomographic plane measurement method using a transmission electron microscope (TEM). From the viewpoint of fixability, a large amount of wax needs to be contained in the wax toner, and it is preferable that the wax be included in the outer shell resin layer in terms of the storage stability and fluidity of the toner. When the toner is not included, the wax cannot be dispersed uniformly, and as a result, the particle size distribution is widened, and the toner is easily fused to the mounting. As a specific method of encapsulating the wax, the polarity of the material in the aqueous medium is set smaller than that of the main monomer in the wax, and then a small amount of a polar resin or monomer is added. A toner having a so-called core-shell structure in which wax is coated with an outer shell resin layer can be obtained. Control of the particle size distribution and the particle size of the toner can be achieved by changing the type or amount of a poorly water-soluble inorganic salt or dispersant acting as a protective colloid; mechanical device conditions, such as the peripheral speed of the rotor, the number of baths Stirring conditions such as stirring blade shape or container shape, or
By controlling the solid content concentration in the aqueous solution, the predetermined toner of the present invention can be obtained.

As a specific method for measuring the tomographic plane of the toner in the present invention, the toner can be obtained by sufficiently dispersing the toner in an epoxy resin curable at room temperature, and then curing it in an atmosphere at a temperature of 40 ° C. for 2 days. The cured product is stained with ruthenium tetroxide or, if necessary, with osmium tetroxide, and then a flaky sample is cut out using a microtome with diamond teeth, and a transmission electron microscope (TEM) is performed. The tomographic morphology of the used toner was measured. In the present invention, it is preferable to use a ruthenium tetroxide dyeing method in order to give a contrast between materials by utilizing a slight difference in crystallinity between the wax used and the resin constituting the outer shell resin layer.

In the case where the direct polymerization method is used in the toner production method of the present invention, the toner can be specifically produced by the following production method. A wax, a coloring agent, a charge control agent, a polymerization initiator, and other additives are added to the monomer, and the monomer system uniformly dissolved or dispersed by a disperser such as a homogenizer or an ultrasonic disperser is used as a dispersion stabilizer. Is dispersed in an aqueous phase containing the same using a conventional stirrer or a stirrer such as a homomixer or a homogenizer. Preferably, the stirring speed and time are adjusted so that the monomer droplets have the desired size of the toner particles, and the granulation is performed. After that, due to the action of the dispersion stabilizer, the particle state is maintained,
In addition, stirring may be performed to such an extent that settling of particles is prevented.
The polymerization is carried out at a polymerization temperature of 40 ° C. or higher, preferably 50 to 90 ° C. The temperature may be raised in the latter half of the polymerization reaction. The medium is preferably distilled off.
After completion of the reaction, the generated toner particles are collected by washing and filtration, and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer system.

When a toner is directly obtained by a polymerization method, the polymerizable monomer may be a styrene-based monomer such as styrene, o (m-, p-)-methylstyrene, m (p-)-ethylstyrene or the like. Body; methyl (meth) acrylate, (meth)
Ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate,
(Meth) such as dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate ) Acrylic ester monomers: Ene monomers such as butadiene, isoprene, cyclohexene, (meth) acrylonitrile and acrylamide are preferably used.

In the present invention, a polar resin is preferably used in combination to form a core-shell structure in the toner. Examples of polar resins such as polar polymers and polar copolymers that can be used in the present invention are given below.

Examples of the polar resin include a polymer of a nitrogen-containing monomer such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate or a copolymer of a nitrogen-containing monomer and a styrene-unsaturated carboxylic acid ester; Nitrile monomers such as vinyl chloride; halogen-containing monomers such as vinyl chloride; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated dibasic acids; unsaturated dibasic acid anhydrides; A polymer or a copolymer of the polymer and a styrene monomer; a polyester; an epoxy resin. More preferred are a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, a saturated polyester resin, and an epoxy resin.

Examples of the polymerization initiator include, for example, 2,2'-
Azobis- (2,4-dimethylvaleronitrile), 2,
2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2 '
Azo or diazo polymerization initiators such as azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butylhydro Peroxide, di-t-butyl peroxide,
Peroxide initiators such as dixyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis (4,4-t-butylperoxycyclohexyl) propane and tris- (t-butylperoxy) triazine A polymeric initiator having a peroxide in the side chain; persulfates such as potassium and ammonium persulfate; hydrogen peroxide; These can be used alone or in combination of two or more.

The polymerization initiator is preferably added in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer.

In the present invention, a known crosslinking agent or chain transfer agent may be added to control the molecular weight. The preferred addition amount is 0.001 to 15 parts by weight based on 100 parts by weight of the polymerizable monomer. Department.

In the present invention, a suitable inorganic compound or organic compound is used as a dispersion medium for producing a polymerization toner by a polymerization method using emulsion polymerization, dispersion polymerization, suspension polymerization, seed polymerization, or heteroaggregation. It is preferred to use a compound stabilizer. As a stabilizer for inorganic compounds,
For example, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica And alumina. As stabilizers for organic compounds,
For example, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and its salts, starch, polyacrylamide, polyethylene oxide, poly (hydroxystearic acid-g-methyl methacrylate-) (eu-methacrylic acid) copolymer and a nonionic or ionic surfactant.

When the emulsion polymerization method and the hetero-aggregation method are used, an anionic surfactant, a cationic surfactant,
Zwitterionic surfactants and nonionic surfactants are used as stabilizers. It is preferable to use 0.2 to 30 parts by weight of these stabilizers based on 100 parts by weight of the polymerizable monomer.

When an inorganic compound is used among these stabilizers, a commercially available one may be used as it is. However, in order to obtain fine particles, the inorganic compound stabilizer is produced in a dispersion medium. Is also good.

For finely dispersing these stabilizers, a surfactant may be used in an amount of 0.001 to 0.1 part by weight based on 100 parts by weight of the polymerizable monomer. This surfactant is for promoting the stabilizing action of the dispersion stabilizer. Specific examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate.

As the colorant used in the polymerization method toner in the present invention, it is necessary to pay attention to the polymerization inhibitory property and the water phase transfer property of the colorant. It is better to perform a hydrophobic treatment without any. In particular, many dyes and carbon blacks have polymerization inhibitory properties, so care must be taken when using them.
As a preferable method for surface-treating the dye system, a method in which a polymerizable monomer is previously polymerized in the presence of these dyes is mentioned, and the obtained colored polymer is added to the monomer system. Carphocene black may be treated with a substance that reacts with the surface functional groups of carbon black, such as polyorganosilixane, in addition to the same treatment as the above dye.

[0132]

[0133]

[0134]

[0135]

Further, the melting point of the wax of the toner is higher than the glass transition temperature of the binder resin, and the temperature difference is preferably 100 ° C. or less, more preferably 75 ° C. or less, and further preferably 50 ° C. or less. .

When this temperature difference exceeds 100 ° C.,
The low-temperature fixability decreases. Furthermore, if this temperature difference is too close, the temperature range in which both the storability of the toner and the high-temperature offset resistance are compatible is narrowed. Therefore, the temperature difference is preferably 2 ° C. or more. The glass transition temperature of the binder resin is preferably from 40 ° C. to 90 ° C., more preferably 5 ° C.
The temperature is preferably 0 to 85 ° C.

When the glass transition temperature of the binder resin is lower than 40 ° C., the storage stability of the toner is lowered and the fluidity is deteriorated, so that a good image cannot be obtained.

When the glass transition temperature of the binder resin exceeds 90 ° C., the low-temperature fixing property is inferior and the transparency of full-color transparency is deteriorated. In particular, the halftone portion tends to be dull and a projection image without saturation is likely to be obtained.

In the present invention, the glass transition temperature (Tg) of the binder resin was measured by a measurement according to ASTM D3418-8. For example, PerkinElmer DS
This is performed using C-7. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. For the sample, an aluminum pan was used, an empty pan was set for control, and the temperature was raised at a rate of 10 ° C./mi.
n. At a temperature in the range of 20 to 200 ° C.

In the present invention, the toner can be used for either a one-component developer or a two-component developer.

In the case of a magnetic toner in which a magnetic substance is contained in a toner as a one-component developer, there is a method of using a magnet built in a developing sleeve to transport and charge the magnetic toner. Further, when a non-magnetic toner containing no magnetic material is used as a one-component developer, a blade and a fur brush are used to forcibly triboelectrically charge the toner with a developing sleeve and adhere the toner on the developing sleeve. There is a method of transporting.

When used as a two-component developer, a carrier is used together with the toner. The carrier used in the present invention is not particularly limited, but is mainly composed of iron, copper, zinc, nickel, cobalt, manganese, and a single ferrite and a composite ferrite composed of a metal oxide such as chromium. . Carrier shape is also important because saturation magnetization and electric resistance can be controlled over a wide range. For example, select a shape such as spherical, flat, or irregular, and also control the fine structure of the carrier surface state, for example, surface irregularities. Is preferred. In the present invention, the carrier is fired and granulated of the metal oxide, in advance, after generating carrier core particles, in addition to the method of coating the resin, from the meaning of reducing the load on the toner of the carrier, After kneading the inorganic oxide and the resin,
A method for obtaining a low-density inorganic oxide dispersion carrier by pulverizing and classifying, and a method for directly obtaining a spherical inorganic oxide dispersion carrier by subjecting a kneaded product of an inorganic oxide and a monomer to suspension polymerization in an aqueous medium. It is possible to use the obtained one.

It is particularly preferable that the surface of the carrier is coated with a resin. As the method, any conventionally known method of coating a resin with a carrier, such as a method of dissolving or suspending a coating material such as a resin in a solvent, applying the coating material, and attaching the coating material to a carrier, or a method of simply mixing with a powder, can be applied.

The coating material on the carrier surface varies depending on the toner material. For example, polytetrafluoroethylene,
Monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, metal compound of ditersharry butylsalicylic acid, styrene resin, acrylic resin, polyamide, polyvinyl butyral, nigrosine, amino acrylate resin, basic dye and its lake, Examples include silica fine powder and alumina fine powder. These are suitably used alone or in combination.

The amount of coating (coating) of the coating material is preferably 0.01 to 30% by weight, more preferably 0.1 to 20% by weight, based on the weight of the carrier after the processing.

The average particle size of these carriers is preferably 1
It is good to have 0-100 micrometers, More preferably, it is 20-50 micrometers.

In a particularly preferred embodiment, the surface of the ferrite is formed by combining (T) a fluorine-based resin and a styrene-based resin (for example, a combination of polyvinylidene fluoride and a styrene-methyl methacrylate resin; Combination with styrene-methyl methacrylate resin, combination of fluorine-based copolymer and styrene-based copolymer), preferably in a ratio of 90:10 to 20:80, more preferably 70:30 to 30:70. Or (ii) a silicone resin, preferably 0.01 to 5% by weight, more preferably 0.1 to 3% by weight.
Coated ferrite carriers.

As the fluorine-based copolymer, a vinylidene fluoride-tetrafluoroethylene copolymer (10:90 to 9
0:10). As the styrene-based copolymer, a styrene-2-ethylhexyl acrylate copolymer (2
0: 80-80: 20), styrene-2-ethylhexyl acrylate-methyl methacrylate copolymer (20-6)
0: 5 to 30:10 to 50).

The coated ferrite carrier has a sharp particle size distribution, provides favorable triboelectricity to the toner used in the present invention, and has the effect of improving electrophotographic properties.

In the present invention, when a two-component developer is prepared by mixing a toner and a carrier, the mixing ratio is 2% by weight to 15% by weight, preferably 4% by weight as a toner concentration in the developer. Good results are obtained with 13% by weight. When the toner density is less than 2%, the image density is low. When the toner density is more than 15%, fog and scattering in the machine are increased, and the useful life of the developer is shortened.

Further, the magnetic properties of the carrier are preferably as follows. The saturation magnetization is preferably ^{20 to} 90 Am ² / kg, and more preferably 30 to 70 Am ² / kg in order to achieve higher image quality. When the saturation magnetization is larger than 90 Am ² / kg, it is difficult to obtain a high quality toner image. Saturation magnetization is 20 Am ² /
If the weight is less than kg, carrier adhesion is likely to occur because the magnetic binding force is also reduced.

Next, a preferred heat fixing device used in the image forming method and the heat fixing method of the present invention will be described.

In the present invention, the heating member in contact with the toner image of the heat fixing device is for applying heat for contacting the toner image on the recording material and fixing the toner image to the recording material. The heating member contacts a toner image in (i) a heating roller fixing method described later,
A heating roller which is a roller-shaped member for applying heat of a heating means provided inside to the toner image, and (ii) is in contact with the toner image in the film heat fixing method and opposite to the surface of the film-shaped member which is in contact with the toner image (Iii) the film-shaped member itself is in contact with the toner image in the film heat-fixing method, and the film-shaped member itself is electromagnetically acted upon by the action of a magnetic field. It includes a fixing film that is a film-like member that applies heat generated by induced heat to a toner image.

FIG. 1 is a schematic view showing an example of a heat fixing device of a roller heat fixing system.

The apparatus of this embodiment has a cylindrical heating roller 101 having a heating means such as a heater 101a inside. When fixing, the heating roller 101 rotates clockwise.

Reference numeral 102 denotes a pressure roller serving as a cylindrical pressure rotating body.
Reference numeral 02 presses against the heating roller 101 and rotates counterclockwise.

The recording material P as a material to be heated, to which the unfixed toner T adheres as a toner image, is conveyed from the right (upstream side) in the drawing by the conveyance belt 103, and is pressed against the heating roller 101 and the pressure roller 102. The unfixed toner image carried on the recording material P by being pressed and heated by the unit is fixed to the recording material P by a heating roller 101 as a heating member which is in pressure contact with the toner image, and is (Downstream).

Reference numerals 104a and 104b denote separation claws used for separation in order to prevent the recording material P from being wound around the heating roller 101 or the pressure roller 102 and causing a conveyance failure.

Reference numeral 106 denotes a felt oil pad having a suitable viscosity and impregnated with a release agent such as silk cone oil, and 105 denotes a cleaning roller in which brush fibers are implanted in a cylindrical shape. The cleaning roller 105 rotates to remove toner residue adhering to the peripheral surface of the heating roller and to supply the release agent appropriately. 106 may be omitted.

For example, the heating roller 101 has a thickness of 2 to 5
An aluminum pipe having a thickness of about mm is used as a core metal, and the peripheral surface thereof is coated with 200 to 500 μm thick silicone rubber or Teflon.

The pressure roller 102 is, for example, about 10 m
An SUS pipe having a diameter of mφ is used as a core metal, and its peripheral surface is coated with silicone rubber to a thickness of about 3 mm.

FIG. 5 is a schematic view showing another example of the heat fixing device of the roller heat fixing method described with reference to FIG.

Another heating and fixing device shown in FIG. 5 is a roller heating and fixing device shown in FIG. 1 in which a cleaning roller 105 having brush-like fibers planted in a cylindrical shape is formed of silicone rubber, fluoro rubber or fluoro resin into a cylindrical shape. The cleaning roller 107 is replaced with the oil pad 106 in a felt shape. Components having the same configuration as in FIG. 1 use the same reference numerals as in FIG.

In the heat fixing device of the embodiment shown in FIG. 5, the cleaning roller 107 rotates to remove the toner residue adhered to the peripheral surface of the heating roller.

Since the contact angle C of the cleaning roller 107 at 100 ° C. with the wax contained in the toner is within the range of 0 to 60 as described above, the cleaning roller 107 adheres to the peripheral surface of the heating roller. The toner residue and the cleaning roller 107 can be removed satisfactorily.

Further, in the present invention, a heat fixing device of a film heat fixing method can be used in place of the heat fixing device of the roller heat fixing method.

The heat fixing device of the film heat fixing method is as follows.
Heat roller method, hot plate method, belt heating method, flash heating method, compared with other known heating and fixing devices such as oven heating method, a low heat capacity linear heating element as a heating element, a thin film as a film Since a low heat capacity type can be used, power saving and shortening of wait time (quick start property) are possible, and furthermore, the temperature rise in the apparatus can be suppressed; the fixing point and the separation point can be set separately. Therefore, the offset can be prevented; and the various drawbacks of the other devices can be solved;

The heat fixing device of the film heating type is not limited to the fixing device, but is widely used as a device for heating a recording material carrying an image to improve the surface property or a device for temporarily attaching the material. Can be used as a means / apparatus for heat treatment.

FIG. 2 shows an outline of a film heat fixing type apparatus (image heat fixing apparatus).

Reference numeral 116 denotes a heater (ceramic heater) fixedly supported by a support (not shown). This heating element 11
A heat-resistant film (fixing film) 111 is brought into close contact with a pressure roller 112 as a pressure rotating body, and is slid and conveyed while being guided by guides 120 and 120. The heat-resistant film 111 is sandwiched between the heat-resistant film 111 of the press-contact nip portion (fixing nip portion) N formed by the heating element 116 and the pressure roller 112 as a pressure member, and the pressure roller 112. A recording material P to be fixed with an image as a heating material is introduced while being guided by a guide 120,
The recording material P is held together with the heat-resistant film 111 by sandwiching the press-contact nip portion N and transported in the direction of arrow a, so that the heat of the heating body 116 is transferred through the heat-resistant film 111 to the recording material P.
And heat-fixes the unfixed toner image T carried on the recording material P to the surface of the recording material P. That is, the unfixed toner image carried on the recording material P is fixed to the recording material by the fixing film 111 as a heating member that comes into pressure contact with the toner image. The recording material P that has passed through the pressure nip N is separated from the surface of the film 111 and conveyed.

The heating body 116 is an elongated heat-resistant, insulating and good heat-conductive substrate 117 whose longitudinal direction is perpendicular to the conveying direction a of the heat-resistant film 111 or the recording material P as a material to be heated. A resistance heating element 115 formed along the length of the substrate at the center in the short direction on the front side of the substrate, power supply electrodes (not shown) at both longitudinal ends of the resistance heating element 115,
Linear heating with low heat capacity as a whole having a heat-resistant overcoat layer 118 that protects the surface of the heating element that regulates the resistance heating element, and a temperature sensing element 114 provided on the back side of the substrate, such as a thermistor that detects the temperature of the heating element. Body.

The heating element 116 is fixedly arranged by exposing the surface side on which the resistance heating element 115 is formed and facing downward to a heater support having rigidity and heat insulation properties.

The heating element 116 is heated by the power supply to both end electrodes of the resistance heating element 115 and generates heat over the entire length thereof. The temperature increase is detected by the temperature detection element 114, and the detected temperature is detected. The power supply to the resistance heating element 115 is controlled so that the temperature of the heating element is maintained at a predetermined temperature by being fed back to a temperature control circuit (not shown). That is, at the time of fixing, the temperature detecting element (thermistor) 114
Of the resistance heating element 115 is controlled so that the detection output of the resistance heating element 115 becomes constant. A heating device using alternating magnetic field injection may be used instead of the ceramic heater.

The heat-resistant film 111 is formed in an endless belt shape, and one of the rollers stretched around the heat-resistant film 111 is used as a driving roller, and is rotated and conveyed by a frictional force between the driving roller and the inner peripheral surface of the film. , Pressure roller 11
2 as a drive roller, or a structure in which the roller is transported by a frictional force between the drive roller in contact with the outer surface of the film other than the pressure roller 112 and the outer peripheral surface of the film, or the heat-resistant film 111 is formed into a roll-wound long film. There is a configuration in which this is fed out and carried out.

The pressure roller 112 as the pressure rotating body is the pressure roller 1 of the heat roller type heat fixing device shown in FIG.
12, a solid elastic roller (hereinafter referred to as a solid roller) composed of a metal core 112a and a heat-resistant rubber layer 112b having good releasability such as silicone rubber. The film 111 is sandwiched with a predetermined pressing force by
It is arranged so as to be in pressure contact with the surface of the 16. When the pressure roller 112 is a film drive roller, a rotational force is transmitted to the roller 112 from a drive unit (not shown), and the roller 112 is rotated counterclockwise in the direction of arrow b.

In the present invention, as a preferred embodiment of the heating roller as the heating member, a heat resistant rubber 112b
A fluorine-based resin layer 112d having a specific contact angle with the wax in the toner on the outermost surface layer, and a fluorine resin having a higher hardness than the heat-resistant rubber layer 112b of the base layer between the base layer and the outermost surface layer. This is an elastic roller provided with a rubber layer 112c with a layer thickness of 5 to 10 μm. Further, it is more preferable that the fluororesin of the outermost surface layer is mainly composed of FEP (tetrafluoroethylene-hexafluoropropylene copolymer).

With the above configuration, the elastic roller has excellent releasability over a long period of time and good adhesion between the layers, so that the elastic roller can have excellent durability and low roller hardness.

In the present invention, as a preferred embodiment of the film fixing type heat fixing device, as shown in FIG. 2, the above-mentioned elastic roller is used as a pressure rotating member, and a heat-resistant member is provided between the pressure rotating member and the heating member. The recording material P as a material to be heated is introduced between the heat-resistant film and the pressure rotating body in the press-contact nip portion formed by the heating body and the pressure rotating body with the heat-resistant film therebetween. This is a heating device in which the recording material is transported together through the press-contact nip portion and the heat of the heating body is applied to the material to be heated via the heat-resistant film.

FIG. 6 is a schematic view showing another example of the heat fixing device of the film heat fixing method described with reference to FIG.

The heat fixing device shown in FIG. 6 is a device in which a cleaning roller 121 is provided in the heat fixing device shown in FIG. Components having the same configuration as in FIG. 2 use the same reference numerals as in FIG.

As the cleaning roller 121, a roller in which the surface of a pipe-like base such as an iron hollow pipe is coated with a tube whose contact angle is adjusted by adding a filler to a resin material such as PEA resin is used.

In the heat fixing apparatus of the embodiment shown in FIG.
11 while rotating while contacting the surface of the heat-resistant film 1
11 removes toner residue adhering to the surface.

Since the contact angle C at 100 ° C. with the wax contained in the toner is in the range of 0 ° to 60 ° as described above, the cleaning roller 121 as the cleaning member The adhered toner residue can be satisfactorily removed by the cleaning roller 121.

Further, as another preferred embodiment of the heat fixing device of the film heating type, a heat-resistant member such as a heat-resistant film or belt having a conductive layer and a pressure member having a conductive layer, and a magnetic field applied to these conductive layers are provided. Heating means for generating an eddy current to generate heat by generating an eddy current, and heating the recording material as a material to be heated by sandwiching and transporting the recording material in a press-contact nip portion between the heat-resistant member and the pressing member. Device.

In the present invention, as a preferred embodiment of the heat-resistant member such as a heat-resistant film or belt as the heating member, a fluororesin containing FEP as a main component is provided on the outermost surface layer and an elastic layer is provided inside the resin. Is more preferred.

Therefore, according to the present invention, the heat-fixing device of the heating roller type, the heat-fixing device of the film heating type, and the other heat-fixing devices other than the above-mentioned ones are used to fix the unfixed toner carried on the recording material. Since the heating member that is in pressure contact with the toner image needs to satisfy the relationship between the wax contained in the toner and the above-described specific contact angle, the outermost surface layer of the heating member has at least a repeating unit of tetrafluoroethylene in the main chain. And preferably a FEP or PF having a fluoroalkoxy group and / or a fluoroalkyl group in a side chain.
A (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) is preferable, and in view of prevention of toner contamination, it is more preferably formed by FEP having a fluoroalkyl group in a side chain. Is good.

In the heat fixing method of the present invention, a toner image carrying step of carrying a toner image formed of a color toner on a recording material, and an unfixed toner image carried on the recording material is referred to as a toner image. The image forming apparatus has a fixing step of fixing the recording material by a heat fixing device having a heating member to be in pressure contact with the recording material, and uses the above-described heat fixing device in this fixing step.

Further, in the image forming method of the present invention, an electrostatic latent image forming step of forming an electrostatic latent image on the latent image holding member, and developing the electrostatic latent image with a color toner to form a toner image A developing step, a transfer step of transferring the toner image to a recording material, and fixing of the unfixed toner image carried on the recording material to the recording material by a heat fixing device having a heating member that presses against the toner image. Has a fixing process,
In the fixing step, the above-described heat fixing device is used.

Next, an example of the image forming method of the present invention will be described more specifically with reference to FIG.

FIG. 3 is a schematic diagram showing an example of an image forming apparatus capable of performing the image forming method of the present invention.

This image forming apparatus is configured as a full-color copying machine. As shown in FIG. 3, the full-color copying machine has a digital color image reader unit 35 at the upper part and a digital color image printer unit 36 at the lower part.

In the image reader section, the original 30 is placed on the original platen glass 31 and is exposed and scanned by the exposure lamp 32, so that the reflected light image from the original 30 is condensed on the full color sensor 34 by the lens 33, and the color image is reflected. Obtain a decomposed image signal. The color-separated image signal is processed by a video processing unit (not shown) through an amplifier circuit (not shown) and sent to a digital image printer unit.

In the image printer section, the photosensitive drum 1, which is a latent image holding member, is a photosensitive member such as an organic photoconductor, and is supported rotatably in the direction of the arrow. Around the photosensitive drum 1, a pre-exposure lamp 11, a corona charger 2 as a primary charging member, a laser exposure optical system 3 as a latent image forming means, a potential sensor 12, four developing devices 4Y of different colors, 4C, 4M, 4K, on-drum light amount detection means 1
3. The transfer device 5A and the cleaning device 6 are arranged.

In the laser exposure optical system 3, an image signal from the reader unit is converted into an image scan exposure optical signal by a laser output unit (not shown), and the converted laser light is reflected by the polygon mirror 3a. Is projected on the surface of the photosensitive drum 1 via the lens 3b and the mirror 3c.

At the time of image formation, the printer unit
Is rotated in the direction of the arrow, and after the charge is eliminated by the pre-exposure lamp 11, the photosensitive drum 1 is uniformly negatively charged by the charger 2 to irradiate a light image E for each separation color, and the latent image is formed on the photosensitive drum 1. To form

Next, the latent image on the photosensitive drum 1 is developed by operating a predetermined developing device, and a visible image, that is, a toner image is formed on the photosensitive drum 1 using a resin-based negative toner. The developing units 4Y, 4C, 4M, and 4K alternately approach the photosensitive drum 1 in accordance with the respective separation colors and perform development by the operation of the eccentric cams 24Y, 24C, 24M, and 24K.

The transfer device 5A includes a transfer drum 5, a transfer charger 5b, a suction charger 5c for electrostatically attracting a recording material and a suction roller 5g opposed thereto, an inner charger 5d, an outer charger 5e, It has a separation charger 5h.
The transfer drum 5 is rotatably supported so as to be rotatable, and a transfer sheet 5f, which is a recording material carrier that carries a recording material in an opening area around the transfer drum 5, is integrally adjusted on a cylinder. A polycarbonate film or the like is used for the transfer sheet 5f.

The recording material is conveyed from the recording material cassette 7a, 7b or 7c to the transfer drum 5 through the recording material conveyance system, and is carried on the transfer sheet 5f. Transfer drum 5
The recording material carried thereon is repeatedly conveyed to a transfer position facing the photosensitive drum 1 as the transfer drum 5 rotates, and is transferred onto the photosensitive material by the action of the transfer charger 5b while passing through the transfer position. 1 is transferred.

In the above image forming step, yellow (Y),
By repeating the process for magenta (M), cyan (C), and black (K), a color image in which four color toner images are superimposed and transferred on the recording material on the transfer drum 5 is obtained.

In the case of single-sided image formation, the recording material onto which the toner images of four colors have been transferred in this way is separated by the action of the separation claw 8a, the separation push-up roller 8b, and the separation charger 5h.
The sheet is separated from the transfer drum 5 and sent to the heat fixing device 9.
The heat fixing device 9 includes a heat fixing roller 9a having a heating unit therein and a pressure roller 9b. The full-color image carried on the recording material is fixed on the recording material by passing the recording material through the pressure contact portion between the heat fixing roller 9a and the pressure roller 9b as a heating member. That is, in this fixing step, toner color mixing, color development, and fixing to the recording material are performed to form a full-color permanent image, which is then discharged to the tray 10 to complete one full-color copy. On the other hand, the photosensitive drum 1 is subjected to the image forming process again after the residual toner on the surface is cleaned and removed by the cleaning device 6.

In the image forming method of the present invention, a toner image obtained by developing the electrostatic latent image formed on the latent image holding member can be transferred to a recording material via an intermediate transfer member.

That is, in this image forming method, the toner image formed by developing the electrostatic latent image formed on the latent image holding member is transferred to an intermediate transfer member, and the toner image transferred to the intermediate transfer member is Is transferred to a recording material.

An example of an image forming method using an intermediate transfer member will be specifically described with reference to FIG.

In the apparatus system shown in FIG. 4, the cyan developing device 54-1, the magenta developing device 54-2, the yellow developing device 54-3, and the black developing device 54-4 are respectively provided with a cyan developer having a cyan toner and a magenta developing device. A magenta developer having a toner, a yellow developer having a yellow toner, and a black developer having a black toner have been introduced. An electrostatic latent image is formed on a photosensitive member 51 as a latent image holding member by a latent image forming means 53 such as a laser beam. By a developing method such as a magnetic brush developing method, a non-magnetic one-component developing method or a magnetic jumping developing method,
The electrostatic charge image formed on the photoconductor 51 is developed with these developers, and a toner image of each color is formed on the photoconductor 51.
The photosensitive member 51 is a photosensitive drum or a photosensitive belt having a conductive substrate 51b and a photoconductive insulating material layer 51a such as amorphous selenium, cadmium sulfide, zinc oxide, an organic photoconductor, and amorphous silicon formed on the conductive substrate 51b. is there. The photoconductor 51 is rotated in a direction indicated by an arrow by a driving device (not shown). As the photoconductor 51, a photoconductor having an amorphous silicon photosensitive layer or an organic photosensitive layer is preferably used.

As the organic photosensitive layer, either a single layer type in which the photosensitive layer contains a charge generating substance and a substance having a charge transporting property in the same layer, or a function-separated type photosensitive layer comprising the charge transporting layer and the charge generating layer as components. It may be. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated on a conductive substrate in this order is one of preferred examples.

As the binder resin for the organic photosensitive layer, a polycarbonate resin, a polyester resin, or an acrylic resin has good cleaning properties, and poor cleaning, toner fusion to the photoreceptor, and filming hardly occur.

In the present invention, in the charging step, there are a non-contact type with the photosensitive member 51 using a corona charger and a contact type with a contact charging member such as a roller, and both types are used. For efficient uniform charging, simplification, and low ozone generation, a contact type as shown in FIG. 4 is preferably used.

A charging roller 52 as a primary charging member
Is a conductive elastic layer 5 having a central core 52b and an outer periphery.
2a as a basic configuration. Charging roller 52
Is pressed against the surface of the photoconductor 51 with a pressing force, and is rotated by the rotation of the photoconductor 51.

[0210] Preferred process conditions when a charging roller is used include a contact pressure of the roller of 5 to 500 g /
cm, when a voltage obtained by superimposing an AC voltage on a DC voltage is used, AC voltage = 0.5 to 5 kVpp, AC frequency =
50 to 5 kHz, DC voltage = ± 0.2 to ± 5 kV.

Other contact charging members include a method using a charging blade and a method using a conductive brush. These contact charging members have the effects of eliminating the need for high voltage and reducing the generation of ozone.

The material of the charging roller and the charging blade as the contact charging member is preferably conductive rubber, and a release coating may be provided on the surface thereof. As the release coating, a nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride), or a fluorine acrylic resin can be used.

[0213] The toner image on the photoreceptor has a voltage (for example, ± 0.
(± 1 kV) is applied to the intermediate transfer member 55 to which the voltage is applied. The intermediate transfer member 55 is a pipe-shaped conductive core 55b.
And a medium resistance elastic layer 55a having an outer peripheral surface thereof. The cored bar 55b may be formed by providing a conductive layer (for example, conductive plating) on the surface of plastic.

The middle resistance elastic layer 55a is made of silicone rubber,
Teflon rubber, chloroprene rubber, urethane rubber, EP
An elastic material such as DM (ethylene-propylene-diene terpolymer) is mixed with a conductivity-imparting agent such as carbon black, zinc oxide, tin oxide, and silicon carbide to disperse the electric resistance (volume resistivity). It is a solid or foamed layer adjusted to a medium resistance of 10 ⁵ to 10 ¹¹ Ωcm.

The intermediate transfer member 55 is arranged in parallel with the photosensitive member 51 so as to be in contact with the lower surface of the photosensitive member 51, and is rotated at the same peripheral speed as the photosensitive member 51 in the counterclockwise direction indicated by the arrow. I do.

In the process in which the first color toner image formed and carried on the surface of the photoconductor 51 passes through the transfer nip where the photoconductor 51 and the intermediate transfer member 55 are in contact with each other, the transfer nip is applied by the transfer bias applied to the intermediate transfer member 55. The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer body 55 by the electric field formed in the intermediate transfer member 55.

The untransferred toner on the photosensitive member 51 that has not been transferred to the intermediate transfer member 55 is removed by the photosensitive member cleaning member 5.
8 and is collected in the photoconductor cleaning container 59.

A transfer means is provided in parallel with the intermediate transfer body 55 and is brought into contact with the lower surface of the intermediate transfer body 55. The transfer means is, for example, a transfer roller 57 and has the same circumference as the intermediate transfer body 55. Rotate in the clockwise direction of the arrow at speed.
The transfer roller 57 may be disposed so as to be in direct contact with the intermediate transfer body 55,
5 and the transfer roller 57.

The transfer roller 57 basically has a core metal 57b at the center and a conductive elastic layer 57a forming the outer periphery thereof.

As the intermediate transfer member and the transfer member used in the present invention, general materials can be used.
In the present invention, the voltage applied to the transfer member can be reduced by setting the volume resistivity of the transfer member smaller than the volume resistivity of the intermediate transfer member, and a good toner image can be formed on the transfer material and the transfer can be performed. The material can be prevented from winding around the intermediate transfer member. In particular, it is preferable that the volume resistivity of the elastic layer of the intermediate transfer member is at least 10 times higher than the volume resistivity of the elastic layer of the transfer member.

The hardness of the intermediate transfer member and the transfer member is determined according to JIS.
It is measured according to K-6301. The intermediate transfer member used in the present invention is preferably composed of an elastic layer belonging to the range of 10 to 40 degrees. The hardness of the elastic layer of the transfer member used in the present invention is higher than the hardness of the elastic layer of the intermediate transfer member, and preferably has a value of 41 to 80 degrees in order to prevent the recording material from winding around the intermediate transfer member. . If the hardness of the elastic layer of the transfer member is lower than the hardness of the elastic layer of the intermediate transfer member, a concave portion is formed on the transfer member side, and the recording material is likely to be wound around the intermediate transfer member.

As the transfer member, for example, a transfer roller is used, and the transfer roller 57 is rotated at a constant speed or at a different peripheral speed from the intermediate transfer member 55. The recording material 56 is conveyed between the intermediate transfer member 55 and the transfer roller 57, and at the same time, a bias having a polarity opposite to that of the triboelectric charge of the toner is applied to the transfer roller 57 from the transfer bias means, so that the recording material 56 Is transferred to the surface side of the recording material 56.

The untransferred toner remaining on the intermediate transfer member that has not been transferred to the recording material 56 is removed by the cleaning member 6 for the intermediate transfer member.
0 and is collected in the intermediate transfer body cleaning container 62. The toner image transferred to the recording material 56 is fixed on the recording material 56 by the heat fixing device 61.

As the material of the transfer roller, the same material as that of the charging roller can be used. Preferred transfer process conditions include a contact pressure of the roller of 2.94 to 49.
0 N / m (3-500 g / cm) (more preferably 1
9.6 N / m to 294 N / m), DC voltage = ± 0.2
±± 10 kV.

If the linear pressure as the contact pressure is less than 2.94 N / m, it is not preferable because the conveyance of the recording material and the occurrence of transfer failure tend to occur.

For example, the conductive elastic layer 5 of the transfer roller 57
Reference numeral 7b denotes an electric resistance value (volume resistivity) obtained by mixing and dispersing a conductivity imparting agent such as carbon black, zinc oxide, tin oxide, or silicon carbide in an elastic material such as polyurethane rubber or EPDM (ethylene propylene diene terpolymer). ) To 10 ⁶
This is a solid or foamed layer adjusted to have a medium resistance of ¹⁰ to 10 ¹⁰ Ωcm.

Hereinafter, the structure of the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Example 1 Example 1 450 g of a 0.1 M Na ₃ PO ₄ aqueous solution was charged into 710 g of ion-exchanged water and heated to 60 ° C., and then a TK homomixer (manufactured by Tokushu Kika Kogyo) was used. 1300 rpm
And stirred. 1.0M-CaCl ₂ aqueous solution 68
g was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

160 g of styrene 34 g of n-butyl acrylate 15 g of copper phthalocyanine pigment 3 g of metal ditertiary butyl salicylic acid compound 10 g of saturated polyester (acid value 11, peak molecular weight 8500) Monoester wax 40 g (Mw: 500, Mn: 400, Mw / Mn: 1.25, melting point: 70 ° C., viscosity: 6.5 mPa · s, Vickers hardness: 1.1, SP value: 8.6)

The above-mentioned formulation was heated to 60 ° C., and was subjected to 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo).
To dissolve and disperse uniformly. In addition, polymerization initiator 2,
2'-azobis (2,4-dimethylvaleronitrile) 1
0 g was dissolved to prepare a polymerizable monomer composition. Said,
The above polymerizable monomer composition was charged into an aqueous medium,
Under a N ₂ atmosphere at ℃ 1 with a TK homomixer
The mixture was stirred at 0000 rpm for 20 minutes to granulate the polymerizable monomer composition. Thereafter, the temperature was raised at 80 ° C. while stirring the aqueous medium with a paddle stirring blade, and a polymerization reaction was performed for 10 hours.

After the completion of the polymerization reaction, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, and then filtered, washed with water and dried to obtain polymer particles (toner particles).

The obtained polymer particles were analyzed by a transmission electron microscope (T
The core-shell structure in which the wax was encapsulated in the outer resin layer was confirmed by the tomography method of the polymer particles using EM).

The binder resin of the polymer particles obtained had the following physical properties (Tg: 60 ° C.).

With respect to 100 parts by weight of the obtained polymer particles (toner particles), the specific surface area by the BET method was 100 m ² /
g of hydrophobic titanium oxide (2.0 parts by weight) was externally added to obtain a cyan toner having an average particle diameter of 6.2 μm.

To 7 parts by weight of this cyan toner, 93 parts by weight of a 35 μm ferrite carrier coated with silicone were mixed, and a two-component developer No. 1 was prepared. It was set to 1.

This developer no. 1 and a commercially available full-color copying machine CLC-8 as an image forming apparatus shown in FIG.
00 (manufactured by Canon), the fixing device was changed to a roller having a surface layer coated with 10 μm of FEP for both the heating roller and the pressure roller, and the configuration was modified to remove the oil application mechanism as shown in FIG. Using two types of original documents of 50% and 10,000 sheets, a paper passing test was performed on each of 10,000 sheets, and the evaluation was made based on the following evaluation method.

At this time, the adhesion angle between the fixing roller and the wax was A = 69 °, B = 74 °, and BA = 5 °.

-Evaluation Method- (1) OHP Transmittance The transmittance was measured using a Shimadzu self-recording spectrophotometer UV2200 (manufactured by Shimadzu Corporation), the transmittance of the OHP film alone was taken as 100%, and the toner weight per unit area. 1.0mg /
The transmittance of OHP at cm ² is magenta toner (650 nm) and yellow toner (500 n).
m), for a cyan toner (600 nm). A: 60% or more B: 55% or more and less than 60% C: 50% or more and less than 55% D: less than 50%

(2) Image Glossiness Unevenness The maximum value of the glossiness when fixing an A4 solid image with a toner weight per unit area of 1.0 mg / cm ² using CLC-SK paper (manufactured by Canon). Evaluation is based on the difference between the minimum values. The glossiness at this time was measured using a handy gloss meter gloss checker IG-310 (incident angle: 60 degrees: manufactured by Horiba, Ltd.). A: 3 or less B: More than 3 to 6 or less C: More than 6 to 10 or less D: More than 10

(3) Offset resistance 10,000 sheets were continuously fed, and evaluated based on the following evaluation criteria. A: No staining is observed on the front and back surfaces of the recording paper up to 10,000 sheets. B: Soil is slightly observed on the back surface of the recording paper when 10,000 sheets are passed. C: Soil was observed on the back surface of the recording paper between 5,000 and 10,000 during paper passing. D: Dirt is observed on the back surface of the recording paper by 5,000 sheets during paper passing.

(4) Image homogeneity Using CLC-SK paper, 0.5 mg / unit area
An A4 solid image of cm ² is fixed. The image density is measured, and the image homogeneity is evaluated based on the difference between the maximum and the minimum. A: 0.05 or less B: More than 0.05 to 0.1 or less C: More than 0.1 to 0.15 or less D: More than 0.15

(5) Storage Property 5 g of a toner adjusted to a desired particle size and optionally having an external additive added thereto is added to a 100 cc polycup, and allowed to stand in a dryer at 50 ° C. for 3 days. Let it.

As a means for checking the cohesiveness of the sample, the degree of cohesion was measured using a vibrating sieve of a powder tester (manufactured by Hosokawa Micron Corporation) to evaluate the storage stability.

The measuring method was as follows:
h, 200 mesh, 100 mesh in order of narrow opening, that is, 400 mesh, 200 mesh, 100 mesh so that 100 mesh is at the top.
Set in the order of the screen.

The above-mentioned sample was added to the set 100 mesh screen, the input voltage to the shaking table was adjusted to 18 V, and the amplitude of the shaking table at that time was adjusted to be within a range of 0.5 mm, and the time was adjusted for 15 seconds. Vibration is applied, and then the weight of the sample remaining on each screen is measured, and the degree of cohesion is obtained based on the following equation.

At this time, based on the degree of aggregation of the toner not placed in the dryer at 50 ° C., the degree of storage stability was determined by the rate of change of the degree of aggregation.

[0247]

[Outside 4]

The measuring environment is 23 ° C. and 65% RH. A: less than 20% B: 20% or more and less than 25% C: 25% or more and less than 30% D: 30% or more

Comparative Example 1 Paraffin wax (Mw: 570, Mn: 380, Mw / M) was used in place of the monoester wax used in Example 1.
n = 1.50, melting point: 69 ° C., viscosity: 6.8 mPa ·
developer No. s, Vickers hardness: 0.7, SP value: 8.3 2 was prepared and evaluated. The contact angle at this time was A = 83 ° B = 92 ° BA = 9 °, and it is presumed that the contact angle was large and a satisfactory image was not achieved.

Comparative Example 2 An evaluation was performed in the same manner as in Example 1 except that PTFE was used instead of the FEP used as the surface material of the heating roller and the pressure roller used in Example 1, but the evaluation was satisfactory. No results were obtained. This is presumably because the contact angle was inappropriate.

Comparative Example 3 An evaluation was performed in the same manner as in Example 1 except that RTV silicone rubber was used instead of the FEP used as the surface material of the heating roller and the pressure roller used in Example 1, but
No satisfactory results were obtained. This is presumably because the contact angle was inappropriate.

Comparative Example 4 In place of the monoester wax used in Example 1, the paraffin wax used in Comparative Example 1 was fractionated by molecular weight (Mw: 580, Mn: 415,
Mw / Mn = 1.4, melting point: 70 ° C., viscosity: 6.8 mP
a.s, Vickers hardness: 0.7, SP value: 8.3) except that developer No. No. 3 was prepared and evaluated. As in Comparative Example 1, satisfactory OHP permeability was not obtained.

Comparative Example 5 In place of the monoester wax used in Example 1, acrylic acid-modified wax (Mw: 1800, Mn: 129)
0, Mw / Mn = 1.4, melting point: 98 ° C., viscosity: 7.1
mPa · s, Vickers hardness: 0.8, SP value: 10.
8), except that developer No. 8) is used. 4 was prepared and evaluated. As a result, the storage stability and the offset resistance were deteriorated. This is presumably because the SP value of the wax was as large as 10.8 and the wax was not uniformly included in the toner.

Comparative Example 6 In place of the monoester wax used in Example 1, a fluorine-modified wax (Mw: 600, Mn: 410, Mw /
Mn = 1.46, melting point: 95 °, viscosity: 8.3 mPa ·
s, Vickers hardness: 1.4, SP value: 8.0). 5 was prepared and evaluated, and no good image was obtained. This is presumably because BA was large and sufficient fixability could not be achieved.

[0255]

Comparative Example 8 In place of the monoester wax used in Example 1, natural carnauba wax (Mw: 900, Mn: 530, M
w / Mn = 1.70, melting point: 65 °, viscosity: 6.3 mP
a.s, Vickers hardness: 6.8, SP value: 8.7), except that developer No. 7 was prepared and evaluated. As a result, the storage stability deteriorated. This is Mw / M
It is presumed that because n was large, it was difficult to make the wax uniform in the toner.

Example 2 An image was formed in the same manner as in Example 1 except that PFA was used in place of FEP used as the surface material of the heating roller and the pressure roller used in Example 1. The result was obtained.

Example 3 A diester wax (Mw: 480, Mn: 410, Mw / M) was used in place of the monoester wax used in Example 1.
n: 1.17, melting point: 73 ° C., viscosity: 10.5 mPa ·
s, Vickers hardness: 1.0, SP value: 9.1) except that developer No. 8 was prepared and evaluated, and good results were obtained.

Example 4 In place of the monoester wax used in Example 1, a tetraester wax (Mw: 430, Mn: 320, Mw:
/ Mn: 1.34, molecular weight 850 with shoulder, melting point: 73 ° C, viscosity: 11.6 mPa · s, Vickers hardness: 1.2, SP value: 8.5) Agent No. 9 was prepared and evaluated, and good results were obtained.

[0260]

Example 6 An olefin-modified wax (Mw: 1800, Mn: 128) was used in place of the monoester wax used in Example 1.
0, Mw / Mn: 1.41, melting point: 100 °, viscosity: 1
2.5 mPa · s, Vickers hardness: 3.2, SP value:
Developer No. 8.4) in the same manner except that developer No. 8.4) is used. 11
Was prepared and evaluated. As a result, good results were obtained although OHP permeability was slightly lowered due to high Vickers hardness.

Example 7 The same procedure as in Example 1 was repeated except that the monomers used in Example 1 were changed to 160 g of styrene, 30 g of n-butyl acrylate, and 20 g of methacrylic acid. 12 was prepared and evaluated. As a result, good results were obtained although the OHP permeability was slightly lowered. This is presumably because the difference between the SP values of the binder resin and the wax was larger than that in Example 1.

The developer No. used in Example 1-7 and Comparative Example 1-8 described above. Table 1 shows the physical properties of 1-12, and Table 2 shows the evaluation results of Example 1-7 and Comparative Example 1-8.

[0264]

[Table 1]

[0265]

[Table 2]

Example 8 The fixing device of the full-color copying machine CLC-800 used in Example 1 was modified to that shown in FIG. 2 and the same operation was carried out except that the surface material of the fixing film was FEP. As shown in Table 2, good results were obtained.

[0267]

[Table 3]

Example 9 A quinacridone pigment was used in place of the copper phthalocyanine pigment used in Example 1, and C.I. I. Pigment Yellow 180 and carbon black, respectively, to prepare a magenta toner, a yellow toner, and a black toner. 13, No. 14 and No. 15 were each obtained.

The two-component developer No. 1, No. 13, N
o. 14 and No. Using the commercially available full-color copying machine CLC-800 used in Example 1 with 15 four-color developers,
An unfixed full-color image was formed, and a full-color fixed image was obtained using the same fixing device as in Example 1. As a result, color reproducibility of pale colors was excellent, and good results were obtained. Furthermore, when a full-color image was projected with OHP,
A very clear and good projected image was obtained.

Example 10 Commercially available full-color copying machine CLC-80 used in Example 9
0, a two-component developer N was used in the same manner as in Example 9 using a full-color image forming apparatus using an intermediate transfer member shown in FIG.
o. 1, No. 13, No. 14 and No. An unfixed full-color image was formed using 15 four-color developers, and a full-color colored image was obtained using the same fixing device as that used in Example 9. As a result, good results were obtained as in Example 9.

Example 11 Instead of the copper phthalocyanine pigment used in Example 1, a silane coupling agent-treated magnetic iron oxide (average particle size 0.25 μm) was used.
m) Toner particles were prepared using 200 g, and a magnetic toner was obtained in the same manner except that hydrophobic silica was used as an external additive to obtain a magnetic one-component developer 16.

Except that the black developing device 54-4 holding the black toner of the full-color image forming apparatus shown in FIG. 4 used in the tenth embodiment is changed to a developing device capable of developing the magnetic one-component developer 16. An unfixed full-color image was formed in the same manner as in Example 10, and fixing was performed in the same manner as in Example 10, to obtain a full-color colored image. as a result,
Good results were obtained as in Example 10.

Example 12 The developer No. used in Example 1 was used. 3, the fixing device of a commercially available full-color copying machine CLC-800 (manufactured by Canon Inc.) was used as the image forming apparatus shown in FIG.
The roller was changed to a μm-coated roller, and the cleaning roller was modified to abut on the surface of the heating roller as shown in FIG. Was.

At this time, the contact angle between the heating roller and the wax was A = 69 ° B = 74 ° BA = 5 °

As the cleaning roller 107 shown in FIG. 5, an HTV silicone rubber (symbol Q) having a half of the outer diameter of the fixing roller and a rubber hardness of 30 according to JIS A was used. At this time, the contact angle between the cleaning roller and the wax was C = 60 °. The same evaluation as in Example 1 was performed with respect to OHP transmittance, image gloss unevenness, and offset resistance.

Further, the cleaning property was evaluated according to the following evaluation method.

(6) Cleaning Performance The cleaning performance was evaluated by fixing the 50% original document at 1/4 the speed at which plain paper was fixed, and then passing plain paper in the blank state at normal speed. The value of the Macbeth density on the surface of the plain paper after passing the paper was determined based on the following evaluation criteria.

The Macbeth density was measured using a Macbeth densitometer RD91.
The reflection density was measured using a filter of Model 8 (manufactured by Macbeth), and the average value of 10 measurements was taken as the Macbeth density.

(Evaluation Criteria) A: 0.1 or less B: More than 0.1 to 0.2 or less C: More than 02

Comparative Example 9 Developer No. 1 used in Example 12 Developer No. 1 used in Comparative Example 2 instead of Evaluation was performed in the same manner as in Example 12 except that Sample No. 2 was used. The contact angle at this time was A = 83 ° B = 92 ° B−A = 9 ° C = 65 °, and it is presumed that the contact angle was large and a satisfactory image was not achieved.

Comparative Example 10 An evaluation was performed in the same manner as in Example 12 except that PTFE was used instead of the FEP used as the surface material of the heating roller and the pressure roller used in Example 12, and the evaluation was satisfactory. No results were obtained. This is presumably because the contact angle was inappropriate.

Comparative Example 11 An evaluation was performed in the same manner as in Example 12 except that RTV silicone rubber was used instead of the FEP used as the surface material of the heating roller and the pressure roller used in Example 12, but No satisfactory results were obtained. This is presumably because the contact angle was inappropriate.

Example 13 PFA was used in place of FEP used as a surface material of the heating roller and the pressure roller used in Example 12, and an RTV having a rubber hardness of 40 as Asker C was used for the cleaning roller.
When image formation was performed in the same manner as in Example 12 except that silicone rubber was used, good results were obtained.

Example 14 The developer No. used in Example 12 Developer No. 1 used in Example 3 in place of 8 and evaluation was performed in the same manner as in Example 12 except that fluorine rubber (symbol FKM) was used for the cleaning roller. As a result, good results were obtained.

Example 15 The developer No. used in Example 12 Developer No. 1 used in Example 4 in place of Evaluation was performed in the same manner as in Example 12 except that No. 9 was used, and good results were obtained.

The above Examples 12-15 and Comparative Example 9-1
Table 4 shows the evaluation results of No. 1.

[0287]

[Table 4]

Example 16 The fixing device of the full-color copying machine CLC-800 used in Example 12 was modified to that shown in FIG. 6, the surface material of the fixing film was FEP, and the cleaning roller 121 was PF
A and a suitable filler are added, a 50 μm tube adjusted so that the contact angle C is 55, and a hollow iron pipe so that the outer diameter is formed to １ ／ of the belt circumference. The same procedure was carried out except for the above, and good results were obtained as shown in Table 5.

[0289]

[Table 5]

Example 17 Commercially available full-color copying machine CLC-8 used in Example 12
In the same manner as in Example 19, the two-component developer N
o. 1, No. 13, No. 14 and No. A full-color fixed image was obtained using 15 four-color developers. As a result, the color reproducibility of pale colors was excellent, and good results were obtained. Further, when a full-color image was projected by OHP, a very clear and good projected image was obtained.

Example 18 Commercially available full-color copying machine CLC-8 used in Example 17
4 was replaced with a full-color image forming apparatus using an intermediate transfer member as shown in FIG. 1, No. 13, No. 14 and No. An unfixed full-color image was formed using 15 four-color developers, and a full-color colored image was obtained using the same fixing device as that used in Example 17. As a result, good results were obtained as in Example 17.

Embodiment 19 The black developing unit 54-4 holding the black toner of the full-color image forming apparatus shown in FIG. 4 used in Embodiment 18 and used in Embodiment 11 for developing the magnetic one-component developer 16 can be developed. An unfixed full-color image was formed in the same manner as in Example 18 except that the image forming apparatus was changed to the image forming apparatus.
Fixing was performed in the same manner as in Example 8 to obtain a full-color colored image. As a result, good results were obtained as in Example 18.

[0293]

According to the present invention, the specific wax is used as the wax contained in the toner, and the contact angle between the wax and the heating member is set in a specific range. When applied to OHP, it is possible to obtain a clear full-color translucent image having excellent transparency.

Further, when the contact angle C between the cleaning member and the wax contained in the toner at 100 ° C. is set in the range of 0 to 60, the toner residue adhering to the heating member surface can be removed satisfactorily. The durability of a large number of sheets is improved.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a heating roller type fixing device used in the present invention.

FIG. 2 is a schematic view showing an example of a film heating type fixing device used in the present invention.

FIG. 3 is a schematic view showing an example of an image forming apparatus used in the image forming method of the present invention.

FIG. 4 is a schematic view showing an example of an image forming apparatus using an intermediate transfer member used in the image forming method of the present invention.

FIG. 5 is a schematic view showing another example of a heating roller type fixing device used in the present invention.

FIG. 6 is a schematic view showing another example of a film heating type fixing device used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Photosensitive drum (latent image holding body) 4Y, 4C, 4M, 4K Developing device 5A Transfer device 9 Heat fixing device 9a Heating roller 9b Pressure roller 51 Photoconductor (latent image holding member) 54-1 Cyan developing device 54-2 Magenta developing device 54-3 Yellow developing device 54-4 Black developing device 55 Intermediate transfer member 56 Recording material 57 Transfer roller (transfer member) 61 Heat fixing device 101 Heat roller 102 Pressure roller 107 Cleaning roller (cleaning member) 111 Fixing film 112 Pressure roller P Recording material T Toner

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-356057 (JP, A) JP-A-4-106554 (JP, A) JP-A-4-107566 (JP, A) JP-A-1- 260458 (JP, A) JP-A-3-284781 (JP, A) JP-A-2-162382 (JP, A) JP-A-6-123994 (JP, A) JP-A-7-98511 (JP, A) JP-A-6-337540 (JP, A) JP-A-6-337541 (JP, A) JP-A-2-199462 (JP, A) JP-A-7-301951 (JP, A) JP-A-7-87296 (JP, A) JP-A-3-114064 (JP, A) JP-A-8-54750 (JP, A) JP-B-49-209 (JP, B1) (58) Fields investigated (Int. Cl. ⁷⁾ , DB name) G03G 9/08

Claims (47)

(57) [Claims] A latent image forming step of forming an electrostatic latent image on a latent image holding member; a developing step of developing the electrostatic latent image with a color toner to form a toner image; A transfer step of transferring, and an image forming method having a fixing step of fixing the toner image transferred to the recording material to the recording material by a heating fixing device having a heating member that presses against the toner image, wherein the color toner is It has at least a binder resin, a colorant and a wax, and the wax has a weight average molecular weight / number average molecular weight (Mw / Mn) of 1.45 or less in a molecular weight distribution measured by GPC. And a solubility parameter of 8.4 to 10.5, wherein the contact angle between the wax and the heating member at 100 ° C. is A, and the contact angle of the wax and the heating member at 200 ° C. When the antennae and B, contact angle A and B, an image forming method characterized in that it satisfies the following relationship 60 ° ≦ A ≦ 80 ° 10 ° ≧ B-A ≧ 3 °. 2. The wax has a weight average molecular weight (Mw) of 200 to 2,000 and a number average molecular weight (Mn) of 150 to 2,000 in a molecular weight distribution measured by GPC. Item 2. The image forming method according to Item 1. 3. The melting point (mp) of the wax is higher than the glass transition temperature (Tg) of the binder resin, and the melting point (mp) of the wax and the glass transition temperature (Tg) of the binder resin are higher.
temperature difference between g), the image forming method according to claim 1 or 2, characterized in that at 100 ° C. or less. 4. The color toner melts a toner material containing at least the binder resin, the colorant and the wax.
The image forming method according to any one of claims 1 to 3, characterized in that it comprises a kneading step and the resulting kneaded product color toner particles prepared by the steps of pulverizing the. Wherein said color toner, the polymerizable monomer, of claims 1 to 3, characterized in that it comprises a coloring agent and a color toner particles prepared by direct polymerization of a monomer composition comprising at least the wax The image forming method according to any one of the above. 6. The image forming method according to claim 5 , wherein the color toner particles are prepared by directly polymerizing the monomer composition in an aqueous medium. 7. The color toner particles according to claim 1, wherein the monomer composition is prepared by suspending and dispersing the monomer composition in an aqueous medium and directly polymerizing the suspension by suspension polymerization.
7. The image forming method according to item 6 . 8. The heat fixing device according to claim 1, wherein the heat fixing device uses a roller heat fixing system having a heat roller and a pressure roller that is in pressure contact with the heat roller, and the heat roller is used as the heating member. Item 8. The image forming method according to any one of Items 1 to 7 . 9. The heat fixing device employs a film heat fixing method of heating and fixing the toner image while pressing a fixing film against the toner image, wherein the fixing film is used as the heating member. Claims 1 through
8. The image forming method according to any one of 7 . At least the surface of 10. The heating member is an image according to any one of claims 1 to 9, characterized in that it is formed by a copolymer having repeating units of at least tetrafluoroethylene backbone Forming method. 11. At least a surface of the heating member is formed of a copolymer having at least a repeating unit of tetrafluoroethylene in a main chain and a fluoroalkoxy group or a fluoroalkyl group in a side chain. the image forming method according to any one of claims 1 to 9, characterized in that. 12. The heating member according to claim 1, wherein at least a surface of the heating member is formed of a copolymer having at least a repeating unit of tetrafluoroethylene in a main chain and a fluoroalkyl group in a side chain. claim 1
10. The image forming method according to any one of the above items 9 . 13. The image forming method according to claim 11 or 12, characterized in that the fluoroalkyl group is 3 methyl fluoride group. 14. The heat fixing device uses a film heat fixing method of heating and fixing the toner image while pressing a fixing film against the toner image, wherein the fixing film is used as the heating member. 14. The fixing film according to claim 1, wherein at least a surface of the fixing film is formed of a copolymer having at least a repeating unit of tetrafluoroethylene in a main chain .
The image forming method according to any one of the above. 15. At least a surface of the fixing film,
15. The image forming apparatus according to claim 14 , wherein the copolymer is formed of a copolymer having at least a repeating unit of tetrafluoroethylene in a main chain and having a fluoroalkoxy group or a fluoroalkyl group in a side chain. Method. 16. The heating member according to claim 16, wherein at least a surface of the heating member is formed of a copolymer having at least a repeating unit of tetrafluoroethylene in a main chain and a fluoroalkyl group in a side chain. Item 15. The image forming method according to Item 14 . 17. The image forming method according to claim 15 or 16, characterized in that the fluoroalkyl group is 3 methyl fluoride group. 18. A first transfer step of transferring the toner image formed on the latent image holding member to an intermediate transfer member, and a first transfer step of transferring the toner image transferred to the intermediate transfer member to the recording material. 2
Claims 1 to 17, characterized in that it has a transfer step
The image forming method according to any one of the above. 19. The image forming method includes a step of cleaning a surface of the heating member by bringing a cleaning member into contact with a surface of the heating member of the heat fixing device, wherein the cleaning member and the wax are provided. when the contact angle is C at 100 ° C. with, contact angle C is claims 1 to 18 Noi, characterized in that it satisfies the following relationships 0 ° ≦ C ≦ 60 °
An image forming method according to any of the above. 20. The image forming method includes a step of cleaning a surface of the heating member by bringing a cleaning member into contact with a surface of the heating member of the heating and fixing device. 2000 weight average molecular weight (Mw) and 150-2000 number average molecular weight (Mw)
n) wherein the contact angle between the cleaning member and the wax at 100 ° C. is C, the contact angle C satisfies the following relationship: 0 ° ≦ C ≦ 60 ° Claims 1 to 18
An image forming method according to any of the above. At least the surface of 21. The cleaning member, an image forming method according to claim 19 or 20, characterized in that it is formed by a silicone rubber or fluorine rubber. At least the surface of 22. The cleaning member, an image forming method according to claim 19 or 20, characterized in that it is formed by a fluororesin. 23. The toner image, a cyan toner, an image forming method according to any one of claims 1 to 22, characterized in that a full-color toner image formed by at least combining the magenta toner and yellow toner. 24. The toner image, a cyan toner image according to the magenta toner, any one of claims 1 to 22, characterized in that the yellow toner and the black toner is a full color toner image formed by at least combining Forming method. 25. A heat fixing method for fixing a toner image formed of a color toner on a recording material to the recording material by a heat fixing device having a heating member for pressing the toner image against the toner image, wherein the color toner includes at least a binder. A resin, a colorant, and a wax, wherein the wax has a weight average molecular weight / number average molecular weight (Mw / Mn) of 1.45 or less in a molecular weight distribution measured by GPC, and 8 And a contact angle between the wax and the heating member at 100 ° C. is A and a contact angle between the wax and the heating member at 200 ° C. is B. The heat fixing method, wherein the contact angles A and B satisfy the following relationship: 60 ° ≦ A ≦ 80 ° 10 ° ≧ BA−3 ° 26. The wax according to claim 26, wherein the wax has a weight average molecular weight (Mw) of 200 to 2,000 and a number average molecular weight (Mn) of 150 to 2,000 in a molecular weight distribution measured by GPC. Item 26. The heat fixing method according to Item 25 . 27. The melting point (mp) of the wax is higher than the glass transition temperature (Tg) of the binder resin, and the melting point (mp) of the wax and the glass transition temperature (Tg) of the binder resin are
27. The heat fixing method according to claim 25 , wherein the temperature difference from g) is 100 ° C. or less. 28. The color toner particles prepared through a step of melting and kneading a toner material containing at least the binder resin, the colorant and the wax, and a step of pulverizing the obtained kneaded material. The heat fixing method according to any one of claims 25 to 27 , comprising: 29. The color toner, comprising: a polymerizable monomer;
Heat fixing method according to any one of claims 25 to 27, characterized in that it comprises a coloring agent and a color toner particles prepared by direct polymerization of at least comprising monomer composition the wax. 30. The heat fixing method according to claim 29 , wherein the color toner particles are prepared by directly polymerizing the monomer composition in an aqueous medium. 31. The color toner according to claim 30 , wherein the color toner particles are prepared by suspending and dispersing the monomer composition in an aqueous medium and directly polymerizing the suspension by suspension polymerization. Heat fixing method. 32. The heating and fixing device uses a roller heating and fixing system having a heating roller and a pressure roller pressed against the heating roller, and the heating roller is used as the heating member. Item 32. The heat fixing method according to any one of Items 25 to 31 . 33. The heat fixing device uses a film heat fixing method of heating and fixing the toner image while pressing a fixing film against the toner image, wherein the fixing film is used as the heating member. Claim 25
33. The heat-fixing method according to any one of Items 1 to 32 . 34. The heating device according to claim 25 , wherein at least the surface of the heating member is formed of a copolymer having at least a repeating unit of tetrafluoroethylene in a main chain. Fixing method. 35. At least the surface of the heating member is formed of a copolymer having at least a repeating unit of tetrafluoroethylene in a main chain and having a fluoroalkoxy group or a fluoroalkyl group in a side chain or both. The heat fixing method according to any one of claims 25 to 33, wherein: 36. At least the surface of the heating member is formed of a copolymer having at least a repeating unit of tetrafluoroethylene in a main chain and a fluoroalkyl group in a side chain. Item 25
35. The heat fixing method according to any one of to 33 . 37. A heat fixing method according to claim 35 or 36, characterized in that the fluoroalkyl group is 3 methyl fluoride group. 38. The heat fixing device uses a film heat fixing method of heating and fixing the toner image while pressing a fixing film against the toner image, wherein the fixing film is used as the heating member. 34. The fixing film according to claim 25 , wherein at least a surface of the fixing film is formed of a copolymer having at least a repeating unit of tetrafluoroethylene in a main chain.
37. The heat fixing method according to any one of 37 . 39. At least a surface of the fixing film,
39. The heat fixing method according to claim 38 , wherein the heat fixing is performed by using a copolymer having at least a repeating unit of tetrafluoroethylene in a main chain and a fluoroalkoxy group or a fluoroalkyl group or both in a side chain. Method. 40. The heating member according to claim 40, wherein at least a surface of the heating member is formed of a copolymer having at least a repeating unit of tetrafluoroethylene in a main chain and a fluoroalkyl group in a side chain. Item 40. The heat fixing method according to Item 39 . 41. A heat fixing method according to claim 39 or 40, characterized in that the fluoroalkyl group is 3 methyl fluoride group. 42. The image forming method according to claim 42, further comprising a step of cleaning the surface of the heating member by bringing a cleaning member into contact with the surface of the heating member of the heat fixing device. when the contact angle is C at 100 ° C. with, contact angle C is the claim 25 to 41, characterized in that it satisfies the following relationships 0 ° ≦ C ≦ 60 °
The heat fixing method according to any one of the above. 43. The image forming method has a step of cleaning a surface of the heating member by bringing a cleaning member into contact with a surface of the heating member of the heating and fixing device. 2000 weight average molecular weight (Mw) and 150-2000 number average molecular weight (Mw)
n) wherein the contact angle between the cleaning member and the wax at 100 ° C. is C, the contact angle C satisfies the following relationship: 0 ° ≦ C ≦ 60 ° Claims 25 to 41
The heat fixing method according to any one of the above. At least the surface of 44. The cleaning member is heat fixing method according to claim 42 or 43, characterized in that it is formed by a silicone rubber or fluorine rubber. At least the surface of 45. The cleaning member is heat fixing method according to claim 42 or 43, characterized in that it is formed by a fluororesin. 46. The toner image, a cyan toner, heat fixing method according to any one of claims 25 to 45, characterized in that a full-color toner image formed by at least combining the magenta toner and yellow toner. 47. The toner image is heated according to any one of claims 25 to 45, characterized in that the cyan toner is a full color toner image formed by a magenta toner, a yellow toner and a black toner were at least combined Fixing method.