JP2000098651A - Method for fixing toner image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a method for fixing a toner image by which adhesion of a toner on a fixing roller surface can be effectively prevented without supplying oil or the like to the fixing roller or the like, and the transparency or haze of an OHP image after fixing is not damaged, and to provide a method for fixing a toner image by which a high quality image can be stably obtd. without decreasing developing capability even when a toner produced by a polymn. method is used as a two-component developer. SOLUTION: An image formed with a toner carried on a recording material is heated and/or pressurized by a fixing member in order to fix the image on the recording material, wherein the toner contains at least a binder resin, coloring agent and wax. The wax contains at least silicone polymer, silicone oil and silica fine particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[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.
Many methods are known, as described in Japanese Patent Publication No. JP-B-43-24748 and Japanese Patent Publication No. 43-24748. Generally, using a photoconductive substance, an electric latent image is formed on a photoreceptor by various means, and then the latent image is developed using toner,
If necessary, using a direct or indirect means, after transferring the toner image to a transfer material such as paper, heating, pressure,
A copy is obtained by fixing under heat and pressure or solvent vapor. The toner remaining on the photoreceptor without being transferred is cleaned and removed by various methods, and then the above-described steps are repeated to form a plurality of images.

A general method for forming a full-color image will be described. The photosensitive member of a photosensitive drum is uniformly charged by a primary charger, and image exposure is performed by a laser beam modulated by a magenta image signal of a document. Then, an electrostatic latent image is formed on the photosensitive drum, and the electrostatic latent image is developed by a magenta developing device having magenta toner, thereby forming a magenta toner image. Next, the magenta toner image developed on the photosensitive drum as described above is transferred onto the conveyed transfer material by a transfer charger using direct or indirect means.

[0004] On the other hand, the photosensitive drum after the development of the electrostatic latent image is discharged by a discharging charger, cleaned by cleaning means, and charged again by a primary charging device. Thus, a cyan toner image is formed. Further, the cyan toner image thus formed is transferred in a superimposed manner onto the transfer material on which the magenta toner image has already been transferred in the above-described process. Further, in the same manner as above, the formation of the yellow color image and the black color image is sequentially performed in the same manner, and the four color toner images are transferred onto the transfer material. Subsequently, the four color toner images formed on the transfer material are fixed by the action of heat and / or pressure by a fixing roller to form a full color image.

[0005] In recent years, such a device has begun to be used not only in office copying machines for copying original documents, but also in the field of printers as personal computer output devices or personal copies for individuals. Further, in addition to the field represented by the laser beam printer, the development of a plain paper facsimile machine or the like to which a basic engine is applied has been rapidly developing.

[0006] For this reason, smaller, lighter, faster, higher image quality, and higher reliability have been strictly pursued, and machines have become simpler in various aspects. ing. As a result, the performance required of the toner has become higher, and if the improvement of the performance of the toner cannot be achieved, a machine having higher performance cannot be realized. Further, in recent years, demands for color copying have rapidly increased in accordance with various copying needs, and further higher image quality, higher resolution, and the like are desired in order to more faithfully copy an original color image.
From these viewpoints, the toner used in the method for forming a color image needs to have good contact properties and color mixing when heat is applied to the toner, and has a low softening point and a low melt viscosity. It is desirable to use a toner having a high melting property.

That is, if a toner having a high sharp-melting property as described above is used, the color reproduction range of a copy can be widened,
A color copy faithful to the original image can be obtained.
However, a color toner having a high sharp melt property generally has a high affinity with a 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 plurality of toner layers of magenta, cyan, yellow, and black are formed on a transfer material, offset is particularly likely to occur due to an increase in toner layer thickness. The tendency is remarkable.

Conventionally, for the purpose of suppressing toner adhesion to the surface of a fixing roller, a resin coating layer made of a material having excellent releasability with respect to the toner, for example, a silicone rubber or a fluorine resin is formed on the surface of the roller. Further, on the surface of the resin coating layer, a liquid having high releasability such as silicone oil or fluorine oil is applied to prevent offset and prevent fatigue of the roller surface, and the surface of the fixing roller is coated with these liquids. Coating has been performed. However,
Although this method is extremely effective in preventing toner offset, it requires a device for supplying a liquid having high releasability for preventing offset, so that the fixing device becomes complicated and large-scale. Of course, the oil application causes the resin coating layer constituting the fixing roller to peel off, and consequently has an adverse effect of promoting the shortening of the service life of the fixing roller. In general, various papers, coated papers, plastic films, and the like are used as a transfer material on which a toner image is fixed using such a fixing device. In particular, in recent years, attention has been paid to a need for a transparency film (OHP) having excellent characteristics, which is mainly used for presentation and used when forming a transmission image using an overhead projector.

[0009] In particular, the OHP has a low oil absorption capacity unlike paper, so that the currently available copy OHP does not
The stickiness due to the oil application performed in the fixing process described above is inevitable, and a large problem remains in the quality of the formed image. Further, at the time of fixing, there is a high possibility that the highly releasable liquid applied to the surface of the fixing roller, such as silicone oil, evaporates due to heat and contaminates the inside of the apparatus, and that problems such as processing of collected oil are generated. . On the other hand, as an alternative that can effectively prevent offset without using a supply device for applying silicone oil or the like to the surface of the fixing roller, a liquid for preventing offset is immersed in the toner during heating. It is conceivable that the toner is ejected and supplied to a fixing roller, and a method of adding a release agent such as low molecular weight polyethylene or low molecular weight polypropylene to the toner has been proposed.

However, in order to obtain a sufficient effect on the addition of the release agent, if such an additive is added in a large amount to the toner, filming on the photoreceptor or the surface of the toner carrier such as a carrier or a sleeve is not performed. , And image deterioration, which causes a practical problem. Therefore, a small amount of release agent is added to the toner to such an extent that the image is not deteriorated, and a small amount of release oil is supplied in combination with this.
Alternatively, a device that uses a member such as a web of a take-up type, for example, a web, or a device that cleans using a cleaning pad is used.

However, particularly in the full color field, conventional means for incorporating a release agent in a toner, when OHP is used as a material to be transferred, causes a high crystallization of the release agent and a deformation with resin. For example, the transparency and haze of the image after fixing are slightly reduced due to a cause such as a difference in deposition rate.

It is known that a wax is contained as a release agent in a toner.
04, JP-B-52-3305, JP-A-57
The technology is disclosed in, for example, US Pat.
Also, JP-A-3-50559 and JP-A-2-7986
0, JP-A-1-109359, JP-A-62
JP-A-14166, JP-A-61-273554, JP-A-61-94062, JP-A-61-13
No. 8259, JP-A-60-252361, JP-A-60-252360, JP-A-60-2173
No. 66 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, but deteriorate the blocking resistance and increase the temperature of copiers and the like. When exposed to heat, the developability deteriorates, and when the toner is left for a long period of time, the wax migrates to the toner surface to deteriorate the developability.

[0013] None of the conventional toners satisfy all of the above aspects, and have some problems. For example, high-temperature offset and developability are excellent, but low-temperature fixability is just one step away, or low-temperature offset and low-temperature fixability are excellent, but blocking resistance is slightly inferior, and developability at elevated temperatures in the machine. There have been adverse effects such as lowering, inadequate offset resistance at low and high temperatures, and extremely poor OHP transparency. In particular, regarding the improvement of the transparency of an OHP image, a proposal is made to add a crystallization nucleating agent or the like to the wax in order to reduce the crystallization of the wax itself (JP-A-4-149559, JP-A-4-1074).
No. 67) or using a wax having a low degree of crystallinity (see Japanese Patent Application Nos. 3-091108 and 3-242397), and further using a binder resin (binder resin). Is proposed to improve the surface smoothness of the toner layer after fixing by adding a substance having good compatibility and a lower melt viscosity than the binder resin to the binder resin. Have been.

As one of the release agents having relatively good transparency and low-temperature fixing performance, montan wax which is a mineral wax is known. For example, as a montan wax, a molecular weight of about 800 represented by the following structural formula:
The wax can be added as a release agent to the toner, as disclosed in JP-A-1-185660 and JP-A-1-185.
661, JP-A-1-185662, JP-A-1-185661, and JP-A-1-238672.

[0015]

Embedded image However, none of these could sufficiently satisfy the required performance in terms of transparency of the OHP image and haze (haze value).

On the other hand, in order to inhibit the crystallinity of the release agent itself, use of an ester wax in which the structural symmetry of the release agent itself is broken has been disclosed in Japanese Patent Application No. 5-1185.
No. 17, Japanese Patent Application No. 5-126180, Japanese Patent Application No. 5-126
No. 181 and fairly good results have been obtained. Furthermore, even in recent full-color fixing devices,
High durability and high reliability have been demanded, and without improving the fixing device, only improving the binder resin and release agent that constitute the toner, from high image area image to low image area image, and furthermore, It is difficult to stably realize an image forming method applicable to a wide range up to a full-color OHP image over a long period of time. Therefore, further improvement of the toner composition and improvement of the fixing process are desired.

Further, in order to exhibit good low-temperature fixability and offset resistance, the wax contained in the toner may be:
Its molecular weight distribution has at least two peaks and / or shoulders, and has a weight average molecular weight (Mw) of 400 to 4000 and a number average molecular weight (Mn) of 20.
It is known that the use of a material having a value of 0 or more and 4000 or less can inhibit the crystallinity of the wax and further improve the transparency of the OHP image.

However, the toner containing the wax having the molecular weight distribution described above uses a polymerization method in which a polymerizable monomer is polymerized in an aqueous medium during the production process. At this time, the presence of emulsified particles due to the wax is inevitable, because the emulsified particles adhere to the surface of the generated toner particles, for example,
When mixed with a carrier and used as an image forming agent as a two-component developer, when the toner rubs against the carrier, the emulsified particles may adhere to the carrier surface, so that the toner may not be sufficiently charged. In some cases, the developing ability may be reduced.

[0019]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a fixing roller without supplying a liquid such as silicone oil having a high releasability to the fixing roller. The toner is prevented from adhering to the surface and no offset occurs.
An object of the present invention is to provide a method for fixing a toner image in which the transparency and haze of an OHP image after fixing are not impaired. Furthermore, an object of the present invention is to provide a two-component developer in which a toner is produced by a polymerization method and mixed with a carrier. It is an object of the present invention to provide a method for fixing a toner image, which can be sufficiently stably secured and a high-quality image can be stably obtained.

[0020]

The above object is achieved by the present invention described below. That is, the present invention provides a method for fixing a toner image, in which an image formed by toner carried on a recording material is heated and / or pressed by a fixing member and fixed on the recording material, wherein the toner comprises at least A method for fixing a toner image, comprising a binder resin, a colorant, and a wax, wherein the wax contains at least a silicone polymer, a silicone oil, and silica fine particles.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The present inventors have conducted intensive studies to solve the above-mentioned problems of the prior art, and as a result, as a release agent added to the toner to prevent offset to the fixing roller and improve low-temperature fixing property. If a wax containing silicone polymer, silicone oil, and ultrafine silica is used, the occurrence of offset is suppressed and a high-quality image without fog is obtained.
In addition, it has been found that when OHP is used as the material to be transferred, the transparency and haze of the OHP image after fixing are not impaired. Further, if a wax containing a silicone polymer, silicone oil, and ultrafine silica is used as a release agent to be added to the toner, it is caused by the addition of the wax generated when the toner is manufactured using a polymerization method. It is also found that the toner adhesion of the emulsified particles is effectively masked, so that carrier contamination which occurs when used as a two-component developer can be effectively prevented.

First, the wax added as a release agent to the toner used in the toner image fixing method of the present invention will be described. The wax used in the present invention is characterized by containing a silicone polymer, a silicone oil, and ultrafine silica. Hereinafter, these materials will be described.

In the present invention, a silicone polymer (silicone resin) represented by the following structural formula can be suitably used as the silicone polymer contained in the wax.

[0024]

Embedded image That is, by blending the above-mentioned silicone resin into wax, when a toner image formed by a toner containing the wax is heat-fixed, it is transparent and very flexible. It becomes possible to form a film.

However, since the silicone resin having the structure shown above is insoluble in wax,
As it is, it cannot be blended in a good condition in the wax. Therefore, in the present invention, by using silicone oil in combination with a silicone polymer,
Incorporate the silicone polymer in the wax in good condition. As the silicone oil used at this time, it is preferable to use a solution of decamethylcyclotetrasiloxane, which is a cyclic volatile silicone oil having the following structure.

[0026]

Embedded image Octamethylsiloxane can be effectively used for the same purpose. As commercially available products, SH344 and DC345 manufactured by Dow Corning Toray Co., Ltd. can be used. In the present invention, a study experiment was performed using these without particular purification.

Further, in order to reduce stickiness caused by a low molecular weight component of the silicone resin, silica fine particles are further added to the wax contained in the toner used in the present invention. According to the study of the present inventors, ultrafine particles having a particle diameter of 0.015 μm, spherical particles having a spherical shape, and a surface area of 110 m ² /
It was found that excellent effects were exhibited when lipophilic spherical silica fine particles as g were contained.

The wax contained in the toner used in the present invention has a compounding agent comprising the above-mentioned silicone polymer, silicone oil, and ultrafine silica, and the compounding method described below may be used. it can. That is, when a toner is manufactured by a method of melt-blending using a media type disperser or the like set at a temperature equal to or higher than the melting point of the wax in which these compounding agents are blended, or when a toner is produced by a polymerization method, the wax to be blended is mixed with It is also possible to blend them with a media-type dispersing machine after melting them, or to add these compounding agents from outside as a masking agent after the polymerization process is completed. Examples of the media type dispersing machine used at this time include a ball mill, a sand mill, an attritor, an apex mill, a co-ball mill, and a handy mill.

The wax containing the above-mentioned compounding agent used in the present invention has an appropriate affinity with the binder resin constituting the toner in order to exhibit good low-temperature fixability and offset resistance in the toner. It is preferable to use a low crystalline material having high hydrophobicity and a low melting point. Further, the molecular weight distribution of the wax has at least two peaks and / or shoulders in the distribution curve, the weight average molecular weight (Mw) is 400 or more and 4,000 or less, and the number average molecular weight (Mn) is 200 or more and 4, It is preferable to use those having a molecular weight of 000 or less. Further, as a result of the study of the present inventors, the above-mentioned molecular weight distribution may be achieved by a single wax, or may be achieved by having a plurality of waxes together, and satisfy the above-mentioned molecular weight distribution. As a result, it has been found that the use of a wax can inhibit the crystallinity of the wax, and in particular, can further improve the transparency of an OHP image.

In this case, the method of blending two or more waxes is not particularly limited,
For example, when a toner is produced by a method of melt blending using a media type disperser or the like set to a melting point of the wax to be blended or a polymerization method, the wax to be blended is melted into a polymerizable monomer, and the medium is melted. It is possible to use a method of blending with a disperser or the like. As the media type disperser used at this time, for example, a ball mill, a sand mill, an attritor, an apex mill, a co-ball mill, a handy mill and the like can be used. Further, when blending two or more waxes, additives such as a pigment as a colorant, a charge control agent, and a polymerization initiator may be added.

The molecular weight distribution of the wax used in the present invention was measured by GPC under the following measurement conditions. (GPC measurement conditions) • Apparatus: GPC-150C (Waters) • Column: GMH-HT 30 cm, 2 columns (manufactured by Tosoh Corporation) • Temperature: 135 ° C. • Solvent: o-dichlorobenzene (0.1% ionol added) Flow rate: 1.0 ml / min ・ Sample: 0.4 ml of 0.15% sample is injected

In calculating the molecular weight of the wax, GPC is measured under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used. Furthermore, the average molecular weight was calculated by converting into polyethylene using a conversion formula derived from the Mark-Houwink viscosity formula. As described above, the wax contained in the toner used in the present invention has a weight average molecular weight (Mw) of 400 or more and 4000 or less and a number average molecular weight (Mw).
n) is preferably 200 or more and 4000 or less, more preferably Mw is 450 or more and 3500 or less, still more preferably 500 or more and 3000 or less, and Mn is 200 or more and 3 or less.
It is desired to be 500 or less, more preferably 250 or more and 3000 or less. That is, when a wax having Mw of less than 400 and Mn of less than 200 is used, the blocking resistance of the toner is significantly deteriorated. On the other hand, Mw is 4,0
When the Mn is more than 4,000, the crystallinity of the wax itself is developed, and when a fixed image of the toner is formed on an OHP image or the like, the transparency of the image tends to be significantly impaired. .

The wax containing the silicone polymer, silicone oil, and ultrafine silica described above is used in an amount of 1 to 40 parts by weight, more preferably 100 parts by weight, based on 100 parts by weight of the binder resin constituting the toner. 2-30
It is preferred that the content be in the range of parts by weight. Further, the preferred amount of the wax to be added depends on the method for producing the toner,
For example, in a dry toner manufacturing method in which a mixture having a binder resin, a colorant, and a wax is melt-kneaded, the cooled kneaded material is pulverized, and then classified to obtain toner particles, the binder resin 10 is used.
1 to 10 parts by weight, more preferably 2 to 0 parts by weight
It is preferable that the amount be 7 to 7 parts by weight. In addition, a polymerizable monomer composition comprising a mixture of a polymerizable monomer, a colorant, and a wax, is granulated, and the polymerizable monomer is polymerized to directly obtain toner particles. In the production method, it is preferable to use 2 to 40 parts by weight, more preferably 5 to 30 parts by weight, and still more preferably 10 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer.

In the polymerizable toner manufacturing method as compared with the above-mentioned dry toner manufacturing method, since a generally used release agent has a lower polarity than the binder resin, a large amount of the toner particles is contained in the toner particles by the polymerization method in which the polymerization reaction is carried out in an aqueous medium. The release agent is easily included. For this reason, compared with a toner obtained by a dry toner manufacturing method, a toner obtained by a polymerizable toner manufacturing method can generally use a larger amount of a release agent. Therefore,
The use of the toner obtained by the polymerizable toner production method has a higher effect in preventing offset to a fixing roller or the like that occurs when a toner image is heated and fixed. Further, the amount of wax added to the toner is less than the lower limit described above, it is difficult to obtain the effect of preventing offset, and when the wax is contained beyond the upper limit, the blocking resistance is reduced, and the offset resistance is reduced. This also tends to have an adverse effect, and tends to cause drum fusion and sleeve fusion. Further, in the case of a polymerization method toner, a toner having a wide particle size distribution tends to be generated.

In order to obtain a sufficiently transparent OHP image with a low heat capacity of a fixing device when a toner image is heated and fixed, it is generally necessary to lower the crystallinity of a release agent contained in the toner. Is the most important. However, as a secondary effect, in order to impart more sufficient transparency to the OHP image, it is necessary to suppress the existence of partially undissolved toner grain boundaries that cannot be dissolved after fixing, When the release agent layer formed between the fixing member and the fixing member has crystallinity, irregular reflection of light occurs, whereby the effective light transmittance is reduced, resulting in a reduction in haze. It is necessary to prevent this. 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 toner layer formed after the dissolution and the release agent layer is large, this also tends to cause irregular reflection of light. . Such an increase in irregular reflection of light leads to a decrease in brightness of a projected image and a decrease in color sharpness. In particular, when a transmission-type overhead projector is used, this problem is further increased than when a reflection-type overhead projector is used.

That is, in order to lower the crystallinity of the release agent layer, it is important to lower the crystallinity of the release agent alone. Further, in order to prevent unmelted toner grain boundaries from being present in the toner fixing layer, the glass transition temperature (T
It is effective to make the melting point (mp) of g) and the release agent approximately the same. In addition, in order to dissolve quickly with a low energy amount, it is particularly preferable to use a material having a small melting enthalpy (ΔH), which is the latent heat of the release agent.
The solubility parameter (SP) between the binder resin and the release agent is set so that the molten release agent quickly moves between the binder resin layer and the fixing member to quickly form the anti-offset layer. It is preferable that the difference be adjusted to an appropriate value.

Preferred examples of the wax selected from the above-mentioned viewpoints, which is a component of the toner used in the toner image fixing method of the present invention, will be described in detail below. First, as the wax suitably used in the present invention, a wax having a refractive index close to the refractive index of the binder resin constituting the toner is preferable. As the binder resin of the toner, generally, a polyester resin,
Since styrene-acrylic resin, epoxy resin, or styrene-butadiene resin is often used, it is preferable to use a resin having a refraction rate close to those of these resins. In the present invention, as a method of measuring the refractive index of a resin, first, using a resin to be measured, 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 thereon and measuring the rate of refraction is exemplified. Further, as a measuring instrument that can be used at this time, for example, an Appe segregation meter 2T manufactured by Atago Co., Ltd. can be mentioned. The wax used in the present invention has a refractive index difference between the binder resin and the wax of 0.18 as measured at a temperature of 25 ° C.
It is particularly effective to use a material having a value of 0.10 or less, more preferably 0.10 or less. When the difference in the refractive index exceeds 0.18, the transparency of the OHP image is easily reduced, and particularly, the halftone projection image is not preferable because the brightness becomes low.

The wax used in the present invention is preferably from 30 to
Preferably, it has a melting point of 150 ° C, and more preferably, has a melting point of 50 to 120 ° C.
That is, if the melting point of the wax contained in the toner is lower than 30 ° C., the blocking resistance of the toner, the resistance to contamination of the sleeve when a large number of sheets are copied, and the ability to prevent contamination of the photoconductor are likely to be reduced. On the other hand, when the melting point of the wax contained in the toner exceeds 150 ° C., particularly when the toner is manufactured by a pulverization method, a great amount of energy is required to uniformly mix the wax in the binder resin. . Further, even when a toner is produced by a polymerization method, when a wax having a melting point of more than 150 ° C. is used, an apparatus for increasing the viscosity used to promote uniformity of the wax contained in the binder resin is used. Since the size is increased and the limit of the amount of wax compatible with the binder resin is reduced, it becomes difficult to contain a large amount of wax.

The wax used in the present invention is preferably selected so that the difference in solubility parameter (SP) between the binder resin and the release agent becomes an appropriate value. In the present invention, it is preferable to appropriately select a material having an SP value in the range of 7.5 to 9.7. That is, a wax having an SP value of less than 7.5 has poor compatibility with the binder resin to be used, and as a result, it is difficult to obtain a good dispersion state in the binder resin. In this case, since the wax easily adheres to the developing sleeve, the charge amount of the toner may easily change. Further, ground fog, density fluctuation at the time of toner replenishment, and the like are likely to occur. On the other hand, when a wax having an SP value exceeding 9.7 is used, when the toner is stored for a long period of time,
Blocking between toners easily occurs. Furthermore, because the compatibility of the wax with the binder resin becomes too good,
At the time of heat fixing, it is difficult to form a sufficient release layer between the fixing member and the binder resin layer of the toner, and the offset phenomenon is likely to occur.

In the present invention, the solubility parameter (S
P) value is determined by the Fedors method using the additive nature of atomic groups [Poly. Eng. Sci. , 14 (2) 147
(1974)]. The wax contained in the toner used in the present invention is preferably a substance having good compatibility with the binder resin (binder resin) and having a lower melt viscosity than the binder resin. As a method for measuring the melt viscosity of wax, HAAK is used.
A method using a cone plate type rotor (PK-1) with VT-5000 manufactured by E Company.

The wax used in the present invention has a melt viscosity at 100 ° C. of 1 to 50 mPas. sec, more preferably 3 to 30 mPas. sec
Is used. That is,
1 mPas. When a wax having a melt viscosity lower than 2 sec is contained in the toner, when the toner layer is thinly coated on the developing sleeve by a blade or the like in a non-magnetic one-component developing method, the developing sleeve is mechanically sheared. It is easy to cause pollution. Also, in the two-component developing method, when development is performed using a two-component developer in which a toner is mixed with a carrier, the toner is liable to be damaged due to a shear force between the carrier and the toner. , Toner crushing and the like are likely to occur. Melt viscosity of wax is 50mPa
s. If the time exceeds sec, the viscosity of the dispersoid becomes too high when producing the toner using the polymerization method, so that it is not easy to obtain a toner having a fine particle diameter having a uniform particle diameter, The toner tends to have a wide particle size distribution.

The wax used as a releasing agent in the toner used in the present invention preferably has a Vickers hardness in the range of 0.3 to 5.0, more preferably 0.5 to 5.0. It is particularly effective to use a wax in the range of from 3.0 to 3.0. That is, a toner containing a wax having a Vickers hardness lower than 0.3 is liable to be crushed at a cleaning portion of a photosensitive drum of a copying machine or the like in multi-sheet copying, and toner is easily fused on the drum surface. As a result, black streaks are likely to occur on the image as a result. In addition, when multiple image samples formed by fixing the toner image are stored in a stack, the toner is transferred to the back surface, so that so-called show-through is easily generated, which is not preferable. On the other hand, in the case of a toner containing a wax having a Vickers hardness of more than 5.0, a fixing device used at the time of heat-fixing requires more pressing force than necessary. It is not preferable. That is, in this case, it is not preferable to use a fixing device having a normal pressing force because the offset resistance tends to decrease.

The hardness of the wax is measured, for example, by a measuring method using a Shimadzu Dynamic Ultra Micro Hardness Tester (DUH-200). The measurement conditions were using a Vickers indenter,
10 at a load speed of 9.67 mg / sec under a load of 0.5 g.
After being displaced by μm, the sample is held for 15 seconds, and the Vickers hardness is determined by analyzing the dents formed on the sample.
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.

Further, the wax used in the present invention has a crystallinity of 10 to 50%, more preferably 20 to 3%.
It is preferable to use 5%. That is, if a wax having a crystallinity of less than 10% is used, the toner storability and fluidity are liable to be deteriorated.
This is not preferable because the transparency of the P image is easily lost. The degree of crystallinity of the wax used in the present invention 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.

[0045]

(Equation 1) In addition, as a measuring device for measuring the crystallinity of wax,
For example, Rikuflex RU300 manufactured by Rigaku Denki Co., Ltd.
(Cu target, point focus, output 50kV
/ 250 mA). As the measurement conditions, a transmission method and one rotation method are used, and the measurement angle is 2θ = 5 to 35 °.

As the wax preferably used in the toner used in the toner image fixing method of the present invention, it is preferable to use an ester wax having the above-mentioned various properties. As a method for producing the ester wax, for example, a synthesis method by an oxidation reaction, a synthesis from a carboxylic acid and a derivative thereof, an ester group introduction reaction represented by a Michael addition reaction, and the like are used. Particularly preferred production methods for producing the ester wax used in the present invention include, for example, dehydration condensation from a carboxylic acid compound and an alcohol compound, as shown in the following formula, from the variety of raw materials and ease of reaction. Preferable examples include a method of synthesizing using a reaction, or a reaction between an acid halide and an alcohol compound.

[0047]

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

Other materials constituting the toner used in the toner image fixing method of the present invention will be described below. As the binder resin, which is the main raw material constituting the toner,
Any of the following resins can be used. For example, styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene and a homopolymer of a substituted product thereof; styrene-p-
Chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer Coalesce, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, Styrene-based copolymers such as styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin-modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester Street fat Polyurethane, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum resin, or the like can be used. Among these, a particularly preferred binder is a styrene copolymer or a polyester resin.

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

The binder resin used in the present invention has a THF-soluble component having a number average molecular weight of 3,000 to 1,000.
It is preferred to use those of 000. The styrene-based polymer or styrene-based copolymer may be cross-linked with a cross-linking agent for the binder resin, or may be a mixed resin thereof.

In the present invention, a compound having two or more polymerizable double bonds may be mainly used as a crosslinking agent for the binder resin. 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 divinyl aniline, divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups, alone or as a mixture. The addition amount is preferably 0.001 to 10 parts by weight based on 100 parts by weight of the polymerizable monomer.

The toner used in the present invention may contain a charge control agent. The following substances control the toner to be negatively charged. For example, an organic metal compound and a chelate compound are effective, and examples thereof include a monoazo metal compound, an acetylacetone metal compound, an aromatic hydroxycarboxylic acid, and an aromatic dicarboxylic acid-based metal compound. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. Also, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarenes, silicon compounds, styrene-
An acrylic acid copolymer, a styrene-methacrylic acid copolymer, a styrene-acryl-sulfonic acid copolymer, a non-metal carboxylic acid compound, and the like can be given.

The following substances control the toner to be positively charged. Modified products such as nigrosine and fatty acid metal salts, guanidine compounds, imidazole compounds, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and analogs thereof Onium salts such as certain phosphonium salts and their lake pigments, triphenylmethane dyes and these lake pigments (phosphor tungstic 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, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate;
Diorganotin borates such as dicyclohexyltin borate; these can be used alone or in combination of two or more. Among these, nigrosine,
A charge control agent such as a quaternary ammonium salt is particularly preferably used. These charge control agents are preferably used in an amount of 0.01 to 20 parts by weight (more preferably 0.5 to 10 parts by weight) based on 100 parts by weight of the resin component.

As the colorant used in the present invention, as the black colorant, carbon black, a magnetic substance, or a substance toned to black using a yellow / magenta / cyan colorant shown below is used. As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds and allylamide compounds are used. Specifically, C.I.
I. Pigment Yellow 12, 13, 14, 15, 1
7, 62, 74, 83, 93, 94, 95, 109, 1
10, 111, 128, 129, 147, 168, 18
0 and the like are preferably used. As magenta colorants, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds,
Naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. l. Pigment Red 2, 3, 5, 6, 7, 2,
3, 48; 2, 48; 3, 48; 4, 57; 1, 81;
1, 144, 146, 166, 169, 177, 18
4, 185, 202, 206, 220, 221, 254
Is particularly preferred.

As the cyan coloring agent used in the present invention, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like can be used.
Specifically, C.I. l. Pigment Blue 1, 7, 15,
15: 1, 15: 2, 15: 3, 15: 4, 60, 6
2, 66 and the like can be particularly preferably used. These colorants can be used alone or as a mixture or in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, lightness, weather resistance, OHP transparency, and dispersibility in toner. The amount of the coloring agent is 1 to 100 parts by weight of the resin.
Used in an amount of up to 20 parts by weight.

Further, the toner used in the present invention is:
It may be a magnetic toner containing a magnetic material. In this case, the magnetic material can also serve as a colorant.
In the present invention, the magnetic material contained in the magnetic toner includes iron oxide such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and aluminum, cobalt, copper, lead, magnesium, and tin of these metals. , Zinc, antimony, beryllium, bismuth,
Cadmium, calcium, manganese, selenium, titanium,
Alloys of metals such as tungsten and vanadium and mixtures thereof can be given.

Further, it is desirable that the above-mentioned magnetic materials used in the present invention are more preferably surface-modified. In particular, when used in a polymerization method toner,
It is preferable that the material has been subjected to a hydrophobic treatment with a surface modifier which is a substance having no polymerization inhibition. Examples of the surface modifier include a silane coupling agent and a titanium coupling agent.

The magnetic material used in the present invention has an average particle size of 2 μm.
m or less, preferably about 0.1 to 0.5 μm. As the amount to be contained in the toner, the resin component 1
The amount may be about 40 to 150 parts by weight with respect to 00 parts by weight. The magnetic properties at 10K oersteds applied, the coercive force (H _c) 20 to 300 oersted, a saturation magnetization (sigma _s)
50-200 emu / g, residual magnetization (σ _r ) 2-20 e
It is preferable to use those having mu / g.

As an additive for imparting various toner properties, from the viewpoint of durability when internally added to the toner or when externally added to the toner, 1/5 of the volume average diameter of the toner particles is used. The particle diameter is preferably as follows. Here, the particle size of the additive means an average particle size obtained by observing the surface of the toner particles with an electron microscope. Examples of additives that can be used in the present invention for the purpose of imparting properties of the toner include the following.

As the fluidity imparting agent, metal oxides such as silicon oxide, aluminum oxide and titanium oxide, carbon black, carbon fluoride and the like can be used. These are each more preferably subjected to a hydrophobic treatment. Examples of the abrasive include metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (calcium sulfate, Barium sulfate, calcium carbonate, etc.). As the lubricant, for example, fluorine resin powder (vinylidene fluoride,
Polytetrafluoroethylene, etc.) and fatty acid metal salts (zinc stearate, calcium stearate, etc.). Examples of the charge control particles include metal oxides (such as tin oxide, titanium oxide, zinc oxide, silicon oxide, and aluminum oxide), and carbon black.

These additives are used in an amount of 0.1 to 10 parts by weight, 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. The toner of the present invention can be used as a normal one-component developer and a two-component developer. For example, when using 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. . When using a non-magnetic toner that does not contain a magnetic material, a blade and a fur brush are used to forcibly frictionally charge the toner with a developing sleeve to charge the toner, thereby causing the toner to adhere to the developing sleeve. There is a method of transporting.

On the other hand, when the toner is used as a generally used two-component developer, the toner having the above-described structure is mixed with a carrier and used. The carrier used in this case is not particularly limited, but is mainly composed of a single ferrite and a composite ferrite composed of iron, copper, zinc, nickel, cobalt, manganese, and chromium elements. In addition, the carrier shape is also important because the saturation magnetization electric resistance can be controlled in a wide range.For example, a spherical shape, a flat shape, an irregular shape, etc. are selected, and the fine structure of the carrier surface state, for example, the surface irregularity is also controlled. Is preferred. As a method for producing a carrier, generally, a method is used in which a carrier is cored in advance by baking and granulating an inorganic oxide to coat the surface with a resin. From the point of lightening the load, after kneading the inorganic oxide and the resin, pulverizing and classifying to obtain a low-density dispersed carrier, and further, directly kneaded the inorganic oxide and the monomer in an aqueous medium A method of obtaining a polymerized carrier to obtain a spherical dispersion carrier by suspension polymerization can also be used.

In the present invention, when a toner image is formed using a two-component developer, it is particularly preferable to use a system in which the surface of the carrier is coated with a resin or the like.
Conventional methods for coating the surface of the carrier with a resin or the like include a method of dissolving or suspending a coating material made of a resin or the like in a solvent, applying the solution, and attaching the material to the carrier surface, a method of simply mixing with a powder, and the like. Any of the known methods can be applied.

The fixing substance to be adhered to 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,
It is appropriate to use polyvinyl butyral, nigrosine, amino acrylate resin, basic dyes and lakes thereof, silica fine powder, alumina fine powder, or the like alone or in combination, but it is not necessarily limited thereto. The treatment amount of the carrier surface with the above compound is generally 0.1 to 30% by weight (preferably 0.5 to 20% by weight) based on the total amount of the carrier. The average particle size of these carriers is 10
１００100 μm, preferably 20-50 μm.

A particularly preferred embodiment of the carrier for use in the present invention is ferrite, and the surface thereof is
A combination of a resin such as a fluorine-based resin and a styrene-based resin, for example, polyvinylidene fluoride and a styrene-methyl methacrylate resin; polytetrafluoroethylene and a styrene-methyl methacrylate resin, a fluorine-based copolymer and a styrene-based copolymer; 90:10 to 20: 8
0, preferably a mixture in a ratio of 70:30 to 30:70, or a silicone resin or the like.
Coated ferrite carriers coated with 0.01 to 5% by weight, preferably 0.1 to 1% by weight can be mentioned.
As the above-mentioned fluorine-based copolymer, vinylidene fluoride-
Tetrafluoroethylene copolymer (10:90 to 90:
10), and styrene-based copolymers such as styrene-2-ethylhexyl acrylate (20:80 to 8
0:20), styrene-2-ethylhexyl acrylate-methyl methacrylate (20-60: 5-30: 10)
50) is exemplified.

The coated ferrite carrier has a sharp particle size distribution, and exhibits favorable triboelectric charging properties to the toner suitably used in the present invention. Further, there is an effect of improving electrophotographic characteristics. In the case of preparing a two-component developer by mixing with the toner, the mixing ratio is preferably from 2% by weight to 15% by weight, preferably from 4% by weight to 13% by weight, as a toner concentration in the developer. Is obtained.
That is, if the toner concentration is less than 2% by weight, the image density becomes low and it becomes impractical. If the toner concentration is less than 15% by weight, fog and scattering in the machine are increased, and the service life of the developer tends to be shortened.

Further, the magnetic properties of the carrier used in the present invention are preferably as follows. Saturation magnetization is 20 to 90 Am ²
/ Kg is preferred. Further, in order to achieve high image quality, it is preferably 30 to 70 Am ² / kg. That is, if it is larger than 90 Am ² / kg, it becomes difficult to obtain a high quality toner image. 20
If it is less than Am ² / kg, the magnetic binding force is reduced, so that carrier adhesion is likely to occur.

The method for producing the pulverized toner used in the present invention includes, for example, a binder resin, the above-described ester wax containing at least a silicone polymer, a silicone oil, and silica fine particles, and a pigment as a colorant. , A dye or a magnetic substance, a charge control agent, if necessary, and other additives, and the like. The mixture is sufficiently mixed with a mixer such as a Henschel mixer or a ball mill, and then heated.
A metal compound, a pigment, a dye, a magnetic substance, and the like are dispersed or dissolved while melt-kneading using a hot kneader such as a kneader or an extruder to make the resins mutually compatible.
Thereafter, the melt-kneaded material is cooled and solidified, and then pulverized and classified to obtain a toner having a desired particle size that can be suitably used in the present invention. Further, if necessary, the desired additives are sufficiently mixed with a mixer such as a Henschel mixer to obtain a developing toner having characteristics that can be suitably used in the present invention.

The method for producing the polymerized toner used in the present invention includes a method described in JP-B-56-13945 and the like, in which a molten mixture is atomized into air using a disk or a multi-fluid nozzle to obtain a spherical toner. JP-B-36-10231, JP-A-59-53856, JP-A-59-61
No. 842, a method of directly producing a toner using a suspension polymerization method, and a method of dispersing a polymer which is soluble in a monomer and directly produces a toner using an insoluble aqueous organic solvent. Polymerization method, or emulsion polymerization method represented by soap-free polymerization method in which a toner is produced by directly polymerizing in the presence of a water-soluble polar polymerization initiator, or after forming primary polar emulsion polymerization particles in advance and having an opposite charge The toner can be manufactured using a heteroaggregation method or the like in which polar particles are added and associated.

However, in the dispersion polymerization method, although the obtained toner shows an extremely sharp particle size distribution, the range of selection of materials to be used is narrow, and the use of an organic solvent requires treatment of waste solvent and removal of the solvent. From the viewpoint of flammability, there is a problem that the manufacturing apparatus is complicated and easily complicated. Emulsion polymerization represented by soap-free polymerization is effective because the particle size distribution of the toner is relatively uniform.
When the used emulsifier or initiator terminal is present on the surface of the toner particles, the environmental characteristics are likely to deteriorate. Accordingly, in the present invention, it is particularly preferable to produce the toner by a suspension polymerization method under normal pressure or under pressure, which can relatively easily obtain a fine particle toner having a sharp particle size distribution. A so-called seed polymerization method in which a monomer is once more adsorbed on the obtained polymer particles and then polymerized using a polymerization initiator can also be suitably used for the production of the toner used in the present invention.

A more preferable form of the toner used in the present invention is a toner in which, when the tomographic plane of the toner is measured by using a transmission electron microscope (TEM), particularly, the ester wax is encapsulated in the outer resin layer. It is. The toner having such a form can be easily manufactured by using a direct polymerization method. From the viewpoint of fixability, it is necessary to include a large amount of ester wax in the toner, and it is necessary to include the ester wax in the outer shell resin. That is, the toner in the case where the ester wax is not encapsulated cannot be sufficiently pulverized unless a special freeze-pulverization is used in the pulverization step, and as a result, only a substance having a wide particle size distribution can be obtained. Toner fusion also occurs, which is extremely undesirable. In addition, in this freezing and pulverization, since it is necessary to take measures to prevent dew condensation on the apparatus, the apparatus becomes complicated, and if the toner absorbs moisture due to dew condensation, the workability of the toner is reduced. Need to be added.

As a specific method for encapsulating the ester wax in the toner, the polarity of the material in the aqueous medium is set smaller than that of the main monomer in the ester wax, and a small amount of the resin having a large polarity is used. Alternatively, by adding a monomer, a toner having a so-called core-shell structure in which an ester wax is covered with an outer shell resin can be obtained. Control of the particle size distribution and particle size of the toner can be achieved by changing the type or amount of the hardly water-soluble inorganic salt or dispersant that acts as a protective colloid, or by mechanical device conditions, for example,
By controlling the peripheral speed of the rotor, the number of passes, the stirring conditions such as the shape of the stirring blade, the shape of the container, or the solid content concentration in the aqueous solution, a toner in a desired form can be obtained.

In the present invention, a specific method for measuring the tomographic plane of the toner is as follows. After sufficiently dispersing the toner in an epoxy resin which is curable at room temperature, the toner is dispersed in an atmosphere at a temperature of 40 ° C.
Cured for days, the resulting cured product is ruthenium tetroxide,
After dyeing with osmium tetroxide, if necessary, a flaky sample was cut out using a microtome provided with diamond teeth, and the tomographic morphology of the toner was measured using a transmission electron microscope (TEM). In the present invention, it is preferable to use a ruthenium tetroxide dyeing method in order to provide a contrast between materials by utilizing a slight difference in crystallinity between the ester wax used and the resin constituting the outer shell. Observation of the toner used in the present invention by the above method revealed that the ester wax was clearly encapsulated in the outer shell resin.

When 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. Contains ester wax, colorant, charge control agent, polymerization initiator, and other additives in the monomer, and contains a dispersion stabilizer containing a monomer system uniformly dissolved or dispersed by a homogenizer, ultrasonic disperser, etc. In an aqueous phase to be dispersed using a conventional stirrer, a homomixer, a homogenizer, or the like. 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. Thereafter, by the action of the dispersion stabilizer, stirring may be performed to such an extent that the particle state is maintained and the particles are prevented from settling. Polymerization temperature is 40
The polymerization is carried out at a temperature of at least 50 ° C., generally from 50 to 90 ° C. In addition, the temperature may be raised in the latter half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers and by-products which cause odor at the time of fixing the toner, the second half of the reaction or After completion, the aqueous medium may be partially distilled off. After completion of the reaction, the generated toner particles are collected by washing and filtration, and then dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as an aqueous dispersion medium based on 100 parts by weight of the monomer system.

When a toner is directly obtained by a polymerization method, styrene, o (m
-, P-)-methylstyrene, m (p-)-ethylstyrene and other styrene monomers; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acryl Butyl acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate,
(Meth) acrylate monomers such as 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate; butadiene, isoprene, cyclohexene, (meth) acrylonitrile, and acrylic Ene monomers such as acid amides are preferably used.

In the present invention, in order to form a core-shell structure, it is essential to use a polar resin in combination. Polar polymers and copolymers usable in the present invention are exemplified below. Dimethylaminoethyl methacrylate, polymers of nitrogen-containing monomers such as diethylaminoethyl methacrylate,
Or a copolymer with styrene-unsaturated carboxylic acid ester or the like, a nitrile monomer such as acrylonitrile, a halogen-containing monomer such as vinyl chloride, an unsaturated carboxylic acid such as acrylic acid or methacrylic acid, or the like. Saturated dibasic acids,
Unsaturated dibasic acid anhydrides, polymers such as nitro monomers or copolymers with styrene monomers, polyesters,
Epoxy resins and the like can be mentioned. More preferred are a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, a saturated polyester resin, an epoxy resin, and the like.

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-based polymerization initiators such as azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide , Di-t-butyl peroxide, dixyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis (4,4
Peroxide initiators such as -t-butylperoxycyclohexyl) propane and tris- (t-butylperoxy) triazine, polymer initiators having a peroxide in a side chain, and persulfates such as potassium persulfate and ammonium persulfate. Salts, hydrogen peroxide and the like are used. The polymerization initiator is preferably added in an amount of 0.5 to 20 parts by weight of the polymerizable monomer, alone or
You may use together.

In the present invention, a known crosslinking agent or chain transfer agent may be added to control the molecular weight.
The preferable addition amount is 0.001 to 15 parts by weight. In the present invention, emulsion polymerization, dispersion polymerization, suspension polymerization,
Seed polymerization, polymerization method using hetero-aggregation method, etc.
It is preferable to use any suitable dispersion stabilizer for the dispersion medium used in producing the polymerization toner. For example, as inorganic compounds, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate , Bentonite, silica, alumina and the like. As an organic compound, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose,
Polyacrylic acid and its salts, starch, polyacrylamide, polyethylene oxide, poly (hydroxystearic acid-g-methyl methacrylate-eu-methacrylic acid) copolymer, and nonionic or ionic surfactants are used. .

When the emulsion polymerization method and the heteroaggregation method are used, an anionic surfactant, a cationic surfactant, an amphoteric ionic surfactant and a nonionic surfactant are used. 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. Among the dispersion stabilizers listed above, when an inorganic compound is used, a commercially available one may be used as it is, but in order to obtain fine particles, the inorganic compound may be generated in a dispersion medium. Good. For fine dispersion of these dispersion stabilizers, 0.001 to 0.1 parts by weight of a surfactant may be used. This is to promote the intended action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, and lauryl acid. sodium,
Potassium stearate, calcium oleate and the like can be mentioned.

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 migration property of the colorant. It is better to perform a hydrophobic treatment without inhibiting polymerization. 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, there is a method in which a polymerizable monomer is polymerized in advance in the presence of these dyes, and the obtained colored polymer is added to the monomer system. The carbon black may be treated with a substance that reacts with the surface functional group of the carbon black, for example, a polyorganosiloxane, in addition to the same treatment as the above dye.

[0081]

EXAMPLES Example 1 0.1 g of ion-exchanged water was added to 710 g of ion-exchanged water.
450 g of a 1M-Na ₃ PO ₄ aqueous solution was charged, heated to 60 ° C., and then stirred at 13,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). 1.0
68 g of an M-CaCl ₂ aqueous solution was gradually added to obtain an aqueous medium containing fine particles of Ca ₃ (PO ₄ ) ₂ as a dispersion stabilizer.

On the other hand, a polymerizable monomer composition was prepared according to the following procedure. -Styrene 166 g-n-butyl acrylate 34 g-Copper phthalocyanine pigment 15 g-Ditertiary butyl salicylic acid metal compound 3 g-Saturated polyester (acid value 11, peak molecular weight 8,500) 10 g-Internally added monoester wax 40 g

The internally added monoester wax in the above composition was previously prepared by adding 100 g of the monoester wax (Mw = 5).
00, Mn = 400, viscosity = 6.5 mPas, SP value =
8 to 6), 5 g of silicone polymer, 15 g of silicone oil, ultrafine silica (particle size: 0.015 μm)
m, shape: spherical particles, surface area: 110 m ² / g, 1 g of lipophilic treatment), then heated to 60 ° C., and 12,000 r using a TK homomixer (manufactured by Tokushu Kika Kogyo).
A material obtained by uniformly dissolving and dispersing these materials under the condition of pm was used.

All of the above formulations were mixed and heated to 60 ° C.
12, using a TK homomixer (manufactured by Tokushu Kika Kogyo)
Each material was uniformly dissolved and dispersed by stirring at 000 rpm. To this, 10 g of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was added and dissolved to prepare a polymerizable monomer composition. Into the aqueous medium prepared above, the polymerizable monomer composition obtained above is put, and at 60 ° C. under a N ₂ atmosphere, using a TK homomixer under the conditions of 10,000 rpm for 20 minutes. After stirring, the polymerizable monomer composition was granulated. Thereafter, the temperature was raised to 80 ° C. while stirring with a paddle stirring blade.
The polymerization reaction was performed for 0 hour to obtain toner particles.

After the completion of the polymerization reaction, the mixture was cooled, and hydrochloric acid was added.
After dissolving calcium phosphate added as a dispersion stabilizer, the mixture was filtered, washed with water and dried to obtain colored polymer particles. Next, BET was performed on 100 parts by mass of the obtained particles.
By externally adding 2.0 parts by mass of hydrophobic titanium oxide having a specific surface area of 100 m ² / g, a toner having an average particle size of 6.2 μm was obtained. A two-component developer 1 was obtained by mixing 93 parts by mass of 35 μm silicone-coated chlorite carrier with 7 parts by mass of this toner.

Using this developer 1, the fixing unit of a commercially available full-color copying machine CLC800 (manufactured by Canon) was improved, the oil application mechanism to the roller was removed, and the surfaces of the heating roller and the pressure roller were both FEP-coated. Covered with 10μ
An endurance test was performed with a copying machine having a configuration using a roller having a resin coating layer having a thickness of m. As a method, a paper passing test of 10,000 sheets was performed for each of two types of original documents having an image area on paper of 20% and 50%, respectively. As a result, the image area on paper is 20% and 50%.
No fogging occurred for up to 10,000 sheets of durable copies. This is presumably because the emulsified particles of the monoester wax attached to the surface of the toner particles generated by the conventional polymerized toner particles were effectively masked by the toner of the present embodiment.
Further, when an OHP image was formed using the developer 1,
An image with less stickiness can be formed than in the conventional case,
When a transmission image was observed by an overhead projector using the formed OHP image, a high-quality image having excellent transparency and without haze was obtained.

Comparative Example 1 Instead of using the internally added monoester wax used in Example 1, a monoester wax 100 g (Mw = 500, Mn = 400, viscosity =
A polymerized toner and a two-component developer 2 were prepared in the same manner as in Example 1 except that 6.5 mPas and an SP value of 8 to 6) were used alone. About the obtained developer 2, Example 1
The evaluation was performed in the same manner as in the above. The evaluation was 5,000 for an image with an image area of 20% and 1,0 for an image with an image area of 50%.
Fogging occurred on each of the 00 sheets. 0 with a Macbeth densitometer.
It was 3. This is probably because the emulsified particles contaminated the carrier. Further, when an OHP image was formed in the same manner as in Example 1, the image was more sticky than that obtained in Example 1. Further, when a transmission image was observed with an overhead projector,
An image inferior in transparency to the image formed in was obtained.

(Example 2) Instead of using the internally added monoester wax used in Example 1, diester wax (Mw = 480, Mn = 410, viscosity 10.3).
Polymerized toner and two-component developer 3 were obtained in the same manner as in Example 1 except that the internally added diester wax obtained using 5 mPas, SP value = 9-1) was used. When this developer 3 was evaluated in the same manner as in Example 1,
As in the case of Example 1, good results were obtained.

Example 3 Instead of using the internally added monoester wax used in Example 1, a tetraester wax (Mw = 430, Mn = 380, M
w850 with shoulder, viscosity = 11.6 mPas,
A polymerized toner and a two-component developer 4 were obtained in the same manner as in Example 1 except that the internally added tetraester wax obtained by using the SP value of 8 to 5) was used. When this developer 4 was evaluated in the same manner as in Example 1,
As in the case of Example 1, good results were obtained.

(Example 4) Instead of the copper phthalocyanine pigment used in Example 1, quinacridone pigments and C.I. I. Pigment Yellow 180 and carbon black, except that Pigment Yellow 180 and Carbon Black were used.
Polymerized toner of each color of magenta, yellow and black and a two-component developer were obtained. When a full-color image was formed using these developers in the same manner as in Example 1, a good image excellent in color reproducibility of a light color as an intermediate color was obtained. Further, the durability test and the formation of an OHP image were performed and evaluated in the same manner as in Example 1. As a result, good results were obtained as in Example 1.

Example 5 200 g of magnetic iron oxide obtained by further treating the toner composition of Example 1 with a silane coupling agent
(Average particle size 0.25 μm) Polymerized magnetic toner A was obtained in the same manner as in Example 1 except that hydrophobic silica was used as an external additive. With respect to the magnetic toner A, an image forming test similar to that in Example 1 was performed by using a copying machine having a configuration in which the surface layer of a fixing unit of a commercially available copying machine OP8582 (manufactured by Canon) was modified to FEP, and similarly evaluated. As a result, good results were obtained as in the case of Example 1.

[0092]

As described above, according to the present invention,
When OHP is used as the material to be transferred, no toner is effectively attached to the surface of the fixing roller without supplying a liquid such as silicone oil with high release properties to the fixing roller, etc., and no offset occurs. Further, there is provided a method for fixing a toner image without impairing the transparency and haze of the OHP image after fixing. Further, according to the present invention, even when the toner is produced by a polymerization method and is mixed with a carrier and used as a two-component developer, carrier contamination does not occur and the toner is charged. Provided is a method for fixing a toner image, which can be sufficiently stably secured to obtain a high-quality image stably. This is because, in conventional polymerized toner, the presence of emulsified particles due to the wax contained in the toner is unavoidable, and the emulsified particles adhere to the surface of the generated toner particles. When used, the emulsified particles adhere to the carrier surface when the toner particles rub against the carrier, and the charge-imparting ability of the carrier to the toner is impaired and the developing ability is reduced. By using the wax, the emulsified particles are effectively masked.

Claims (5)

[Claims] An image formed by a toner carried on a recording material is heated and / or pressurized by a fixing member to fix the toner image on the recording material. A method for fixing a toner image, comprising a resin, a colorant and a wax, wherein the wax contains at least a silicone polymer, a silicone oil, and silica fine particles. 2. The method according to claim 1, wherein the toner is a polymerized toner. 3. The weight average molecular weight (Mw) of the wax is:
400 or more and 4,000 or less, and a number average molecular weight (M
2. The method for fixing a toner image according to claim 1, wherein n) is from 200 to 4,000. 4. The method for fixing a toner image according to claim 1, wherein the silicone polymer is represented by the following structural formula. Embedded image 5. The method according to claim 1, wherein the silicone oil is represented by the following structural formula. Embedded image