JP2003098875A - Method for fixing toner in image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for fixing toner which can practically obtain an high quality and stable image, having superior in a fixing property at a low temperature, an heat-resistant offset property, gloss of color toner and transparency of OHP, etc. SOLUTION: A belt-fixing apparatus is provided with a fixing roller 2, a heating roller 1, an endless fixing belt 3 suspended on the heating roller 1 and the fixing roller 2, a pressure roller 4 provided opposite to the fixing roller 2 via the fixing belt 3 and a fixing heater 5 within one or both of the heating roller 1 and the fixing roller 2. In the method for fixing the toner, in which the belt fixing apparatus is used and the pressure roller 4 does not press the fixing roller 2 via the fixing belt 3, contacts the fixing belt 3, and fixes a toner image on a material 13 to be fixed fed between the pressure roller 4 and the fixing belt 3, the toner has a sphere, having circularity of 0.96 or more and resin, having the maximum composition ratio in the toner is denatured polyester resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner fixing method for fixing toner to a transfer material in an image forming apparatus such as a copying machine, a printer and a facsimile, and more specifically, a belt-shaped heat transfer medium is used. The present invention relates to a toner fixing method for fixing toner to a transfer material.

[0002]

2. Description of the Related Art Conventionally, in an image forming apparatus such as a copying machine, a printer or a facsimile which forms a black and white image, a latent image is formed on an image bearing member such as a photosensitive drum or a photosensitive belt by a latent image forming means. Then, the latent image is developed by a developing device to form a toner image, and the toner image is transferred to a transfer paper made of plain paper or special paper as a material to be fixed and fixed by the fixing device.

In a color image forming apparatus such as a color copying machine, a color printer or a color facsimile,
For example, a plurality of latent images are formed on an image bearing member such as a photoconductor drum or a photoconductor belt, and these latent images are developed with toners of respective colors by developing devices to obtain toner images of respective colors. Toner images are overlaid to form a full-color image, which is transferred to a fixing material such as transfer paper, and the color image on the fixing material is fixed by a fixing device.
Especially in recent years, for the purpose of energy saving and downsizing of the device,
A fixing mechanism using a belt-shaped heat transfer medium (hereinafter referred to as “belt fixing”) has been widely used.

In such a belt fixing, the contact time of the toner with the surface of the belt can be lengthened particularly during the fixing, and the fixing can be performed at a lower temperature. The so-called offset phenomenon in which the toner is fused to the surface easily occurs. In particular, color toners need to have appropriate luster in order to provide sufficient transparency and a high-quality feeling, and the molecular weight of the binder resin must be sharpened.
The sharp-melt property is required, but this facilitates the melting of the toner during fixing and the offset phenomenon easily occurs. In addition, when the toner external additive and other components adhere to the belt-shaped heat transfer medium, which causes belt abrasion and scratches, resulting in hot offset and further tearing of the belt itself. There is.

In order to solve the above problems, various proposals have been made so far in terms of fixing mechanism and toner for electrophotography. On the other hand, in the fixing device, oil is applied to the fixing roller in order to prevent offset. In a color image forming apparatus, in order to prioritize high-gloss and high-transparency image quality, it is necessary to use low-viscosity toner of each color, and it is essential to apply oil to the fixing roll to prevent offset. It was

Further, it is known that a fixing release material such as wax is added to the toner to prevent offset in fixing, but when the characteristics of the wax or the dispersed state in the toner are inappropriate. Is a phenomenon in which wax is detached from the toner surface or oozes out due to long-term use in the developing unit, and in a two-component developer, the carrier surface is contaminated. In many cases, the charging characteristics are deteriorated, and in a one-component developer, the toner is often fused to a developing roller or a blade for thinning the toner to hinder the uniform development of the toner. Therefore, from the viewpoint of development, it is preferable that the addition of wax is as small as possible.

In the following, known documents relating to toners and fixing devices will be exemplified, and the constitutions and problems of these conventional techniques will be described. [Patent Document 1] JP-A-7-219274 (Structure) A binder resin and a pigment containing a pigment-dispersing resin obtained by mixing a polyolefin wax and a water-containing paste of the pigment in a resin solution for dispersing the pigment and then heating the mixture. A color toner in which the SP value difference of the dispersion resin is 1.5 to 0.5. (Problem) This is aimed at achieving high dispersion of the polyolefin wax in the binder resin, but it is not sufficient to expect only the effect of the polyolefin wax in order to impart offset resistance.

JP-A-7-31179 (Structure) In the fixing roller using the toner described in JP-A-7-219274, an elastic layer coated with a fluororesin is used as the surface layer. (Issue) Same as above

JP-A-7-333903 (Structure) TH of Mn: 2500-3500, Mw: 50,000-300,000
A toner containing a polyester resin containing no F insoluble matter. (Problem) A large amount of fixing oil is required.

Japanese Unexamined Patent Publication No. 7-333904 (Structure) Wax and a THF insoluble content of 15 to 40% and a polyester resin in which a polyhydric alcohol component is limited are used.
The difference in refractive index between the binder resin and the wax is limited. (Problem) It is difficult to obtain high gloss because it contains a large amount of THF insoluble matter.

JP-A-8-50367 (Structure) In a wax-containing toner, the wax has a maximum molecular weight in each range of 350 to 850 and 900 to 4000, and Mn: 350 to 4000, Mw: 200. Toner containing ~ 4000 ester waxes. (Problem) Sufficient offset resistance cannot be obtained only by limiting the properties of the wax.

Japanese Unexamined Patent Publication ( Kokai ) No. 50-50368 (Structure) An ester compound having the same total carbon number is used.
Binder resin 100 containing ~ 95% by weight of ester wax
A toner containing 3 to 40 parts by weight per part by weight. (Problem) Sufficient offset resistance cannot be obtained only by limiting the properties of the wax.

Japanese Patent Laid-Open No. 3-39971 (Structure) Toluene-insoluble matter- free molecular weight 500-2000
Has a peak in the range of 10,000 to 100,000, Mw: 10,000 to 80,000, M
A color toner containing a resin of n: 1500 to 8000 and having Mw / Mn> 3. (Problem) Sufficient offset resistance cannot be obtained.

JP-A-4-57062 (Structure) Flow Tester Melt Viscosity 10 5 Poise has a softening temperature of 90 to 120 ° C., Mw: 15,000 to 50,000, Mn: 20
Color toner containing resin with Mw / Mn = 5 to 15 at 0 to 10,000 (problem) Sufficient offset resistance cannot be obtained.

[0015] JP-A-6-318001, JP-A No. 8
SUMMARY OF THE INVENTION In the fixing device described in the above-mentioned publication, since the residual heat of the atmosphere of the toner image is generated, the effect of improving the fixability and offset due to the residual heat is low, but the effect is small at high speed. is there. Further, in order to produce the residual heat effect, it is necessary to narrow the distance between the fixing belt B and the recording medium G, and a measure to improve the margin against the deviation of the unfixed toner image becomes an issue.

[0016] There is a fixing step of fixing the toner image through a first belt to the transfer sheet in the fixing device of JP-A-4-273279 Patent Publication (challenge) the publication, then the transport to transport by belt Process,
Since there is a peeling step of peeling the fixed toner image from the belt, the transfer paper and the toner that have undergone the fixing step are further subjected to residual heat of the belt, and the toner is excessively melted and an offset phenomenon easily occurs. The partial temperature unevenness occurs on the image surface of the transfer paper, which causes uneven gloss.

JP-A-11-44969 (Problem) The toner for electrophotography described in the above publication proposes a toner in which a non-linear polyester resin is used as a binder resin and a release agent is contained. Although the properties, gloss and transparency have been improved in low speed machines, the performance in high speed machines is not yet at a satisfactory level and further improvement is required.

[0018]

SUMMARY OF THE INVENTION The first object of the present invention is to use a belt fixing device used in a fixing unit and an image forming method using the fixing unit in view of the above problems of the present situation. By clarifying the interactive characteristics of electrophotographic toner and the effective range of the characteristics, low-temperature fixability,
It is an object of the present invention to provide a toner fixing method capable of obtaining a very stable and good image quality in actual use such as oilless hot offset property, color toner glossiness, and OHP transparency. A second object of the present invention is that the material to be fixed has good transportability and fixability and can sufficiently prevent wrinkles of the material to be fixed and the scratching phenomenon of an unfixed image. It is an object of the present invention to provide a toner fixing method capable of obtaining stable fixing property even in a forming apparatus.

[0019]

The above object can be achieved by the embodiments of the present invention described below. (1) a fixing roller, a heating roller, an endless fixing belt stretched around the heating roller and the fixing roller, and a pressure roller provided to face the fixing roller via the fixing belt, Using a belt fixing device equipped with a fixing heating heater provided inside one or both of the pressure roller and the heating roller, the pressure roller is the fixing roller via the fixing belt. A toner fixing method of fixing a toner image on a material to be fixed conveyed between the pressure roller and the fixing belt by contacting the fixing belt without pressurizing the toner. A toner fixing method characterized by having a spherical shape of 96 or more and containing a modified polyester resin in the resin in the toner. (2) Fixing of a material to be fixed at a contact portion between the pressure roller and the fixing belt, which is in contact with the fixing belt without the pressure roller pressing the fixing roller via the fixing belt. A first fixing step that is performed at a fixing pressure that is set low enough not to cause wrinkles in the material to be fixed, and the pressure roller that the pressure roller contacts by pressing the fixing roller via the fixing belt. The toner fixing method according to (1) above, further comprising: a second fixing step of fixing the material to be fixed at a contact portion with the fixing belt. (3) The fixing pressure in the first fixing step is 1 kg / c.
and m ² or less, the toner fixing method (2), wherein the to the fixing pressure of the portion of the fixing pressure of the portion the second fixing process performing a first fixing step. (4) The toner fixing method according to any one of (1) to (3), wherein the heating roller has a low heat capacity. (5) The toner has a melting point of 60 to 120 as a release agent.
The toner fixing method as described in any one of (1) to (4) above, which contains 1 to 20 wt% of a wax having a temperature of 0 ° C. (6) The wax has a weight average molecular weight of 400 to 500.
0, the acid value is 1 to 30 mgKOH / g, and the toner fixing method according to the above (5) (7) The release agent dispersed in the toner is dispersed evenly in the toner particles. At least three release agent particles are present in at least the toner particles, and the above (1) is provided.
The toner fixing method according to any one of (6) to (6). (8) The wax particles having a dispersion diameter of the wax contained in the toner of 0.1 μm to 2 μm with respect to the wax existing in the toner account for 70% or more of the total number of the wax particles. The toner fixing method according to any one of 1) to (7). (9) The release agent dispersed in the toner is acicularly dispersed in the toner particles, and the release agent has a maximum major axis of 3 or less.
The number of release agent particles having a size of μm or more does not exceed 5% with respect to the total number of release agent particles (1) to
The toner fixing method according to any one of (8). (10) The release agent dispersed in the toner in a needle shape is
The major axis of the release agent with respect to the surface of the toner particles is not present in the horizontal direction along the surface of the particles but is directed toward the inside or dispersed so as not to be exposed on the surface (9). Toner fixing method. (11) The release agent dispersed in the toner is a vegetable wax having a molecular weight of 400 to 2500 and an acid value of 1 to 30 mgKOH / g, and the above (1) to (10). The toner fixing method according to any one of 1) to 4) above. (12) The release agent dispersed in the toner is 50 ° C.
The toner fixing method according to any one of (1) to (11) above, which is an ester wax having a needle penetration degree of 3 or less. (13) The toner is prepared by dissolving / dispersing a toner composition containing at least a modified polyester resin, a colorant and a releasing agent or not containing a releasing agent in an organic solvent, and preparing the composition in an aqueous medium. The toner fixing method as described in any one of (1) to (12) above, which is a toner produced by granulating. (14) The toner comprises a toner composition containing at least a polyester prepolymer, a colorant and a release agent or containing no release agent, dissolved / dispersed in an organic solvent, and the composition has a urea bond. 3. The toner according to any one of (1) to (12) above, which is a toner produced by granulating a polyester in an aqueous medium while producing polyester, and subjecting the polyaddition reaction to the granulation. Toner fixing method. (15) The toner is the modified polyester resin (i)
Together with the unmodified polyester resin (ii), the weight ratio of (i) and (ii) is 5/95 to 80/20.
The toner fixing method as described in (13) or (14) above. (16) THF as a binder component contained in the toner
Molecular weight distribution of soluble component is less than 1000, 5% of components
The toner fixing method according to any one of (1) to (15) above, characterized in that: (17) The glass transition point of at least the polyester resin contained in the toner is 55 to 70 ° C, and the above (1) to (1)
6. The toner fixing method according to any one of 6). (18) THF as a binder component contained in the toner
The toner fixing method according to any one of (1) to (17) above, wherein the insoluble content is 1 to 15%. (19) The binder component contained in the toner is TH
In the molecular weight distribution of the F soluble component, the peak of the molecular weight is 100.
The toner fixing method according to any one of (1) to (18) above, which has a content of 0 to 30,000, 30,000 or more components of 1% or more, and a weight average particle diameter of 3 to 10 μm. (20) THF as a binder component contained in the toner
In the molecular weight distribution of the soluble component, the number average molecular weight is 2000-
15,000 and the weight average molecular weight / number average molecular weight is 1
It is 0.0 or less, and the above (1) to (1
9. The toner fixing method according to any one of 9).

The following is a brief description of the effects produced by the above-mentioned embodiment. According to the first aspect, it is possible to obtain a stable fixing property with a quick start-up in a high-speed apparatus or color image forming apparatus. According to the second aspect, it is possible to provide an image forming method satisfying the fixability and the hot offset resistance in a high speed machine. The release agent dispersed in the toner is uniformly dispersed in the toner particles, at least three release agent particles are present in the toner particles, and the release agent has a dispersion diameter of 0.1 μm to 2 μm. Some toner particles are 7
By occupying 0% by number or more, the oilless property of the release agent is sufficiently exhibited. In Aspect 2, by setting the fixing pressure in the first fixing step to 1 kg / cm ² or less and the fixing pressure in the second fixing step or more, good transportability and low-temperature fixing property of the toner are exhibited. As in aspect 4,
A heater for heating the fixing belt is provided inside the heating roller, and the heating roller has a low heat capacity, so that energy saving can be achieved while maintaining low-temperature fixing property.

TH of the binder component contained in the toner
In the molecular weight distribution of the F-soluble component, the component having a molecular weight of 1000 or less is 5% or less, the glass transition point of the polyester resin contained in the toner is 55 to 75 ° C., and the acid value is 1 to 30 mgKOH / g. And that the binder component contained in the toner has a THF insoluble content of 1 to 15%.
By virtue of the above, it is possible to achieve a stable fixed image and gloss necessary for color toner, and transparency in OHP.

TH of the binder component contained in the toner
In the molecular weight distribution of the F soluble component, the peak of the molecular weight is 100.
0 to 30,000, 30,000 or more components are 1% or more, weight average particle diameter is 3 to 10 μm, and the number average molecular weight is 2,000 to 2,000 in the molecular weight distribution of the THF soluble component of the binder component contained in the toner. 15,000 and
When the weight average molecular weight / number average molecular weight is 10.0 or less, it is possible to obtain a dry toner having a wide fixing width.

In addition, the toner of the present invention has a small wax surface existence ratio in fluidity and is finely dispersed, so that the toner performance is effective for the transparency of the color toner. Therefore, it is possible to design a small-sized and inexpensive color copying machine or printer that does not need to supply fixing oil for these reasons.

Further, according to the method for producing a toner of the present invention, it is possible to finely disperse the toner inside the toner particles, which is difficult to use by the conventional kneading and pulverizing method. In addition, since the wax is encapsulated in the resin in the suspension polymerized toner, the efficiency of the releasing effect is inferior to the amount of the wax as compared with the pulverization. In addition, since it can be easily dispersed in a polyester resin, which was difficult to use as a binder resin in the conventional polymerization method, and the shape of the toner can be controlled, the powder characteristics are good and the transfer Highly efficient toner can be designed.

The method for producing the toner of the present invention is
Compared to pulverized toner, wax can be finely dispersed in the particles, and with the pulverization method, a small particle size toner of 4 to 6 μm was practically difficult in terms of productivity and cost, but it can be achieved very easily. Became. The wax dispersion unit can be finely dispersed, so that the color image quality is high, and especially OHP
It is possible to provide a toner having a good transmission image. By combining the toner of the present invention and the belt fixing device, it is possible to greatly improve the following problems when the conventional belt fixing device and oilless are used.

1) Compared with roller fixing, the surface pressure is less likely to increase, and the release agent is less likely to seep out than oilless. Therefore, it is difficult for the high-speed type of oilless fixing to have a releasing width. 2) Due to the low surface pressure, the glossiness in color does not increase. 3) Since the nip width is wide, wrinkles easily occur.

[0027]

DETAILED DESCRIPTION OF THE INVENTION The toner fixing method of the present invention is used.
Regarding Belt Fixing Device According to the Present Invention FIG. 1 shows an example of a belt fixing device used in the toner fixing method of the present invention, and FIG. This belt fixing device is intended to prevent hot offset and shorten the start-up time so that oil is not used in the fixing device in the color image forming apparatus.

In FIGS. 1 and 2, 1 is a heating roller,
2 is a fixing roller, 3 is an endless fixing belt, 4 is a pressure roller, 5 is a heater for heating the fixing belt, 6 is an inlet guide plate,
Reference numeral 7 is a temperature detecting means including a thermistor, 8 is a portion for performing the first fixing step, 9 is a portion for performing the second fixing step, 10
Reference numeral 11 is a pressure applying means including a pressure spring, 11 is a tension applying means including a tension spring, and 13 is a transfer paper carrying an unfixed toner 13a.

The fixing belt 3 is stretched around the heating roller 1 and the fixing roller 2 (stretched with a predetermined tension), and the pressure roller 4 is provided to face the fixing roller 2 with the fixing belt 3 interposed therebetween. The pressure roller 4 has a portion 9 for performing the second fixing process.
Then, the pressure is applied to the fixing roller 2 via the fixing belt 3, and in the portion 8 where the first fixing process is performed, the fixing roller 2 is pressed against the fixing belt 3 without being pressed.

The heating roller 1 having the heater 5 built therein is made of a metal pipe having a small diameter and a thin wall (for example, a pipe made of aluminum, iron, copper or stainless steel) to have a low heat capacity in order to accelerate the rising of the apparatus. . The fixing belt 3 is heated by the heater 5 via the heating roller 1,
The thermistor 7 detects the surface temperature of the portion of the fixing belt 3 which is heated by the heating roller 1. A temperature control unit (not shown) uses the temperature detection signal from the thermistor 7 to detect the temperature of the heater 5
Is controlled so that the surface temperature of the fixing belt 3 is maintained at a predetermined set temperature.

The fixing roller 2, the heating roller 1, the pressure roller 4, and the fixing belt 3 are rotated by rotational driving by a driving source (not shown). The transfer paper as the material to be fixed is conveyed between the fixing belt 3 and the pressure roller 4, and the toner image on the transfer paper is heated by the fixing belt 3 and fixed on the transfer paper. In the portion 8 in which the first fixing step is performed, the fixing pressure (pressure between the fixing belt 3 and the pressure roller 4) is set low enough to prevent wrinkles on the transfer paper, and in the portion 9 in which the second fixing step is performed. In, the fixing pressure (contact pressure between the fixing belt 3 and the pressure roller 4) is set so as to obtain a desired fixing property.

The heating roller 1 is movably provided, and the fixing belt 3 is pressed by the pressure spring 11 to fix the fixing belt 3.
Tension is applied to the pressure roller 4, and the pressure roller 4
0 is pressed by the fixing belt 2 via the fixing belt 3
Pressurize. The fixing pressure in the first fixing step is set by adjusting the tension of the fixing belt 3 by the tension spring 11, and the fixing pressure in the second fixing step is set by the pressure spring 10. The pressure roller 10 may press the fixing roller 2 so that the pressure roller 4 presses the fixing roller 2 via the fixing belt 3.

In this example of the apparatus, since the heater 5 heats the fixing belt 3 via the heating roller 1 having a low heat capacity,
An instant rise is possible. Also, the fixing process is the first
The fixing step and the second fixing step are sufficiently long (nip time is 50 ms to 20 ms due to the long nip width).
0 ms, which is sufficiently long, and the self-cooling effect of the fixing belt 3 (the surface of the fixing belt 3 is cooled in the fixing step because there is no heat source on the unfixed image surface side of the fixing step portions 8 and 9 of the fixing belt 3). By the action), a temperature range in which the fixing is good is obtained, and the offset margin is increased.

Furthermore, the fixing pressure in the first fixing process 0.5 kg / cm ² or less is a entry side of the transfer paper, preferably by setting 0.2 kg / cm ² or less and sufficiently low, the transfer sheet The rate of occurrence of wrinkles on the transfer paper smoothly entering the fixing nip portion between the fixing belt 3 and the pressure roller 4 is higher than the current level (the degree of wrinkles on the transfer paper is equal to or higher than that of the heat roller fixing device). You can prevent it from happening.

The fixing device used to carry out the toner fixing method of the present invention comprises a fixing roller 2 and a heating roller 1.
An endless fixing belt 3 having a low heat capacity which is stretched between the heating roller 1 and the fixing roller 2; A belt fixing device having the following is a basic configuration.

The heating roller 1 has a heater 5 for heating the fixing belt therein. In order to reduce the heat capacity of the heating roller 1, it is preferable to use a material having a small specific heat and a large thermal conductivity, and for example, a metal such as aluminum, copper, iron or stainless steel is preferable.

The fixing belt 3 is heated by the heater 5 via the heating roller 1. In order to improve the thermal responsiveness of the fixing belt and maintain the flexibility of the fixing belt, the belt material is preferably a substrate having a thickness of 30 to 150 μm or less, such as nickel or polyimide. Also in the releasing layer of the fixing belt 3, in order to improve the thermal response, the thickness is preferably 50 to 300 if it is silicon rubber.
μm, and the thickness is preferably 1 if it is a fluororesin type.
It is 0 to 50 μm.

The temperature detecting means including the thermistor 7 detects the surface temperature of the portion of the fixing belt 3 which is heated by the heating roller 1. The temperature control unit (not shown) is a thermistor 7.
The heater 5 is controlled based on the temperature detection signal so that the surface temperature of the fixing belt 3 is maintained at a predetermined set temperature.

The fixing roller 2, the heating roller 1, the fixing belt 3, and the pressure roller 4 are rotated by a driving source (not shown). The transfer paper as the material to be fixed is conveyed through a fixing nip portion between the fixing belt 3 and the pressure roller 4 as shown by an arrow in the figure, and the toner image on the transfer paper is heated by the fixing belt 3 and fixed on the transfer paper. It

The heating roller 1 does not require a particularly large load due to the constitution of this apparatus. As a force required to stretch the fixing belt 3, if the fixing belt tension is 1 Kgf (9.8 N) / fixing belt tension on one side, the fixing belt 3 sufficiently functions.
Further, since the heating roller 1 as the fixing belt heating means and the fixing nip portion forming means are separated from each other, the heating roller 1 does not require a fixing pressure and a large load is not applied. Therefore, the heating roller 1 can be downsized and thinned to reduce the heat capacity of the heating roller 1, whereby the rising time can be shortened. As the low heat capacity heating roller 1,
A heating roller of 45 cal / ° C. or lower, preferably 15 cal / ° C. or lower is desirable.

Ratio of belt fixing device and heat roller fixing device
Comparing the belt fixing device used in the toner fixing method of the compare present invention and the heat roller fixing device, the fixing lower limit temperature is a belt fixing device, reduced in the same size with increasing both nip time the heat roller fixing device Go. The hot offset generation temperature is a device mechanism that can set the nip width with the fixing roller to a high value.However, in the case of a belt fixing device, it is disadvantageous compared to roller fixing in order to increase the nip because of the belt transport mechanism. It has become a mechanism. For this reason, in the case of an oilless mechanism, the release agent contained in the toner is less likely to exude due to the nip pressure, and the effect of the release agent on hot offset is small and the generated temperature tends to be low. In particular, since it is necessary to satisfy the oilless property and fixing property in a high-speed machine, and hot offset resistance, and energy saving is indispensable in order to make a fixing device compatible with high speeds, conventional toners are also used. Since the performance is not obtained, it is a new oil-less type and has high mold release,
Toner performance with a wide fixing width is required.

Regarding the Toner of the Present Invention The dry toner of the present invention is a composition containing a resin and a colorant, and the resin contains a modified polyester. Further, it is preferable that the resin having the highest composition ratio in the toner is a polyester resin containing a modified polyester resin. In this toner, the toner composition is dissolved / dispersed in an organic solvent, the composition is granulated in an aqueous medium, and a polyaddition reaction is performed under the granulation, or a toner composition containing a prepolymer is added to an organic solvent. It is obtained by dissolving / dispersing in a solvent, granulating this composition in an aqueous medium while producing a polyester having a urea bond, and subjecting the composition to a polyaddition reaction under granulation. It satisfies the hot offset property. At this time, a release agent is contained in the case of the oilless belt fixing device. If necessary, a charge control agent described below may be added to 0.1%.
It is possible to adjust the charge level by adding ~ 5%.

As the releasing agent, wax is usually used in many cases, but the releasing agent is not limited to wax, and any material exhibiting releasing property can be used. The fixing device is not limited to the case of completely oilless case, but there are cases where the roller is impregnated with oil, and in this case, the effect can be obtained even with a small amount of wax.

Among the dry toners, full-color toners are required to have characteristics such as color reproducibility, transparency and gloss which are contradictory to the basic characteristics such as heat resistant storage stability, low temperature fixing property and hot offset resistance. ing. To achieve this, it is essential to improve the dispersibility of colorants and waxes (color reproducibility / transparency) and to have a sharp molecular weight distribution (transparency / glossiness), while maintaining low-temperature fixability. And hot offset resistance must be satisfied.
The toner of the present invention can be obtained by a method of granulating in water, and polyester can be used as a raw material for granulation. Therefore, this granulating method is effective for balancing toner fixing performance and offset performance. This is the preferred method.

Further, the toner of the present invention can use a polyester having a urea bond which is a polar group.
The urea bonding part is easily adsorbed to the pigment, and it has the characteristic that it enables a high degree of dispersion of the pigment. Further, with respect to wax, on the contrary, the urea binding portion causes negative adsorption at the interface with the wax, so that the wax having a low polarity is stably dispersed. Then, by making most of the resin a low molecular weight component having a molecular weight of 30,000 or less and controlling the distribution sharply, it is possible to satisfy low-temperature fixability in addition to glossiness and transparency.

Regarding the hot offset resistance, various studies have been conducted so far for controlling the molecular weight distribution of the binder resin. For example, in order to achieve both of the contradictory properties of low-temperature fixability and hot offset resistance, for example, a binder resin having a wide molecular weight distribution is used, or a polymer component having a molecular weight of several hundreds of thousands or several million and a molecular weight of However, a method has been employed in which a resin having at least two molecular weight peaks of low molecular weight components of several thousands to tens of thousands is mixed and the functions of the respective components are separated. It is more effective for hot offset if the polymer component has a crosslinked structure or is in a gel state. However, in a full-color toner in which glossiness and transparency are required, it is not preferable to introduce a large amount of polymer component. Since the toner of the present invention can elongate the polyester by the urea bond to increase the molecular weight, it is possible to achieve the hot offset property while satisfying the transparency and gloss.

The toner composition is granulated in an aqueous medium, and the molecular weight distribution of the toner binder component subjected to polycondensation reaction under granulation is measured by the following method. Toner about 1
After accurately weighing g in an Erlenmeyer flask, 10 to 20 g of THF (tetrahydrofuran) is added, and the binder concentration is 5 to 10
% THF solution. The column was stabilized in a heat chamber at 40 ° C., and THF as a solvent was flowed through the column at this temperature at a flow rate of 1 ml / min to remove the THF.
Inject 20 μl of sample solution. The molecular weight of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared from the monodisperse polystyrene standard sample and the retention time. The calibration curve is prepared using a polystyrene standard sample. As the monodisperse polystyrene standard sample, for example, a product having a molecular weight of 2.7 × 10 ^{2 to} 6.2 × 10 ⁶ manufactured by Tosoh Corporation is used. A refractive index (RI) detector is used as the detector. Examples of the column include TSKgel and G10 manufactured by Tosoh Corporation.
00H, G2000H, G2500H, G3000H,
G4000H, G5000H, G6000H, G700
OH and GMH are used in combination.

The main peak molecular weight is usually 1000 to 3
0000, preferably 1500 to 10000, more preferably 2000 to 8000. When the amount of the component having a molecular weight of less than 1000 is increased, the heat-resistant storage stability is deteriorated, and when the amount of the component having a molecular weight of 30,000 or more is increased, the low temperature fixing property tends to be lowered, but the reduction can be suppressed as much as possible by balance control. The content of the component having a molecular weight of 30,000 or more is 1% or more, and although it varies depending on the toner material, it is preferably 3 to 6%. If it is less than 1%, sufficient hot offset resistance cannot be obtained, and if it is 10% or more, gloss and transparency may deteriorate.

Mn is 2000-15000 and Mw / Mn
The value of 10 is preferably 10 or less. When the value of Mw / Mn is 10 or more, a problem of microscopic compatibility of the resin occurs and the glossiness decreases. When Mn is 2000 or less, carrier contamination occurs due to low molecular components depending on the dispersant used. At the time of toner production of 15,000 or more, the oily viscosity increases, the dispersion of the colorant decreases, and the color reproducibility of the color toner decreases. Further, in order to improve the release performance of the colorant, it is possible to reduce the amount of the release agent and, instead, contain 1 to 15% of THF insoluble matter in the binder resin to secure hot offset. When wax is used as the release agent, the release performance is improved, but as a side effect, the exposed amount of wax on the particle surface is increased and the fluidity is reduced. In this case, there are cases where the stability of electrification is lacking and cases where the carrier adheres to the carrier and deteriorates the durability of the carrier. In such a case, the THF insoluble content exerts an effect of improving the mold release performance by the combination of the formulation compatibility with the amount of the mold release agent. The method for measuring the THF insoluble content is shown below.

(Method for measuring THF insoluble content) About 1.0 g (A) of resin or toner is weighed. About 50g of THF
Is added and the mixture is allowed to stand at 20 ° C for 24 hours. First, this is separated by centrifugation and filtered using a quantification filter paper of JIS standard (P3801) Type 5C. The solvent component of this filtrate is vacuum dried, and the residual amount (B) of only the resin component is measured. This residual amount is THF
It is the dissolved component. The THF insoluble content (%) is calculated by the following formula. THF insoluble matter (%) = [(A−B) / A] × 100 In the case of toner, the amount of THF insoluble component other than resin (W1)
And the amount of THF-dissolved component (W2) are separately investigated by a known method, and calculated from the following formula. THF insoluble matter (%) = (A-B-W2) / (A-W1)
-W2) x 100

(Regarding Method of Manufacturing Toner of the Present Invention) Next, a method of manufacturing the toner of the present invention will be described. The toner is obtained by dissolving / dispersing a toner composition containing at least a polyester resin or a modified polyester resin, a colorant, and a release agent in an organic solvent, and granulating the composition in an aqueous medium. Further, by using the polyester (i) modified with a urea bond, it is possible to obtain a toner that has undergone a polyaddition reaction under granulation.

The above-mentioned modified polyester resin is
A polyester resin having a bonding group other than an ester bond, or a resin component having a different structure bonded to the polyester resin through a covalent bond, an ionic bond, or the like, for example, a polyester terminal other than an ester bond It refers to the one reacted with. Specifically, a functional group such as an isocyanate group that reacts with an acid group or a hydroxyl group is introduced at the terminal and further reacted with an active hydrogen compound to modify the terminal. Examples of this include a reaction product of a polyester prepolymer (A) having an isocyanate group and an amine (B).

Examples of the compound having a plurality of active hydrogen groups include those having polyester terminals bonded to each other (such as urea-modified polyester and urethane-modified polyester). Further, as a group in which a reactive group such as a double bond is introduced into the polyester main chain and radical polymerization is carried out from the main group to introduce a carbon-carbon bond graft component into the side chain, styrene-modified, acrylic-modified polyester, etc. Can be mentioned. In addition, as a resin obtained by copolymerizing resin components having different constitutions in the main chain of polyester, for example, a resin copolymerized with a silicone resin whose terminal is modified by carboxyl group, hydroxyl group, epoxy group, mercapto group (silicone modified (Such as polyester)
Can be mentioned.

As the polyester prepolymer (A) having an isocyanate group, a polyester which is a polycondensate of a polyol (1) and a polycarboxylic acid (2) and has an active hydrogen group is further reacted with a polyisocyanate (3). Some of them are made. Examples of the active hydrogen group contained in the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group and the like, and among these, the alcoholic hydroxyl group is preferable.

As the polyol (1), a diol (1
-1) and a polyol (1-2) having 3 or more valences, and (1-1) alone or (1-1) and a small amount of (1-).
The mixture of 2) is preferred. As the diol (1-1), alkylene glycol (ethylene glycol, 1,
2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc .; alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetra) Methylene ether glycol, etc.); alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxide of the above alicyclic diol (ethylene Oxides, propylene oxide, butylene oxide, etc.) adducts; alkylene oxides of the above bisphenols (ethylene oxide, propylene oxide, bromine oxide, etc.) (Tylene oxide, etc.) and the like. Of these, preferred ones have 2 carbon atoms.
To alkylene glycol and bisphenol alkylene oxide adducts, particularly preferred are bisphenol alkylene oxide adducts,
And a combination of this and an alkylene glycol having 2 to 12 carbon atoms. As the trivalent or higher valent polyol (1-2), a trivalent or higher valent or higher polyvalent aliphatic alcohol (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or higher phenols (Trisphenol P
A, phenol novolac, cresol novolac, etc.); and alkylene oxide adducts of the above trivalent or more polyphenols.

Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-
2), and (2-1) alone or a mixture of (2-1) and a small amount of (2-2) is preferable. As the dicarboxylic acid (2-1), alkylenedicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) , Naphthalene dicarboxylic acid, etc.) and the like. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). As the polycarboxylic acid (2), an acid anhydride or a lower alkyl ester (such as methyl ester, ethyl ester or isopropyl ester) of the above may be used to react with the polyol (1).

Polyol (1) and polycarboxylic acid (2)
Is usually 2/1 to 1 as an equivalent ratio of hydroxyl group [OH] and carboxyl group [COOH] ([OH] / [COOH]).
/ 1, preferably 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) ); Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); Aroaliphatic diisocyanates (α, α, α ', α'-tetramethylxylylene diisocyanate, etc.); Isocyanurates; Phenol derivatives, oximes , Those blocked with caprolactam and the like; and combinations of two or more of these.

The ratio of the polyisocyanate (3) is the equivalent ratio ([NCO] / [OH]) of the isocyanate group [NCO] to the hydroxyl group [OH] of the polyester having a hydroxyl group.
Usually 5/1 to 1/1, preferably 4/1 to 1.2 / 1,
More preferably, it is 2.5 / 1 to 1.5 / 1. [N
When CO] / [OH] exceeds 5, low temperature fixability deteriorates.
When the molar ratio of [NCO] is less than 1, the urea content in the modified polyester becomes low and the hot offset resistance is deteriorated. The content of the polyisocyanate (3) constituting component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. Is. If it is less than 0.5% by weight, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat resistant storage stability and low temperature fixing property.
On the other hand, if it exceeds 40% by weight, the low temperature fixability is deteriorated.

The number of isocyanate groups contained in one molecule of the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, and more preferably 1.8 to 2 on average. .5. If the number is less than 1 per molecule, the molecular weight of the urea-modified polyester becomes low, and the hot offset resistance deteriorates.

As amines (B), diamine (B
1) Trivalent or higher polyamines (B2), amino alcohols (B3), amino mercaptans (B4), amino acids (B5), and amino acid blocks of B1 to B5 (B6). As the diamine (B1), aromatic diamine (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamine (4,4′-diamino-3,
3'dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc.) and aliphatic diamine (ethylenediamine, tetramethylenediamine,
Hexamethylenediamine) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. The amino groups of B1 to B5 blocked (B6) include amines and ketones of B1 to B5 (acetone, methyl ethyl ketone,
Examples thereof include a ketimine compound and an oxazoline compound obtained from methyl isobutyl ketone). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

Further, if necessary, an elongation terminator may be used to adjust the molecular weight of the urea-modified polyester. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and blocked products thereof (ketimine compounds).

The ratio of amines (B) is such that the isocyanate group in the prepolymer (A) having an isocyanate group is
The equivalent ratio ([NCO] / [NHx]) of [NCO] and the amino group [NHx] in the amine (B) is usually 1/2 to 2 /.
1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. [NCO] / [NH
When x] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) is low and the hot offset resistance is deteriorated. In the present invention, the polyester (i) modified with a urea bond may contain a urethane bond as well as a urea bond. The molar ratio of the urea bond content and the urethane bond content is usually 100/0 to 10/9.
It is 0, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of urea bond is less than 10%, the hot offset resistance is deteriorated.

In the present invention, the polyester (i) modified with the urea bond may be used alone, and the polyester (ii) not modified may be contained as a toner binder component together with the polyester (i).
The combined use of (ii) improves the low-temperature fixing property and the glossiness when used in a full-color device, and is preferable to single use. Examples of (ii) include polycondensates of the same polyol (1) and polycarboxylic acid (2) as the polyester component of (i) above, and preferred ones are also the same as (i). Further, (ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than the urea bond, for example, may be modified with a urethane bond.

It is preferable that at least a part of (i) and (ii) are compatible with each other from the viewpoint of low-temperature fixability and hot offset resistance. Therefore, the polyester component of (i) and (ii)
Are preferably of similar composition. When (ii) is contained, the weight ratio of (i) and (ii) is usually 5/95 to 80/2.
0, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, particularly preferably 7/93 to 2
It is 0/80. When the weight ratio of (i) is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of compatibility between heat resistant storage stability and low temperature fixability. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10
120, particularly preferably 20-80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. (I
The acid value of i) is usually 1 to 30, preferably 5 to 20. By giving an acid value, it tends to be negatively charged.

In the present invention, the glass transition point (Tg) of the toner binder is usually 55 to 75 ° C., preferably 55.
~ 65 ° C. If it is less than 55 ° C, the heat-resistant storage stability of the toner is deteriorated, and if it exceeds 75 ° C, the low-temperature fixability becomes insufficient.
Due to the coexistence of the urea-modified polyester resin, the dry toner of the present invention tends to have good heat-resistant storability even if it has a low glass transition point, as compared with a known polyester-based toner. Here, the glass transition point (Tg) of the resin is SE
Measured with IKO EXSTAR6000TG / DTA6200, heated 10 ℃ / min, MA
The measured value after one thermal history at X200 ° C is used as the measured value.

Release Agent The wax used in the toner of the present invention has a melting point of 60.
A wax having a low melting point of up to 120 ° C. acts more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface, thereby applying a release agent such as oil to the fixing roller. It is effective against high temperature offset without If the melting point is 120 ° C. or higher, the effect of releasability is not sufficient, and if it is 60 ° C. or lower, the toner storability and blocking may deteriorate, which is not preferable. The melting point of the wax in the present invention is the differential scanning calorimeter (DS
The maximum endothermic peak according to C) was used.

The following materials can be used as the wax component functioning as a release agent that can be used in the present invention. That is, as specific examples, waxes and waxes include carnauba wax, cotton wax, wooden wax, plant wax such as rice wax, beeswax, animal wax such as lanolin, ozokerite, mineral wax such as sercine, And and petroleum waxes such as paraffin, microcrystalline and petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones and ethers may be mentioned. Further, 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride, fatty acid amides containing chlorinated hydrocarbons, and low molecular weight crystalline polymer resins such as poly-n-stearyl methacrylate and poly-n-lauryl. A crystalline polymer having a long side chain alkyl group such as a homopolymer or a copolymer of polyacrylate such as methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate) can also be used.

Of these, vegetable wax Mw40
The wax having a range of 0 to 5,000 and an acid value of 1 to 30 is finely dispersed in the polyester resin to a suitable degree, and the transparency required for the color toner is particularly good and suitable for the color toner. An ester wax having a needle penetration degree of 3 or less is suitable for color toners because it has less coloring and odor. For color toners, transparency of OHP paper is often required for presentation, but if the needle penetration degree exceeds 3, the fixing property tends to decrease. The degree of needle penetration is an index of heat resistant storage stability, and the degree of needle penetration is tested as follows. [Heat-resistant storage test method] Inner diameter 25 mm, height 70
10 g of toner is put in a glass bottle of mm and left in a constant temperature bath at 50 ° C. for 24 hours, and then the degree of needle penetration is checked by a JIS-K2530 needle penetration meter. It was confirmed that this permeability depends on the dispersion unit, dispersion diameter, and dispersion form of the wax contained in the toner. Further, since the belt fixing device has a lower surface pressure than the roller fixing, it is disadvantageous for fixing and the effect of the release agent is important. That is, the wax dispersion unit in the toner is made to have a particle size and a shape that are unlikely to affect the permeability, and by controlling the dispersion state in the resin, the permeability of the wax is controlled regardless of the degree of crystallinity of the wax. You can eliminate the problem. This greatly affects not only the transparency but also the hot offset property.

Regarding the dispersibility of wax, the above-mentioned production method (granulation in an aqueous medium) of the present toner shows a great difference as compared with the kneading and pulverizing method and the polymerization method. That is, in the kneading and pulverizing method, there is a limit to fine dispersion in kneading, and it is not easy to make the particle diameter of 2 μm or less. Further, since stress concentration during pulverization occurs at the interface between the wax and the resin, the wax is likely to appear on the surface of the particles, which has a releasing effect on hot offset, but is disadvantageous for improving the transparency of the color toner. On the other hand, in suspension polymerization, it is very difficult to achieve transparency due to inclusion and vinyl polymerization. In the case of a polymerized toner by emulsion polymerization, it is practically difficult to finely disperse wax during vinyl polymerization or toner particle formation process. On the other hand, the above-mentioned method for producing the toner according to the present invention relates to fine dispersion of wax in a shape,
This is a manufacturing method in which the morphology, particle size and the like are relatively easy to control.

Next, a method for specifically measuring the dispersed diameter of the wax will be described. In the present invention, the particle diameter of the wax in the maximum direction is defined as the wax dispersion diameter. Specifically, the toner is embedded in an epoxy resin, ultrathin sliced to about 100 μm, stained with ruthenium tetroxide, and then magnified by a transmission electron microscope (TEM) at a magnification of 1000 to 100.
Observation was carried out at 00 times, a photograph was taken, and the photograph was subjected to image evaluation to observe the dispersed state of the wax and measure the dispersed diameter.

The dispersion diameter of the wax of the present invention is preferably 0.1 to 2 μm with respect to the wax existing in the toner, and the number of wax particles is 70% by number or more based on the total number of wax particles, and more preferably. It is more preferable that the number of wax particles of 0.5 to 1 μm is 70% by number or more based on the total number of wax particles. If there are many particles smaller than 0.1 μm, sufficient releasability cannot be expressed. Further, if the maximum length of particles larger than 3 μm is 5% or more, cohesiveness is likely to be caused, fluidity is apt to be deteriorated, filming may be caused, and color reproducibility and glossiness are remarkably increased in the color toner. Will lower it. Further, the wax dispersed in the toner must be dispersed evenly in the toner particles and at least three wax particles must be present in the toner particles. Three
If it exceeds 0% by number, problems occur in fixability and releasability.

In the wax dispersed state of this photograph, it is an important point that the dispersed wax is dispersed not in the major axis of the wax in the horizontal direction with respect to the toner particle surface but in the inner direction. In other words, the toner in which the wax is dispersed inside the particles has good fluidity of the powder and the fluctuation of the charge is relatively small, but the toner in which the wax particles extend along the surface of the particle and are exposed on the surface has a comparatively good releasability. Although it is suitable, it has problems similar to pulverized toner such as charge stability and fluidity deterioration.

Regarding Coloring Agent As the coloring agent of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G,
5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrasan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Tan, Lead Vermilion, Cadmium Red, Kad Muum Mercury Red, Antimon Zhu,
Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4R
H), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B,
Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake,
Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkali Blue Lake, Peacock Blue Lake, Victoria Blue Rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC),
Indigo, Ultramarine, Navy Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chromium Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B , Green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithobon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight based on the toner.

The colorant used in the present invention can also be used as a master batch compounded with a resin. As the binder resin used in the production of the masterbatch or kneaded with the masterbatch, in addition to the above-mentioned modified and unmodified polyester resins, styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene and their substitution are substituted. Polymer of styrene; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer,
Styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate Copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile- Styrene-based copolymers such as indene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester Le, epoxy resins, epoxy polyol resins, polyurethanes, polyamides, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin,
Examples thereof include terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax, which may be used alone or in combination.

The masterbatch can be obtained by applying a high shearing force to a resin for a masterbatch and a colorant, and mixing and kneading the mixture. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is an aqueous paste containing a colorant water, is mixed and kneaded with a resin and an organic solvent, the colorant is transferred to the resin side, and a method of removing water and an organic solvent component is also a colorant wet cake. Since it can be used as it is, it does not need to be dried and is preferably used.
For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

Charge Control Agent The toner of the present invention may contain a charge control agent, if necessary. All known charge control agents can be used, and examples thereof include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdic acid chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine modified). (Including quaternary ammonium salt),
Examples thereof include alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and salicylic acid derivative metal salts. Specifically, the Nigrosine dye Bontron 03, the quaternary ammonium salt Bontron P-51, the metal-containing azo dye Bontron S-34, and the oxynaphthoic acid metal complex E-8.
2. E-84 of salicylic acid type metal complex, E-89 of phenol type condensate (above, manufactured by Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, T.
P-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEGVP2036,
Copy Charge NX VP434 (above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex.
(Manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, other sulfonic acid groups,
Examples thereof include polymer compounds having a functional group such as a carboxyl group and a quaternary ammonium salt.

In the present invention, the amount of the charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method. Although not limited to, preferably 100 parts by weight of the binder resin,
It is used in the range of 0.1 to 10 parts by weight. Preferably,
The range of 0.2 to 5 parts by weight is preferable. If the amount exceeds 10 parts by weight, the chargeability of the toner is too large, the effect of the main charge control agent is diminished, the electrostatic attraction force with the developing roller is increased, the fluidity of the developer is lowered, and the image density is lowered. Cause decline. These charge control agents and release agents can be melt-kneaded together with the masterbatch and the resin, and, of course, may be added when they are dissolved or dispersed in an organic solvent.

External Additives Inorganic fine particles can be preferably used as an external additive for assisting the fluidity, developability and chargeability of the toner of the present invention. The primary particle size of the inorganic fine particles is 5 mμ to 2
The thickness is preferably μm, particularly preferably 5 mμ to 500 mμ. The specific surface area by the BET method is preferably 20 to 500 m ² / g. The proportion of the inorganic fine particles used is 0.01 to 5% by weight of the toner.
Is preferable, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatom. Examples thereof include soil, chromium oxide, cerium oxide, pengal, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide and silicon nitride. Among them, as the fluidity-imparting agent, it is preferable to use hydrophobic silica fine particles and hydrophobic titanium oxide fine particles in combination.

In particular, when agitating and mixing using both fine particles having an average particle diameter of 50 mμ or less, the electrostatic force with the toner and the Van der Waals force are remarkably improved to obtain a desired charge level. Even by stirring and mixing inside the developing machine for this purpose, the fluidity-imparting agent is not detached from the toner, and good image quality in which no fireflies are generated can be obtained, and the transfer residual toner can be further reduced. It was revealed.

Titanium oxide fine particles are excellent in environmental stability and image density stability, but on the other hand, they tend to deteriorate the charging start-up property. Therefore, when the amount of titanium oxide fine particles added is larger than the amount of silica fine particles added, side effects It is possible that the effect of will increase. However, the addition amount of the hydrophobic silica fine particles and the hydrophobic titanium oxide fine particles is 0.3 to 1.
It was found that in the range of 5 wt%, the desired charge rising characteristics were not significantly impaired and the desired charge rising characteristics were obtained, that is, stable image quality was obtained even when copying was repeated, and toner blowing was suppressed.

Production Method of Modified Polyester Resin The resin for toner binder can be produced by the following method. The polyol (1) and the polycarboxylic acid (2) are mixed in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc.
The resulting water is heated to 280 ° C. and, if necessary, the pressure is reduced to distill off the produced water to obtain a polyester having a hydroxyl group. Next, this is reacted with polyisocyanate (3) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group. Further, the amines (B) are added to (A)
The reaction is carried out at ˜140 ° C. to obtain a polyester (i) modified with a urea bond.

If necessary, a solvent may be used in the reaction of (3) and the reaction of (A) with (B). As usable solvents, aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers Examples thereof include those inert to isocyanate (3) such as the class (tetrahydrofuran etc.). When polyester (ii) not modified by urea bond is used together, it is treated in the same manner as polyester having hydroxyl group (ii)
Is prepared, and this is dissolved in the solution after completion of the reaction of (i) and mixed. The dry toner can be manufactured by the following method, but is not limited to these.

Regarding the Method for Producing Toner in Aqueous Medium As the aqueous medium used in the present invention, water alone may be used.
A solvent miscible with water can also be used together. Examples of miscible solvents include alcohols (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methylethylketone, etc.), and the like.

The toner particles are prepared by dispersing a dispersion of the prepolymer (A) having an isocyanate group in an aqueous medium.
It may be formed by reacting with (B), or the urea-modified polyester (i) produced in advance may be used. As a method for stably forming a dispersion composed of the urea-modified polyester (i) and the prepolymer (A) in an aqueous medium, a toner raw material composed of the urea-modified polyester (i) and the prepolymer (A) in the aqueous medium is used. Examples of the method include adding the composition of (1) and dispersing with a shearing force.
The prepolymer (A) and other toner compositions (hereinafter referred to as toner raw materials) such as colorant, colorant masterbatch, release agent, charge control agent, and unmodified polyester resin are dispersed in an aqueous medium. Although they may be mixed at the time of forming, it is more preferable that the toner raw materials are mixed in advance and then the mixture is added to and dispersed in an aqueous medium. Further, in the present invention, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when the particles are formed in the aqueous medium, and after forming the particles. , May be added. For example, the colorant may be added by a known dyeing method after forming particles not containing the colorant.

The dispersion method is not particularly limited, but known equipment such as low speed shearing method, high speed shearing method, friction method, high pressure jet method, ultrasonic wave, etc. can be applied. The high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the number of revolutions is not particularly limited, but is usually 1000 to 30000 rp.
m, preferably 5000-20000 rpm. The dispersion time is not particularly limited, but is usually 0.1 to 5 minutes in the case of the batch method. The dispersion temperature is usually 0.
-150 degreeC (under pressure), Preferably it is 40-98 degreeC.
The higher temperature is preferable in that the dispersion of the urea-modified polyester (i) and the prepolymer (A) has a low viscosity and the dispersion is easy.

The amount of the aqueous medium used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts of the toner composition containing the urea-modified polyester (i) and the prepolymer (A). If the amount is less than 50 parts by weight, the toner composition is poorly dispersed and toner particles having a predetermined particle size cannot be obtained. If it exceeds 2000 parts by weight, it is not economical. In addition, a dispersant can be used if necessary. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

An anionic surfactant such as an alkylbenzene sulfonate, an α-olefin sulfonate, or a phosphoric ester as a dispersant for emulsifying and dispersing the oily phase in which the toner composition is dispersed in a liquid containing water. , Amine amine type such as alkylamine salt, aminoalcohol fatty acid derivative, polyamine fatty acid derivative, imidazoline, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, chloride Quaternary ammonium salt type cationic surfactants such as benzethonium, nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, Arukiru N, amphoteric surfactants such as N-dimethyl ammonium betaine and the like.

By using a surfactant having a fluoroalkyl group, the effect can be enhanced with a very small amount. The preferred anionic surfactant having a fluoroalkyl group has 2 to 1 carbon atoms.
Fluoroalkylcarboxylic acid of 0 and its metal salt, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (C6 to C11)
Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-
C8) -N-Ethylamino] -1-propanesulfonic acid sodium salt, fluoroalkyl (C11 to C20) carboxylic acid and metal salt, perfluoroalkylcarboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 To C12) sulfonic acid and its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkyl (C6-C
10) Sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate and the like can be mentioned.

The trade name is Surflon S-111,
S-112, S-113 (Asahi Glass Co., Ltd.), Florard F
C-93, FC-95, FC-98, FC-129 (Sumitomo 3M), Unidyne DS-101, DS-10
2, (Taikin Engineering Co., Ltd.), Megafac F-ll0,
F-120, F-113, F-191, F-812, F
-833 (manufactured by Dainippon Ink and Chemicals, Inc.), Ektop EF-10
2, 103, 104, 105, 112, 123A, 12
3B, 306A, 501, 201, 204, (manufactured by Tochem Products), Futgent F-100, F15
0 (manufactured by Neos) and the like.

As the cationic surfactant, an aliphatic quaternary aliphatic primary, secondary or tertiary amine acid having a fluoroalkyl group, an aliphatic quaternary aliphatic quaternary ammonium salt such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, etc. may be used. Ammonium salt, benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt,
As the product name, Surflon S-121 (made by Asahi Glass Co., Ltd.),
Fluorard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikinye Industrial Forest), Megafac F-
150, F-824 (manufactured by Dainippon Ink and Chemicals, Inc.), Ektop EF-132 (manufactured by Tochem Products Co., Ltd.), Futgent F-300 (manufactured by Neos Co., Ltd.) and the like.

Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as a dispersant of an inorganic compound which is poorly soluble in water.

The dispersed liquid droplets may be stabilized with a polymeric protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid,
Acids such as itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or a hydroxyl group-containing (meth) acrylic monomer, for example β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate.
Acrylic acid β-hydroxypropyl, methacrylic acid β-
Hydroxypropyl, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-methacrylic acid
Chloro-2-hydroxypropyl, diethylene glycol monoacrylic acid ester, diethylene glycol monomethacrylic acid ester, glycerin monoacrylic acid ester, glycerin monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide, etc. with vinyl alcohol or vinyl alcohol Ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing a vinyl alcohol and a carboxyl group, such as pinyl acetate, pinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone. Acrylides or their acid chlorides such as methylol compounds, acrylic acid chloride and methacrylic acid chloride , Homopolymers or copolymers such as those having a nitrogen atom such as pinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine, or a hetero ring thereof, polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkyl Amine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester and other polyoxyethylene-based, methyl cellulose Cellulose such as hydroxyethyl cellulose and hydroxypropyl cellulose can be used.

In order to remove the organic solvent from the obtained emulsified dispersion, a method of gradually elevating the temperature of the entire system to completely evaporate and remove the organic solvent in the droplets can be adopted. Alternatively, it is also possible to spray the emulsified dispersion in a dry atmosphere to completely remove the non-water-soluble organic solvent in the droplets to form toner fine particles, and also to evaporate and remove the aqueous dispersant. . As a dry atmosphere in which the emulsion dispersion is sprayed,
A gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, etc., in particular, various air streams heated to a temperature above the boiling point of the highest boiling solvent used are generally used. Spray dryer,
A short time processing such as belt dryer and rotary kiln can obtain the desired quality.

When a dispersion stabilizer that is soluble in an acid such as a calcium phosphate salt or an alkali is used, the calcium phosphate salt is dissolved in an acid such as hydrochloric acid and then washed with water. Remove the salt. It can also be removed by an operation such as decomposition with an enzyme. If a dispersant is used,
The dispersant can be left on the surface of the toner particles, but it is preferable to remove the dispersant by washing after the elongation and / or cross-linking reaction from the viewpoint of charging the toner.

Further, in order to lower the viscosity of the toner composition, a solvent in which the urea-modified polyester (i) or (A) is soluble can be used. It is preferable to use a solvent because the particle size distribution becomes sharp. The solvent has a boiling point of 10
Volatilities below 0 ° C. are preferred from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more kinds. In particular, aromatic solvents such as toluene and xylene and methylene chloride,
Halogenated hydrocarbons such as 1,2-dichloroethane, chloroform and carbon tetrachloride are preferred. Prepolymer (A)
The amount of the solvent used per 100 parts is usually 0 to 300 parts,
Preferably 0 to 100 parts, more preferably 25 to 70 parts.
It is a department. When a solvent is used, it is heated and removed under normal pressure or reduced pressure after the elongation and / or crosslinking reaction.

The extension and / or crosslinking reaction time is selected depending on the reactivity depending on the combination of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C., preferably 4
It is 0 to 98 ° C. Further, a known catalyst can be used if necessary. Specific examples thereof include dibutyltin laurate and dioctyltin laurate.

In order to remove the organic solvent from the obtained emulsified dispersion, a method of gradually elevating the temperature of the entire system to completely evaporate and remove the organic solvent in the droplets can be adopted. Alternatively, it is also possible to spray the emulsified dispersion in a dry atmosphere to completely remove the non-water-soluble organic solvent in the droplets to form fine toner particles, and at the same time, evaporate and remove the aqueous dispersant. .. As a dry atmosphere in which the emulsion dispersion is sprayed,
A gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, etc., in particular, various air streams heated to a temperature above the boiling point of the highest boiling solvent used are generally used. Spray dryer,
A short time processing such as belt dryer and rotary kiln can obtain the desired quality.

When emulsified and dispersed, the particle size distribution is wide, and when washing and drying are carried out while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying it into a desired particle size distribution. The classification operation can remove the fine particle portion by cyclone, decanter, centrifugal separation, etc. in the liquid. Of course, the classification operation may be performed after the powder is obtained after drying, but it is preferable to perform the classification operation in a liquid in terms of efficiency. The obtained unnecessary fine particles or coarse particles can be returned to the kneading step again and used for forming particles. At that time, the fine particles or the coarse particles may be in a wet state. It is preferable to remove the used dispersant from the obtained dispersion as much as possible, but it is preferable to perform it at the same time as the classification operation described above.

The dried toner powder thus obtained is mixed with different kinds of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles and colorant fine particles, and the mixed powder is subjected to mechanical impact. By giving it, immobilization and fusion on the surface can be prevented, and detachment of different particles from the surface of the obtained composite particles can be prevented. Specific means include a method of applying an impact force to the mixture with a blade rotating at a high speed, a method of introducing the mixture into a high-speed air stream and accelerating the particles to collide the particles with each other or the composite particles into an appropriate collision plate. is there. As the equipment, an Ong mill (made by Hosokawa Micron Co., Ltd.), a type I mill (made by Nippon Pneumatic Co., Ltd.) was modified to lower the crushing air pressure, a hybridization system (made by Nara Machinery Co., Ltd.), and a Kryptron system. (Made by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

Two-Component Carrier When the toner of the present invention is used in a two-component developer, it may be used by mixing it with a magnetic carrier. The content ratio of carrier to toner in the developer is 100 parts by weight of carrier. On the other hand, 1 to 10 parts by weight of toner is preferable. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder and magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin and epoxy resin. Further, polyvinyl and polyvinylidene resins such as acrylic resin, polymethylmethacrylate resin, polyacrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin,
Polyvinyl butyral resin, polystyrene resin such as polystyrene resin and styrene-acrylic copolymer resin, halogenated olefin resin such as polyvinyl chloride, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, poly Vinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, Fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, and silicone resins can be used. If necessary, conductive powder or the like may be contained in the coating resin. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. It is preferable that these conductive powders have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control the electric resistance. Further, the toner of the present invention can be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

Toner Circularity Measurement Method The toner average circularity is 0.96 to 1.00, and it is important that the toner has a specific shape and a specific shape distribution. The average circularity is 0.96. In the case of a toner having an irregular shape far below the sphere, that is, a toner containing 30% or more of particles having a circularity of less than 0.95 according to the present invention, a recently demanded high quality image cannot be obtained. Amorphous particles have many points of contact with the smooth medium on the photoconductor, etc., and because the electric charge is concentrated on the tips of the protrusions, the van der Waals force and the image force have a higher adhesive force than spherical particles. . Therefore, in the electrostatic transfer process, the spherical particles were selectively moved in the toner in which irregular-shaped particles and spherical particles were mixed, and the character portion or line portion image omission occurred. The specific method for measuring the circularity is shown below.

As a method of measuring the shape, an optical detection zone method is suitable in which a suspension containing particles is passed through a detection zone on the flat plate, and a CCD camera optically detects and analyzes the particle image. is there. A toner containing 30% or less of particles having an average circularity of 0.96 or more and less than 0.95, which is a value obtained by dividing the perimeter of an equivalent circle with the same projected area obtained by this method by the perimeter of existing particles, is appropriate. It was found to be effective for forming a high-definition image with reproducibility of various densities. More preferably, 10% or less of the particles have an average circularity of 0.98 to 1.00 and a circularity of less than 0.95. This value can be measured as an average circularity by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, a surfactant, preferably an alkylbenzene sulfonate, as a dispersant is added to 0.1 to 100 ml of water in which impure solids are removed in advance in a container.
~ 0.5 ml is added, and about 0.1-0.5 g of the measurement sample is further added. The suspension in which the sample is dispersed is approximately 1 with an ultrasonic disperser.
Disperse for ~ 3 minutes and adjust dispersion concentration to 3000 ~ 1
It is obtained by measuring the shape and distribution of the toner by the above apparatus as ten thousand pieces / μl.

[0104]

The present invention will be further described with reference to the following examples.
The present invention is not limited to this. Below,
"Part" indicates "part by weight". The physical properties of the toner binder used in each example are shown in Table 1.

Example 1 ( Synthesis of Toner Binder ) 780 parts of bisphenol A ethylene oxide 2 mol adduct and 28 parts of isophthalic acid were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube.
0 parts and 2 parts of dibutyltin oxide were added, and the reaction was carried out at 230 ° C. for 6 hours under normal pressure and further for 3 hours under reduced pressure of 10-15 mmHg, then cooled to 160 ° C., and 32 parts of phthalic anhydride was added thereto. Was added and reacted for 2 hours. Then, it was cooled to 80 ° C. and reacted with 198 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate-containing prepolymer (1). Then, 267 parts of prepolymer (1) and 12 parts of isophoronediamine were added to 50 parts.
The reaction was carried out at 0 ° C. for 2 hours to obtain a urea-modified polyester (1) having a weight average molecular weight of 54,000. 724 parts of bisphenol A ethylene oxide 2 mol adduct in the same manner as above,
276 parts of terephthalic acid was subjected to polycondensation under normal pressure at 230 ° C. for 8 hours and then reacted under reduced pressure of 10 to 15 mmHg for 5 hours to obtain an unmodified polyester (a) having a peak molecular weight of 5000. Urea modified polyester (1) 10
0 part and 900 parts of unmodified polyester (a) were dissolved and mixed in 1800 parts of ethyl acetate solvent to obtain an ethyl acetate solution of toner binder (1). Partially dried under reduced pressure to isolate the toner binder (1).

(Preparation of Toner ) 210 parts of an ethyl acetate solution of the above-mentioned toner binder (1) and pentaerythritol tetrabehenate (melting point 81 ° C., needle penetration degree 2.4, molecular weight 4200, acid value 4.0) were placed in a beaker. 20 parts and 4 parts of copper phthalocyanine blue pigment were added and stirred at 60 ° C. with a TK homomixer at 12000 rpm to uniformly dissolve and disperse. 706 parts of deionized water in the beaker,
Hydroxyapatite 10% suspension (Nippon Kagaku Kogyo)
260 parts of Supatite 10 manufactured by Co., Ltd. and 0.2 parts of sodium dodecylbenzenesulfonate were added and uniformly dissolved.
Then, the temperature is raised to 60 ° C. and 1200 with a TK homomixer.
While stirring at 0 rpm, the above toner material solution was added and stirred for 10 minutes. The mixture was then transferred to a Kolben with stir bar and thermometer and slowly stirred for 3 hours to 98
The temperature was raised to 0 ° C. to remove the solvent, followed by filtration, washing and drying, and then air classification was performed to obtain toner particles having a weight average particle diameter of 6 μm. Then, 100 parts of the toner particles were mixed with 0.
5 parts and 0.5 parts of hydrophobized titanium oxide were mixed with a Henschel mixer to obtain a toner (1) of the present invention. The obtained GPC chromatogram is shown in FIG. 4, and the evaluation results are shown in Table 2. Three or more wax dispersions were present in each particle, and 90% of the dispersion diameter was 0.1 to 2 μm. It was not 3 μm or more. The dispersion direction was as shown in FIG.

Example 2 ( Synthesis of Toner Binder ) In the same manner as in Example 1, 2 mol of bisphenol A ethylene oxide adduct 314 was added.
Part, 314 parts of bisphenol A propylene oxide 2 mole adduct, 274 parts of isophthalic acid and 20 parts of trimellitic anhydride were polycondensed, and then 154 parts of isophorone diisocyanate were reacted to obtain a prepolymer (2). Then, 213 parts of the prepolymer (2), 9.5 parts of isophoronediamine and 0.5 part of dibutylamine were reacted in the same manner as in Example 1 to obtain a urea-modified polyester (2) having a weight average molecular weight of 79000. 200 parts of urea-modified polyester (2) and unmodified polyester (a)
800 parts of ethyl acetate / MEK (1/1) mixed solvent 20
It was dissolved in 100 parts and mixed to obtain an ethyl acetate / MEK solution of the toner binder (2). Partially dried under reduced pressure to isolate the toner binder (2). Tg is 65 ° C, acid value is 10
Met. ( Preparation of Toner) The toner (2) of the present invention was prepared in the same manner as in Example 1 except that the melting temperature and the dispersion temperature were changed to 50 ° C.
Got The evaluation results are shown in Table 2. There were three or more wax dispersions in each particle, and the dispersion diameter was 0.1 to 2 μm, 90% of which was 3 μm or more. The dispersion direction was as shown in FIG.

Example 3 (Preparation of Toner Binder ) 30 parts of urea-modified polyester (1) and unmodified polyester (a)
970 parts are dissolved and mixed in 2000 parts of ethyl acetate solvent,
An ethyl acetate solution of toner binder (3) was obtained. Partially dried under reduced pressure to isolate the toner binder (3). ( Production of Toner) A toner (3) having a weight average particle diameter of 6 μm was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (3). The number of particles having a wax dispersion diameter of 0.1 to 2 μm was randomly counted on three screens on a TEM screen photograph, and the result was 85% by number on average. It was not 3 μm or more. Other evaluation results are shown in Table 2.

<Example 4> (Preparation of Toner Binder ) 450 parts of urea-modified polyester (1) and 450 parts of unmodified polyester (a) were dissolved and mixed in 1900 parts of ethyl acetate to prepare a toner binder (4). An ethyl acetate solution of
Partially dried under reduced pressure to isolate the toner binder (4). ( Production of Toner) A toner (4) having a weight average particle diameter of 6.2 μm was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (4). Further, the wax particles having the maximum major axis of the wax of 3 μm or more in the maximum length were confirmed on the TEM cross-sectional photograph in the same manner as in Example 3, and the result was 2%. Furthermore, it was observed that the dispersed state of the wax was dispersed inward. The evaluation results are shown in Table 2.

<Example 5> ( Synthesis of toner binder ) 815 parts of bisphenol A ethylene oxide 2 mol adduct, terephthalic acid 215
Under normal pressure, polycondensed at 200 ° C. for 6 hours, and then 30-
Reacted under a reduced pressure of 50 mmHg for 5 hours to give a peak molecular weight of 4
000 unmodified polyesters (b) were obtained.
100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (b) were added to 2000 parts of ethyl acetate.
And then mixed to obtain ethyl acetate as a toner binder (5). Partially dried under reduced pressure to isolate the toner binder (5). The acid value was 0.5. ( Preparation of Toner) A toner (5) having a weight average particle diameter of 8.2 μm was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (5). The evaluation results are shown in Table 2. Three or more wax dispersions were present in each particle, and 90% of the dispersion diameter was 0.1 to 2 μm. The dispersion direction was as shown in FIG.

Example 6 ( Synthesis of Toner Binder ) 824 parts of 2 mol adduct of bisphenol A ethylene oxide, 276 terephthalic acid
Parts are polycondensed at 210 ° C. for 10 hours under normal pressure, and then 5 to
Reacted under a reduced pressure of 20 mmHg for 5 hours to give a peak molecular weight of 5
000 unmodified polyesters (c) were obtained.
100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (c) were added to 2000 parts of ethyl acetate.
Parts and dissolved to obtain ethyl acetate as a toner binder (6). Partially dried under reduced pressure to isolate the toner binder (6). ( Preparation of Toner) A toner (6) having a weight average particle diameter of 5 μm was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (6). The evaluation results are shown in Table 2. Three or more wax dispersions were present in each particle, and 90% of the dispersion diameter was 0.1 to 2 μm. The dispersion direction was as shown in FIG.

Example 7 ( Synthesis of Toner Binder ) 724 parts of 2 mol adduct of bisphenol A ethylene oxide, 276 terephthalic acid
Parts under normal pressure at 230 ° C. for 8 hours polycondensation, then 10
After reacting under reduced pressure of 15 mmHg for 5 hours, the mixture was cooled to 160 ° C., 32 parts of trimellitic anhydride was added thereto and reacted for 2 hours to obtain an unmodified polyester (d) having a peak molecular weight of 5000. 100 parts of urea-modified polyester (1) and unmodified polyester (d)
900 parts of ethyl acetate / MEK (1/1) mixed solvent 20
It was dissolved in 100 parts and mixed to obtain an ethyl acetate / MEK solution of the toner binder (7). Partially dried under reduced pressure to isolate the toner binder (7). The acid value was 25. ( Preparation of Toner) A toner (7) having a weight average particle diameter of 7.2 μm was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (7). The evaluation results are shown in Table 2.

Example 8 ( Synthesis of Toner Binder ) 608 parts of bisphenol A ethylene oxide 2 mol adduct, terephthalic acid 215
Under normal pressure, polycondensed at 200 ° C. for 6 hours, then 10
After reacting for 5 hours under a reduced pressure of 15 mmHg, the mixture was cooled to 160 ° C., 48 parts of trimellitic anhydride was added and reacted for 2 hours to obtain an unmodified polyester (e) having a peak molecular weight of 15,000. 100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (e) were dissolved and mixed in 2000 parts of ethyl acetate to obtain an ethyl acetate solution of toner binder (8).
Partially dried under reduced pressure to isolate the toner binder (8).
The acid value was 35. ( Production of Toner) A toner (8) having a weight average particle diameter of 7.2 μm was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (8). The evaluation results are shown in Table 2.

<Example 9> ( Synthesis of toner binder ) 624 parts of bisphenol A ethylene oxide 2 mol adduct, terephthalic acid 215
Parts under normal pressure at 200 ° C for 2 hours for polycondensation, then 10
Reacted under a reduced pressure of 15 mmHg for 5 hours to give a peak molecular weight of 1
000 unmodified polyesters (f) were obtained.
100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (f) were added to 2000 parts of ethyl acetate.
Parts and dissolved to obtain an ethyl acetate solution of the toner binder (9). Partially dried under reduced pressure to isolate the toner binder (9). Except for changing the (creation Toner) Toner Binder (1) to the toner binder (9) in the same manner as in Example 1, a weight average particle diameter to obtain toner (9) of 8.1Myuemu. The evaluation results are shown in Table 2.

<Example 10> ( Synthesis of toner binder ) 624 parts of bisphenol A ethylene oxide 2 mol adduct, terephthalic acid 215
Parts were subjected to polycondensation under normal pressure at 200 ° C. for 12 hours, then 10
The reaction was performed at a reduced pressure of -15 mmHg for 5 hours to obtain an unmodified polyester (i) having a peak molecular weight of 30,000. 100 parts of urea-modified polyester (1) and 900 parts of unmodified polyester (i) were mixed with 20 parts of ethyl acetate.
It was dissolved in 100 parts and mixed to obtain an ethyl acetate solution of the toner binder (10). Partially dried under reduced pressure to isolate the toner binder (10). ( Production of Toner) A toner (10) having a weight average particle diameter of 5.2 μm was obtained in the same manner as in Example 1 except that the toner binder (1) was changed to the toner binder (10). The evaluation results are shown in Table 2.

[0116] <Example 11> except that no addition of (Creating toner) pentaerythritoltetrabehenate in the same manner as in Example 1, a weight average particle diameter to obtain toner (11) of 6.8 [mu] m. The evaluation results are shown in Table 2.

<Example 12> ( Production example of prepolymer ) 800 parts of bisphenol A ethylene oxide 2 mol adduct and 200 parts of isophthalic acid were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube.
Parts, 15 parts of terephthalic acid, and 2 parts of dibutyltin oxide were added, and the mixture was reacted at 200 ° C. for 6 hours under normal pressure, further reacted for 5 hours while dehydrating under reduced pressure of 10-15 mmHg, and then cooled to 160 ° C., To this, 30 parts of phthalic anhydride was added and reacted for 2 hours. Then, it was cooled to 80 ° C. and isophorone diisocyanate 17 was added in ethyl acetate.
The reaction was carried out with 0 parts for 2 hours to obtain an isocyanate group-containing prepolymer (1) having a weight average molecular weight of 12,000.

( Production Example of Ketimine Compound ) 30 parts of isophoronediamine and 70 parts of methyl ethyl ketone were charged in a reaction vessel equipped with a stir bar and a thermometer and reacted at 50 ° C. for 5 hours to obtain a ketimine compound (1).

( Production Example of Toner ) 15.4 parts of the above prepolymer (1) and 60 parts of polyester (a) were placed in a beaker.
Parts and 78.6 parts of ethyl acetate were added and dissolved by stirring. Then, 20 parts of pentaerythritol tetrabehenate,
Add 4 parts of copper phthalocyanine blue pigment and add T at 60 ° C.
The mixture was stirred at 12000 rpm with a K type homomixer to be uniformly dissolved and dispersed. Finally, ketimine compound (1) 2.
7 parts was added and dissolved. This is designated as toner material solution (1). In a beaker, 706 parts of ion-exchanged water, 265 parts of 10% suspension of hydroxyapatite (Superpatite 10 manufactured by Nippon Kagaku Kogyo Co., Ltd.) and 0.2 part of sodium dodecylbenzenesulfonate were uniformly dissolved. Then 60 ° C
The temperature was raised to 1, and the above toner material solution (1) was charged and stirred for 10 minutes while stirring at 12000 rpm with a TK homomixer. Then, the mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, heated to 98 ° C., and allowed to react for 2 hours while removing the solvent, filtered, washed and dried, and then classified by wind. As a result, uneven toner particles having a weight average particle diameter of 7 μm were obtained. Next, 0.5 part of hydrophobic silica and 0.5 part of hydrophobized titanium oxide were mixed with 100 parts of toner particles by a Henschel mixer to obtain a 7.5 μm toner (12) of the present invention. The evaluation results are shown in Table 2.

Example 13 A toner (13) is obtained under the same conditions as in Example 12, except that an ester wax (molecular weight 1500, MP85 ° C., needle penetration 2 mm / 50 ° C., acid value 1.5) is used. It was The evaluation results are shown in Table 2.

<Example 14> ( Preparation example of prepolymer ) 955 parts of bisphenol A ethylene oxide 2 mol adduct and 240 parts of isophthalic acid were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube.
Parts, 15 parts of terephthalic acid, and 2 parts of dibutyltin oxide were added, reacted at 200 ° C. for 6 hours under normal pressure, further reacted for 5 hours while dehydrating under reduced pressure of 50 to 100 mmHg, and then cooled to 160 ° C. To this, 32 parts of phthalic anhydride was added and reacted for 2 hours. Then cool to 80 ° C. and add isophorone diisocyanate 1 in ethyl acetate.
By reacting with 70 parts for 2 hours, an isocyanate group-containing prepolymer (2) having a weight average molecular weight of 12,000 was obtained.

( Production Example of Ketimine Compound ) 30 parts of isophoronediamine and 70 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stir bar and a thermometer and reacted at 50 ° C. for 5 hours to obtain a ketimine compound (1).

( Production Example of Toner ) 15.4 parts of the prepolymer (1) and 50 parts of the polyester (a) were placed in a beaker.
Parts and 95.2 parts of ethyl acetate were added and dissolved by stirring. Next, carnauba wax (molecular weight 1800, acid value 2.
5, 20 parts of needle penetration of 1.5 mm / 50 ° C. and 3 parts of copper phthalocyanine blue pigment were added, and the mixture was stirred at 85 ° C. with a TK homomixer at 12000 rpm to uniformly dissolve and disperse. Finally, 2.7 parts of the ketimine compound (1) was added and dissolved. This is a toner material solution (2). 865 parts of deionized water and 10% hydroxyapatite suspension in a beaker (Super Chemical 10 manufactured by Nippon Kagaku Kogyo Co., Ltd.)
245 parts, sodium dodecylbenzene sulfonate 0.
4 parts were added and uniformly dissolved. Then, the temperature is raised to 60 ° C. and T
While stirring at 12000 rpm with a K-type homomixer,
The toner material solution (2) was added and stirred for 10 minutes.
Then, this mixed solution was transferred to a Kolben equipped with a stir bar and a thermometer, heated to 60 ° C. in 2 hours, and the solvent was removed over 2 hours while allowing the urea reaction to be carried out, followed by filtration, washing and drying, Air classification was performed to obtain toner particles having a weight average particle size of 7 μm. Then, 100 parts of the toner particles were mixed with 0.
3 parts and 0.3 part of hydrophobized titanium oxide were mixed in a Henschel mixer to obtain a toner (14) of the invention. The evaluation results are shown in Table 2.

Comparative Example 1 ( Synthesis of Toner Binder ) 395 parts of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid 1
66 parts was polycondensed using 2 parts of dibutyltin oxide as a catalyst to obtain an unmodified polyester (x) having a weight average molecular weight of 8000. The Tg of the unmodified polyester (x) was 57 ° C. ( Preparation of Toner ) 100 parts of the above-mentioned unmodified polyester (x) and 180 parts of ethyl acetate solution were placed in a beaker.
Part, copper phthalocyanine blue pigment 4 parts, rice wax (MP: 82 ° C, needle penetration degree 50 ° C: 9) 5 parts, and put
The mixture was stirred at 0 ° C. with a TK homomixer at 10,000 rpm to uniformly dissolve and disperse it. Next, the toner was formed in the same manner as in Example 1, but in the solvent removal step, the solvent was removed by stirring for 8 hours. A spherical spherical comparative toner (1) having a weight average particle diameter of 6 μm was obtained. Main peak molecular weight M
p is 5000, and the content of Mw = 30,000 or more is 0.3.
%, Mw / Mn was 2. The evaluation results are shown in Table 2.

Comparative Example 2 ( Synthesis of Toner Binder ) In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 343 parts of a 2 mol adduct of bisphenol A ethylene oxide and 166 isophthalic acid were added.
And 2 parts of dibutyltin oxide are added, and 2 at normal pressure
After reacting at 30 ° C. for 8 hours, further reacting under reduced pressure of 10 to 15 mmHg for 5 hours, cooling to 80 ° C., adding 14 parts of toluene diisocyanate in toluene and performing reaction at 110 ° C. for 5 hours, and then removing solvent. , Weight average molecular weight 9
8000 urethane-modified polyester was obtained. 363 parts of a 2 mol adduct of bisphenol A ethylene oxide and 166 parts of isophthalic acid were polycondensed in the same manner as in Example 1 to obtain an unmodified polyester (y) having a peak molecular weight of 3,800, a hydroxyl value of 25 and an acid value of 7. 350 parts of the urethane-modified polyester and 650 parts of unmodified polyester (y) are dissolved in toluene, mixed, and then desolvated,
Comparative toner binder (2) was obtained. The Tg of the comparative toner binder (2) was 58 ° C.

(Preparation of Toner ) 100 parts of comparative toner binder (2), 4 parts of copper phthalocyanine blue pigment, candelilla wax (mp 69 ° C., needle penetration degree 5.8, MW)
900 parts, acid value 16) 10 parts were made into toner by the following method. First, after preliminarily mixing with a Henschel mixer, they were kneaded with a continuous kneader. Next, after finely pulverizing with a jet pulverizer, classify with an air stream classifier to obtain a weight average particle size of 6 μm.
Toner particles were obtained. Then, 100 parts of the toner particles were mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobized titanium oxide by a Henschel mixer to obtain a comparative toner (2). Main peak molecular weight Mp is 3800, Mw = 300
The content of 00 or more was 15%, and Mw / Mn was 6.
The evaluation results are shown in Table 2.

<Evaluation Method><PowderFluidity> Bulk density was measured using a powder tester manufactured by Hosokawa Micron. A toner having a better fluidity has a higher bulk density. The following four grades were evaluated. ×: less than 0.25 Δ: 0.25 to 0.30 ○: 0.30 to 0.35 ◎: 0.35 or more

<Heat-resistant storability> After the toner was stored at 50 ° C. for 8 hours, it was sieved through a 42-mesh sieve for 2 minutes, and the heat-resisting storability was determined by the residual rate on the wire mesh. A toner having a better heat resistant storage stability has a smaller residual rate. The following four grades were evaluated. ×: 30% or more △: 20 to 30% ○: 10 to 20% ◎: less than 10%

<Fixing lower limit temperature> Ricoh type 6200 paper was added to a copying machine MF-200 made by Ricoh Co., Ltd. which uses a Teflon (registered trademark) roller as a fixing roller. It was set and a copy test was conducted. The fixing roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad was 70% or more was defined as the lower limit fixing temperature.

<Hot Offset Occurrence Temperature (HOT)> The fixing was evaluated in the same manner as the above fixing lower limit temperature, and the presence or absence of hot offset on the fixed image was visually evaluated. The fixing roll temperature at which hot offset occurred was defined as the hot offset occurrence temperature.

<Gloss development temperature (GLOSS)> The fixing was evaluated using a fixing device of a commercial color copying machine (PRETER550; manufactured by Ricoh). The fixing roll temperature at which the 60 ° gloss of the fixed image was 10% or more was defined as the gloss development temperature.

<Evaluation Results> As a belt fixing device, FIG.
The toner of Examples 1 to 14 of the present invention and Comparative Toners 1 and 2 were evaluated using an experimental machine having the configuration of FIG.
Comparative toner 1 and comparative toner 2 were evaluated using an experimental machine equipped with the fixing device of FIG. 3 as a roller fixing device.

The experimental conditions when using the belt fixing device are as follows. 1 and 2, a fixing roller 2, a heating roller 1, an endless fixing belt 3 stretched around the heating roller 1 and the fixing roller 2, and the fixing belt 3 as shown in the conceptual diagram of the fixing device. A pressure roller 4 provided to face the fixing roller 2 via a fixing roller 2; and a fixing belt heating heater 5 provided inside the heating roller 1.
By using a belt fixing device for fixing a toner image on a transfer paper as a material to be fixed, which is conveyed between the pressure roller 4 and the fixing belt 3, the pressure roller 4 passes through the fixing belt 3. The fixing pressure of the portion 8 where the first fixing process is performed on the material to be fixed formed by contacting the fixing belt 3 without pressing the fixing roller 2 is set low enough to prevent wrinkling of the material to be fixed. Then, the pressure roller 4 presses the fixing roller 2 through the fixing belt 3 to form the fixing pressure of the portion 9 for performing the second fixing step on the material to be fixed to obtain a desired fixing property. The fixing was performed by setting the fixing pressure.

In the first fixing step, the toner is assumed to be attached by heat conduction, and the fixing belt 3 is not attached to the pressure roller 4 in order to prevent wrinkles of the transfer paper due to the small fixing pressure. It is preferable that it is lightly adhered.

The fixing pressure of 1 Kg / cm ² means that the tension of the fixing belt 3 is 9 kg and the width of the fixing belt 3 is 31 kg, for example.
0 cm, when the contact width of the fixing belt 3 is 3 cm,
9 kg / 310 cm × 0.3 cm≈1 Kg / cm ² . Further, 0.5 kg / cm ² means, for example, 4.5 kg /
It is 310 cm × 0.3 cm≈0.5 Kg / cm ² .
Further, the wrinkle rank means that the degree of wrinkling that occurs on the paper (transfer paper as the material to be fixed) passing through the fixing device is ranked, and rank 3 or higher means that the user does not complain. Rank 5 means that there are no wrinkles, rank 4 means that there are some wrinkles, and rank 3 means that there are wrinkles but no user complaints. Rank 2 has wrinkles that are user complaints, and rank 1 has significant wrinkles. In this evaluation, all of Examples 1 to 14 were performed at a fixing pressure of 1 kg / cm ² . As a result, all the wrinkles were rank 4 or higher.

[0136]

[Table 1]

[0137]

[Table 2]

[0138]

The effects of the present invention are shown below in correspondence with the respective aspects of the present invention described above. (1) According to the first aspect, it is possible to obtain stable fixability with a quick start-up in a high-speed apparatus or a color image forming apparatus. (2) According to the second aspect, it is possible to form an image satisfying the fixability and the hot offset resistance in a high-speed device. (3) In the toner fixing method according to the first and second aspects, the fixing pressure in the first fixing step is set to 1 kg / cm ² or less and the fixing pressure in the second fixing step is set to be equal to or higher than the wrinkle on the material to be fixed Also, the transportability is good, and the low temperature fixing performance of the toner is good. (4) In the toner fixing method according to the first and second aspects, by using a heating roller having a low heat capacity, the rise time can be shortened, and energy saving can be achieved while maintaining the low temperature fixing property. (5) When a wax having a melting point of 60 to 120 ° C. is contained in the toner as a release agent in an amount of 1 to 20%, oilless fixing in a belt fixing device becomes possible. (6) By using a wax having a weight average molecular weight of 400 to 5,000 and an acid value of 1 to 30 as the wax in the fifth aspect, a toner having a wide oilless releasing width can be obtained. (7) Releasing property and glossiness of the toner can be imparted by evenly dispersing the release agent dispersed in the toner in the toner particles and at least three releasing agents are present in the toner particles. it can. (8) The dispersion diameter of the release agent in the toner is 0.1 μm to 2 μm.
When 70% by number or more of the toner particles are present, a highly transparent color toner can be obtained. (9) The release agent in the toner is dispersed like a needle in the toner particles, and the major axis of the release agent is 3 at maximum with respect to the total number of the release agent particles.
When the release agent particles having a size of μm or more do not exceed 5%, a toner having satisfactory fixing performance and glossiness can be obtained. (10) In the aspect 9, the release agent is dispersed with respect to the toner particle surface such that the major axis of the release agent does not exist horizontally along the particle surface but toward the inside or the surface is not exposed. As a result, a toner that secures fluidity and charge stability can be obtained. (11) By using a vegetable wax having a molecular weight of 400 to 2500 and an acid value of 1 to 30 as a release agent dispersed in the toner, a toner having good fixing performance can be obtained. (12) As the release agent dispersed in the toner, 50
By using an ester wax having a degree of needle penetration at 3 ° C. of 3 or less, a dry toner having good fixing performance can be obtained. (13) A toner composition containing at least a modified polyester resin, a colorant, and a releasing agent, or not containing a releasing agent is dissolved / dispersed in an organic solvent, and the composition is granulated in an aqueous medium, and granulated. By carrying out a polyaddition reaction below to produce a toner, a toner satisfying the fixing performance, the gloss performance of the color toner, and the transparency can be obtained. (14) A toner composition containing a prepolymer is dissolved / dispersed in an organic solvent, granulated in an aqueous medium while forming a polyester having a urea bond, and a polyaddition reaction is performed under the granulation to produce a toner. By doing so, it is possible to obtain a toner satisfying the fixing performance, the gloss performance of the color toner, and the transparency. (15) The toner contains the modified polyester resin (i),
Containing an unmodified polyester resin (ii),
By setting the weight ratio of (i) and (ii) to 5/95 to 80/20, a toner satisfying the fixing performance and the charging performance can be obtained. (16) As a binder component in the toner, a component having a molecular weight of 1000 or less in the molecular weight distribution of THF-soluble components is 5
By using a binder whose content is less than 100%, a dry toner having satisfactory heat resistance can be obtained. (17) Glass transition point of polyester resin is 55 to 75
By setting the temperature to ℃, the fixing property of the toner is improved. (18) By using a binder having a THF insoluble content of 1 to 15% as a binder component in the toner, a toner having good releasability can be obtained. (19) As a binder component in the toner, the peak of the molecular weight is 1000 to 3 in the molecular weight distribution of the THF-soluble component.
By using a binder having a content of 0000 and 30,000 or more of 1% or more and a weight average particle diameter of 3 to 10 μm, the releasability of the toner is improved. (20) As a binder component in the toner, the number average molecular weight is 2000 to 15 in the molecular weight distribution of the THF-soluble component.
And the weight average molecular weight / number average molecular weight is 10.
By using a binder of 0 or less, the glossiness of the toner is improved.

[Brief description of drawings]

FIG. 1 is a conceptual diagram of a belt fixing device used in a toner fixing method of the present invention.

2 is a partially enlarged view of FIG.

FIG. 3 is a conceptual diagram of a heat roller fixing device.

FIG. 4 is a GPC chromatogram of the toner of Example 1.

FIG. 5 is a cross-sectional observation view of toner particles of Example 1.

[Explanation of symbols]

1 heating roller 2 fixing roller 3 fixing belt 4 pressure roller 5 heater 6 Entrance guide plate 7 Thermistor 8 First fixing process 9 Second fixing process 10 Pressure spring 11 Tension spring 12 Auxiliary roller 13 Transfer paper 13a Unfixed toner

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/08 384 (72) Inventor Masahiro Watanabe 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72) Inventor Hiroshi Yamada 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Tsuneshin Sugiyama 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Hiroshi Yamashita 1-3-6 Nakamagome, Tokyo, Ota-ku, Tokyo (72) Inventor Kazuto Watanabe 1-3-3 Nakamagome, Tokyo, Ota-ku, Tokyo (72) Inventor, Tomita Masami 1-3-6 Nakamagome, Ota-ku, Tokyo F-term in Ricoh Co., Ltd. (reference) 2H005 AA01 AA06 AA15 AB03 AB06 CA08 CA14 EA03 EA05 EA06 EA07 EA10 2H033 AA02 AA09 AA 10 AA15 BA09 BA10 BA11 BA25 BA27 BA31 BA32 BA58 BB18 BB21 BB28 BB33 BB34

Claims (20)

[Claims] 1. A fixing roller, a heating roller, an endless fixing belt stretched around the heating roller and the fixing roller, and a pressure roller provided to face the fixing roller via the fixing belt. And a belt fixing device provided with a heating heater for fixing provided inside one or both of the pressure roller and the heating roller, the pressure roller is provided with the fixing belt through the fixing belt. A toner fixing method for fixing a toner image on a fixing material conveyed between the pressure roller and the fixing belt by contacting the fixing belt without pressing the fixing roller, wherein the toner has a circularity A toner fixing method characterized in that the toner has a spherical shape of 0.96 or more and that the resin in the toner contains a modified polyester resin. 2. The material to be fixed at a contact portion between the pressure roller and the fixing belt, which is in contact with the fixing belt without the pressure roller pressing the fixing roller via the fixing belt. The first fixing step in which the fixing is performed at a fixing pressure set low enough not to cause wrinkling of the material to be fixed, and the pressing roller contacting the fixing roller by pressing the fixing roller via the fixing belt. 2. The toner fixing method according to claim 1, further comprising a second fixing step of fixing the material to be fixed at a contact portion between the pressure roller and the fixing belt. 3. The fixing pressure in the first fixing step is 1
and kg / cm ² or less, the toner fixing method according to claim 2, characterized in that the on the fixing pressure of the portion of the fixing pressure of the portion the second fixing process performing a first fixing step. 4. The toner fixing method according to claim 1, wherein the heating roller has a low heat capacity. 5. The toner has a melting point of 60 as a release agent.
The toner fixing method according to any one of claims 1 to 4, further comprising: 1 to 20% by weight of wax having a temperature of 120 ° C. 6. The wax has a weight average molecular weight of 400.
6. The toner fixing method according to claim 5, wherein the toner has an acid value of 5,000 and an acid value of 1 to 30 mgKOH / g. 7. The release agent dispersed in the toner is evenly dispersed in the toner particles, and at least three release agent particles are present in at least the toner particles. 7. The toner fixing method according to any one of 6 above. 8. The dispersion diameter of the wax contained in the toner is 0.1 μm to 2 μm with respect to the wax present in the toner.
8. The toner fixing method according to claim 1, wherein the wax particles of m account for 70% by number or more based on the total number of wax particles. 9. A release agent dispersed in the toner is acicularly dispersed in the toner particles, and the number of release agent particles having a maximum major axis length of 3 μm or more is increased. The toner fixing method according to any one of claims 1 to 8, wherein the amount is not more than 5% with respect to the total number of molding agent particles. 10. The release agent dispersed in the toner in the form of needles does not have the major axis of the release agent in the horizontal direction along the surface of the toner particles rather than in the horizontal direction. 10. The toner fixing method according to claim 9, wherein the toner is dispersed so as not to be exposed on the surface. 11. The release agent dispersed in the toner is a vegetable wax and has a molecular weight of 400 to 250.
The toner fixing method according to claim 1, wherein the toner has an acid value of 0 and an acid value of 1 to 30 mgKOH / g. 12. The toner fixing according to claim 1, wherein the releasing agent dispersed in the toner is an ester wax having a needle penetration degree of 3 or less at 50 ° C. Method. 13. A toner composition in which the toner contains at least a modified polyester resin, a colorant and a release agent, or does not contain a release agent, is dissolved / dispersed in an organic solvent,
The toner fixing method according to any one of claims 1 to 12, which is a toner produced by granulating the composition in an aqueous medium. 14. A toner composition in which the toner contains at least a polyester prepolymer, a colorant and a releasing agent or does not contain a releasing agent is dissolved / dispersed in an organic solvent, and the composition is urea-bonded. 13. The toner according to claim 1, wherein the toner is produced by performing granulation in an aqueous medium while producing a polyester having a, and performing a polyaddition reaction under the granulation. Toner fixing method. 15. The toner contains the unmodified polyester resin (ii) together with the modified polyester resin (i), and the weight ratio of (i) to (ii) is 5/95 to.
It is 80/20, It is characterized by the above-mentioned.
The toner fixing method described. 16. The toner according to claim 1, wherein the THF-soluble component of the binder component contained in the toner has a molecular weight distribution of a molecular weight of 1000 or less and a component of 5% or less. Fixing method. 17. The toner fixing method according to claim 1, wherein at least the polyester resin contained in the toner has a glass transition point of 55 to 70 ° C. 18. The toner fixing method according to claim 1, wherein the binder component contained in the toner has a THF insoluble content of 1 to 15%. 19. The binder component contained in the toner has a molecular weight peak in the molecular weight distribution of the THF-soluble component of 1,000 to 30,000, 30,000 or more components of 1% or more, and a weight average particle diameter of 3 to 3. The toner fixing method according to claim 1, wherein the toner fixing method is 10 μm. 20. The number average molecular weight is 2 in the molecular weight distribution of the THF-soluble component of the binder component contained in the toner.
5,000 to 15,000 and weight average molecular weight / number average molecular weight of 10.0 or less.
20. The toner fixing method as described in 19 above.