JPH04211271A - Toner for static electric charge development and heating fixation - Google Patents

Abstract

PURPOSE:To provide the static electric charge development action toner which possesses the superior fixation performance and development performance at low temperature, at low cost. CONSTITUTION:The THF-insoluble portion of the binder resin is less than 10wt.% in the binder resin standard, and the wt. average molecular wt. number average molecular wt. in the GPC of the THF.soluble portion of the binder resin is 18 or less, and one molecular wt. peak value MA exists in the region of molecular wt. of 3,000-20,000, and one molecular wt. peak value MB exists in the region of molecular wt. of 380,000-1,000,000, and the min. value Md of molecular wt. exists between the molecular wt. of 20,000-380,000 and MB/MA is 30-150, and when the area of the molecular wt. distribution curve from the molecular wt. of 400 to Md is set SA, and the area of the molecular wt. distribution curve from the molecular wt. Md to the molecular wt. of 5,000,000 is set SB, and the area surrounded by the molecular wt. distribution curve and the straight line connecting the top point of the molecular wt. peak value MA and the top point of the molecular wt. peak value MB is set Sd, SA:SB:Sd becomes 1:0.3-0.8:0.35-0.8.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is applicable to electrophotography, electrostatic recording,
The present invention relates to a toner for developing an electrostatic image used in an image forming method such as electrostatic printing, and a heat fixing method for the toner.

0002

[Prior Art] Conventionally, as an electrophotographic method, US Pat.
A large number of methods are known, as described in Japanese Patent Publication No. 297,691, Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. 43-24748, etc. Generally, a photoconductive material is used to form an electrical latent image on a photoreceptor, the latent image is then developed with toner, and the toner image is optionally transferred to a transfer material such as paper. , heat, pressure, heating and pressurization, or solvent vapor to obtain a copy. Toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above-described steps are repeated.

[0003] In recent years, such copying devices have begun to be used not only as office copy machines for copying original documents, but also as printers for computer output or as personal copies for individuals. .

[0004] Therefore, miniaturization, weight reduction, higher speed, and higher reliability are being strictly pursued. Additionally, copying machines are becoming constructed of simpler elements in various respects. As a result, the performance required of toner has become more advanced, and unless the performance of toner can be improved, it is no longer possible to create an excellent copying machine.

For example, various methods and apparatus have been developed for the process of fixing toner images onto sheets such as paper. The most common method at present is the compression heating method using a heated roller.

[0006] In the pressure heating method using a heated roller, fixing is carried out by passing the toner image surface of the sheet to be fixed under pressure while contacting the surface of a heated roller whose surface is made of a material that has releasability for the toner. It is something. In this method, the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, so the thermal efficiency when fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. It is very effective in high-speed electrophotographic copying machines. However, in the above method, since the heated roller surface and the toner image contact each other under pressure in a molten state, a part of the toner image adheres to and transfers to the fixing roller surface, and this is transferred again to the next fixing sheet and is offset. This may cause a phenomenon and stain the sheet to be fixed. One of the essential conditions for the heat roller fixing method is to prevent toner from adhering to the surface of the heat fixing roller.

Conventionally, in order to prevent toner from adhering to the surface of the fixing roller, the roller surface is made of a material such as silicone rubber or fluorine-based resin that has excellent releasability to toner, and the surface is further coated with anti-offset and other materials. In order to prevent fatigue on the roller surface, the roller surface is coated with a thin film of a liquid having good mold releasability, such as silicone oil. However, although this method is extremely effective in preventing toner offset, it requires a device for supplying an offset prevention liquid, which poses a problem in that the fixing device becomes complicated.

[0008] This is the opposite direction to miniaturization and weight reduction.
Silicone oil may evaporate due to heat and contaminate the interior of the aircraft. Therefore, we decided to supply offset prevention liquid from the toner during heating without using a silicone oil supply device.
A method of adding a mold release agent such as low molecular weight polypropylene has been proposed. If a large amount of such a release agent is added to obtain a sufficient effect, it may cause filming on the photoreceptor or contaminate the surface of toner carriers such as carriers and sleeves.
The toner image deteriorates and becomes a practical problem. A small amount of release agent is added to the toner without degrading the toner image, a small amount of release oil is supplied, and a device is used to clean the offset toner using a member such as a winding web. things are being done.

However, in view of recent demands for smaller size, lighter weight, and higher reliability, it is necessary and desirable to eliminate these auxiliary devices. Therefore, it will not be possible to address this issue unless further improvements are made in toner fixability and offset resistance. That is difficult to achieve without further improvements in toner binder resins.

As a technique for improving the binder resin of a toner, for example, Japanese Patent Publication No. 51-23354 proposes a toner using a crosslinked polymer as a binder resin. If this method is followed, it will be effective in improving offset resistance and clinging resistance, but on the other hand, if the degree of crosslinking is increased, the fixing point will rise, and the fixing temperature will be sufficiently low, resulting in good offset resistance and clinging resistance. It is difficult to obtain one with sufficient fixing characteristics. Generally, in order to improve fixing properties, it is necessary to reduce the molecular weight of the binder resin to lower its softening point, which is contradictory to measures to improve offset resistance. In order to achieve a low softening point, the glass transition point of the resin inevitably decreases, and an undesirable phenomenon such as blocking of the toner during storage also occurs.

On the other hand, Japanese Patent Application Laid-Open No. 56-158340
A toner comprising a low molecular weight polymer and a high molecular weight polymer is proposed in the publication. Although this binder resin has improved fixing properties, it is still insufficient in terms of anti-offset properties, and it is difficult to achieve high levels of anti-offset properties and fixing properties.

JP-A-58-203453 proposes a toner comprising a low temperature softening resin and a high temperature softening resin. Although this binder resin has improved offset resistance, it is still insufficient in fixing properties, and it is difficult to achieve high levels of offset resistance and fixing properties.

[0013] Japanese Patent Publication No. 60-20411 proposes a method for manufacturing a resin composition comprising a low polymerization degree polymer and a high polymerization degree polymer, and the resin obtained by this manufacturing method is used for toner. When used as a binder resin, although there is a tendency for the pulverization property to be improved, both the fixing property and the anti-offset property are still insufficient, and there is much room for improvement.

Furthermore, regarding toners containing a blend of a low molecular weight polymer and a crosslinked polymer, for example, JP-A-58-86
No. 558 proposes a toner containing a low molecular weight polymer and an infusible high molecular weight polymer as main resin components. If the method is followed, fixing properties and crushability tend to be improved, but the weight average molecular weight/number average molecular weight (Mw/Mn) of the low molecular weight polymer is as small as 3.5 or less, and the insoluble and infusible Since the content of the high molecular weight polymer is as large as 40 to 90 wt%, it is difficult to satisfy high performance in both offset resistance and crushability. In reality, it is extremely difficult to produce toner that fully satisfies fixing properties (especially high-speed fixing), offset resistance, and pulverization properties unless the fixing device is equipped with an offset prevention liquid supply device.

Furthermore, when the amount of insoluble and infusible high molecular weight polymer increases, the melt viscosity becomes extremely high during heat kneading during toner production, so it is necessary to heat knead at a much higher temperature than usual or heat knead with a high shear. As a result, the former has the problem of deterioration of toner properties due to thermal decomposition of other additives, and the latter has the problem that the molecules of the binder resin are excessively cut, making it difficult to achieve the original anti-offset performance.

JP-A-60-166958 proposes a toner comprising a resin composition obtained by polymerization in the presence of low molecular weight polyα-methylstyrene having a number average molecular weight (Mn) of 500 to 1,500. has been done.

In particular, the publication states that the number average molecular weight (Mn) is preferably in the range of 9,000 to 30,000;
If Mn is increased in order to further improve offset resistance, fixing properties and pulverization properties during toner production become practical problems, and therefore it is difficult to satisfy offset resistance and pulverization properties with high performance. In this way, a toner with poor pulverizability during toner production is undesirable because not only does the production efficiency during toner production decrease, but also rough toner tends to be mixed into the toner, which may result in a scattered image.

[0018] JP-A-56-16144 describes a binder resin component having at least one maximum value in each region of molecular weight 103 to 8 x 104 and molecular weight 105 to 2 x 106 in the molecular weight distribution by GPC. Although toners have been proposed, further improvements in fixing properties and anti-offset properties are desired.

[0019] Japanese Unexamined Patent Publication No. 63-223662 has TH
The F-insoluble content is 10 to 60% by weight based on the binder resin, and the molecular weight distribution of the THF-soluble content by GPC is as follows:
Weight average molecular weight/number average molecular weight (Mw/Mn) is 5 or more, has a peak in the molecular weight range of 2 x 103 to 1 x 104, and has a peak or shoulder in the molecular weight range of 1.5 x 104 to 1 x 105. A toner has been proposed in which the binder resin contains 10 to 50% by weight of a component having a molecular weight of 1×10 4 or less. In this case, the pulverization properties, fixing properties, filming and fusing to the photoreceptor, image properties, and offset resistance (especially offset resistance on the high temperature side) are excellent, but the offset resistance and fixing properties of the toner are also excellent. There is a need for improvement. In particular, it is difficult for this resin to meet severe conditions in which both fixing properties at low temperatures and anti-offset properties at high temperatures are required.

[0020] As described above, it is extremely difficult to achieve both high performance related to fixing and crushability. In particular, pulverization during toner production is an important factor as the particle size of toner is becoming smaller in response to the demands for higher quality, higher resolution, and fine line reproducibility of copied images, and the pulverization process Since grinding requires a very large amount of energy, improving crushability is also important from the perspective of energy conservation.

[0021] The toner fusion phenomenon on the inner wall of the pulverizing device also tends to occur with toner having good fixing performance, thereby degrading the pulverizing efficiency. In the copying process, there is a step of cleaning the toner remaining on the photoreceptor after transfer. Nowadays, cleaning using a blade (blade cleaning) has become common in view of the miniaturization, weight reduction, and reliability of devices. With the increase in the lifespan of photoreceptors, the miniaturization of photoreceptor drums, and the increase in speed of systems, toners are required to have greater resistance to fusion and filming to the photoreceptor. In particular, amorphous silicon photoreceptors that have recently been put into practical use are extremely durable, and organic photoconductive photoreceptors (OPC)
) are also extending their lifespans, and as a result, the various performances required of toners are becoming more sophisticated.

[0022] Miniaturization requires that each element be skillfully accommodated in a narrow space. As a result, there is less space for air to flow, and the heat sources of the fixing device and exposure system are very close to the toner hopper and cleaner, so the toner is exposed to a high-temperature atmosphere. Therefore, it has become impossible to put toners into practical use unless they have better anti-blocking properties.

[0023] Therefore, the various performances required of toners, such as fixing properties and anti-blocking properties, are often contradictory in most cases, and it is increasingly desirable to satisfy both of them with high performance. It is being researched, but there is still not enough material available.

As mentioned above, the method for fixing a toner image on a recording material is to use a heated roller maintained at a predetermined temperature and a pressure roller having an elastic layer and pressed against the heated roller. A hot roll fixing method is often used in which a recording material holding an unfixed toner image is held and conveyed while being heated and pressurized.

However, hot roll fixing has the following points to be improved. (1) There is a wait time (time during which image forming operation is prohibited) until the heat roller reaches a predetermined temperature. (2) Maintain the heating roller at an appropriate temperature in order to prevent fixing failure due to fluctuations in the temperature of the heating roller due to passage of recording material or other external factors, and to prevent offset phenomenon to the heating roller. There is a need to. For this purpose, the heat capacity of the heating roller or heating body must be increased, which requires a large amount of electric power. (3) Due to the high temperature of the heating roller and the high ambient temperature, the recording material and the toner on the recording material are slowly cooled down after the recording material passes through the heating roller and is discharged. This may result in paper jams due to offset to the roller or the recording material wrapping around the roller.

[0026] It is possible to realize a fixing method that solves these problems and achieves excellent fixation of toner images on recording materials and prevention of offset, short wait time, and low power consumption. It's long awaited. Such a fixing method depends largely on the characteristics of the toner, and one of the important characteristics is the low-temperature fixability of the toner.

As mentioned above, as means for preventing the occurrence of the offset phenomenon, there are two methods: (1) performing fixing while applying a release agent such as silicone oil to the surface of the heating roller, and (2) using high molecular weight as a toner binder resin. There are two known methods: (1) using a polymer, and (2) incorporating a wax having releasable properties into the toner.

However, in method (2), the oil is heated and generates an odor, and furthermore, a device for supplying the oil is required, which complicates the structure of the fixing device.

In method (2), although the non-offset property of the toner is improved, it is difficult to achieve low-temperature fixing because the melting temperature of the toner increases.

Regarding method (1), for example, Japanese Patent Publication No. 52
-3304 Publication, Japanese Patent Publication No. 52-3305, Japanese Patent Publication No. 57-52574, Japanese Patent Publication No. 53-155655
Japanese Patent Publication No. 58-12580 describes a toner containing a styrene resin and a specific release agent.

However, although these toners are particularly improved in high-temperature side offset phenomenon, the reality is that low-temperature fixability is hardly improved. When these mold release agents are used for binders with low-temperature melting properties, it is difficult to exhibit mold release effects at low temperatures, and low-temperature offset phenomena tend to occur, leading to deterioration of fixing properties. This is the cause of not being able to achieve low-temperature fixing properties.

[0032] As a method for preventing the high-temperature side offset phenomenon, a method is known in which a high molecular weight polymer is contained in the binder resin. For example, JP-A-50-134652, JP-A-54-114245, JP-A-56-1614.
Publication No. 4, JP-A-56-158340, JP-A-5
8-203453.

However, although most of the toners used in these methods have been improved in high-temperature offset phenomenon, further improvement in low-temperature fixability is desired. On the other hand, although low-temperature fixability has been achieved to some extent in some of these methods, further improvements are desired in terms of developability and blocking resistance.

(Object of the Invention) An object of the present invention is to provide a toner that solves the above-mentioned problems.

An object of the present invention is to provide a toner that can be fixed at a low temperature and has excellent offset resistance over a wide temperature range from low to high temperatures.

An object of the present invention is to provide a toner that does not cause fusion or filming on a photoreceptor even after long-term use in a high-speed system.

An object of the present invention is to provide a toner which has excellent anti-blocking properties and can be used satisfactorily even in the high temperature atmosphere of a small machine.

[0038] An object of the present invention is to provide a toner that can be produced efficiently and continuously because the crushed material does not fuse to the inner wall of the device during the crushing step during toner production.

A further object of the present invention is to provide a fixing method that achieves excellent fixation of toner images on recording materials and prevention of offset, while shortening wait time and reducing power consumption. be.

The toner for developing electrostatic images of the present invention is a toner for developing electrostatic images having at least a binder resin and a colorant, in which the THF-insoluble content of the binder resin is less than 10% by weight based on the binder resin, and the binder resin The weight average molecular weight/number average molecular weight (Mw/Mn) in GPC (gel permeation chromatography) of the THF-soluble portion of is 18 or less, and the molecular weight is 3000-3000.
It has one molecular weight peak value MA in the range of 20,000, one molecular weight peak value MB in the range of molecular weight 380,000 to 1,000,000, and has a minimum molecular weight value Md in the molecular weight range of 20,000 to 380,000. , MB/MA is 30 to 150, SA is the area of the molecular weight distribution curve from molecular weight 400 to Md, SB is the area of the molecular weight distribution curve from molecular weight Md to 5 million, and the apex of the molecular weight peak value MA and the molecular weight When the area surrounded by the straight line connecting the apex of peak value MB and the molecular weight distribution curve is Sd, SA:SB:Sd is 1:0.3 to 0.8
:0.35 to 0.8 to achieve the above objective.

Furthermore, the toner for developing electrostatic images of the present invention comprises at least a binder resin, a low-melting point graft-modified polyolefin release agent, and a colorant, in which: A) the binder resin is styrene-acrylic; B)
The weight average molecular weight (Mw) of the low temperature softening resin is 5.0×1
03 to 3.0 x 104, weight average molecular weight/number average molecular weight (Mw/Mn) is 3.0 or less, outflow start point in a flow tester is 75 to 90°C, and softening point is 80 to 110°C. and the glass transition point (Tg) is 55~
70°C, the binder resin contains 50% by weight or more, and C) the high temperature softening resin has a weight average molecular weight (Mw) of 4.0.
×105 to 1.5×106, the weight average molecular weight/number average molecular weight (Mw/Mn) is 3.0 or less, the outflow start point in a flow tester is 110 to 160°C, and the softening point is 150 to The temperature is 230°C, and the glass transition point (T
g) is 55°C or higher, D) the ratio of low temperature softening resin and high temperature softening resin is 50:50 to 90:10 in terms of polymerization ratio, and E) the low temperature softening resin is solution polymerized and high temperature softening F) The low melting point graft modified polyolefin mold release agent has a number average molecular weight (Mn) of 1.0x. 103 or less, the weight average molecular weight (Mw) is 2.5 x 103 or less, and Mw/M
The above object is achieved by n being 3.0 or less, a melting point of 60 to 120° C., and 0.1 to 20% by weight of the toner.

The heat fixing method of the present invention is a method of heat fixing a toner image on a recording material, wherein the toner has at least a binder resin and a colorant, and the THF insoluble content of the binder resin is based on the binder resin. 10% by weight
GPC of the THF soluble content of the binder resin (
The weight average molecular weight/number average molecular weight (Mw/Mn) in gel permeation chromatography) is 18 or less, has one molecular weight peak value MA in the molecular weight range of 3,000 to 20,000, and has a molecular weight of 380,000 to 1,000,000. 1 in area
It has a molecular weight peak value MB of 1, has a molecular weight minimum value Md between 20,000 and 380,000, and has an MB/MA of 30 to 15.
0, the area of the molecular weight distribution curve from molecular weight 400 to Md is SA, the area of the molecular weight distribution curve from molecular weight Md to 5 million is SB, and the peak molecular weight value MA and the peak molecular weight peak value MB are connected. When the area surrounded by the straight line and the molecular weight distribution curve is Sd, SA:SB:
A toner for developing an electrostatic image having an Sd of 1:0.3 to 0.8:0.35 to 0.8. The above object is achieved by heating and fixing using a pressure member that is in pressure contact with the recording material and fixes the recording material to the heating member via the film.

The heat fixing method of the present invention is a method of heat fixing a toner image on a recording material, wherein the toner contains at least a binder resin, a low melting point graft-modified polyolefin release agent, and a colorant; ) The binder resin has two types of styrene-acrylic copolymer low-temperature softening resin and high-temperature softening resin, B)
The weight average molecular weight (Mw) of the low temperature softening resin is 5.0×1
03 to 3.0 x 104, weight average molecular weight/number average molecular weight (Mw/Mn) is 3.0 or less, outflow start point in a flow tester is 75 to 90°C, and softening point is 80 to 110°C. and the glass transition point (Tg) is 55~
70°C, the binder resin contains 50% by weight or more, and C) the high temperature softening resin has a weight average molecular weight (Mw) of 4.0.
×105 to 1.5×106, the weight average molecular weight/number average molecular weight (Mw/Mn) is 3.0 or less, the outflow start point in a flow tester is 110 to 160°C, and the softening point is 150 to The temperature is 230°C, and the glass transition point (T
g) is 55°C or higher, D) the ratio of low temperature softening resin and high temperature softening resin is 50:50 to 90:10 in terms of polymerization ratio, and E) the low temperature softening resin is solution polymerized and high temperature softening F) The low melting point graft modified polyolefin mold release agent has a number average molecular weight (Mn) of 1.0x. 103 or less, the weight average molecular weight (Mw) is 2.5 x 103 or less, and Mw/M
A toner for developing an electrostatic image, in which n is 3.0 or less, a melting point is 60 to 120°C, and is used in an amount of 0.1 to 20% by weight based on the toner, and the toner image is transferred to a recording material. The above object is achieved by heat fixing using a fixedly supported heating body and a pressure member that is in opposing pressure contact with the heating body and fixes the recording material to the heating body via a film.

(Structure of the Invention) In order to achieve the above-mentioned objects, the inventors of the present invention have made extensive studies and found that the TH of the binder resin contained in the toner is
It has been found that this can be achieved when the F-insoluble content is less than 10% by weight and the THF-soluble content has a specific molecular weight distribution in GPC.

Furthermore, it has been found that this effect becomes noticeable when a mold release agent having a specific molecular weight and molecular weight distribution and a specific melting point is contained.

It has also been found that this is particularly well achieved when the binder resin is prepared by mixing a low molecular weight polymer and a high molecular weight polymer in a solvent and then removing the solvent.

[0047] In addition to the conventional heat roll fixing machine, in order to heat and fix the toner image on the recording material,
A heat fixing method that heats and fixes a toner image onto a recording material using a fixedly supported heating body and a pressure member that is in pressure contact with the heating body and brings the recording material into close contact with the heating body through a film. It has been found that this toner is suitable for a fixing method.

T of the binder resin constituting the toner
The HF-insoluble content is less than 10% by weight, preferably 5% by weight or less, based on the binder resin. THF insoluble content is 1
If the content exceeds 0% by weight, offset resistance will improve, but fixing performance will tend to deteriorate, making it difficult to satisfy both requirements to a high degree.

[0049] The THF-insoluble content of the binder resin is determined by GPC.
According to the molecular weight measurement, the weight average molecular weight/number average molecular weight (Mw/Mn) is 18 or less, and the molecular weight is 3000 to 2.
It has one molecular weight peak value MA in the region of 10,000, and has a molecular weight of 3
It has one molecular weight peak value MB in the region of 80,000 to 1,000,000, has a minimum molecular weight value Md in the molecular weight range of 20,000 to 380,000, has an MB/MA of 30 to 150, and has a molecular weight of 400 to Md. Let the area of the molecular weight distribution curve be SA, and the molecular weight M
Let SB be the area of the molecular weight distribution curve from d to 5 million, and let S be the area surrounded by the straight line connecting the apex of molecular weight peak value MA and the apex of molecular weight peak value MB and the molecular weight distribution curve.
When d, SA:SB:Sd is 1:0.3 to 0.8
: The case where it is 0.35-0.8 is preferable.

[0050] If the above conditions are not satisfied, it is difficult to achieve the object of the present invention.

An explanatory diagram of the GPC chromatogram is shown in FIG.

Weight average molecular weight/number average molecular weight (Mw/M
n) is 18 or more, preferably 20 or more, more preferably 25-60. When Mw/Mn is less than 18, fixing properties tend to be improved, but offset resistance decreases.

[0053] Molecular weight range from 3000 to 20,000 and molecular weight 3
One molecular weight peak value (MA
and MB), and has a minimum value of molecular weight in a molecular weight range of 20,000 to 380,000, and MB/MA is 30 to 150, preferably a molecular weight in a range of 5,000 to 15,000 and a molecular weight of 450,000 to 90. This is a case where the molecular weight has one peak value in the range of 10,000 to 300,000, the minimum value in the range of 30,000 to 300,000, and the MB/MA is 40 to 100. If the molecular weight has a minimum value only in the region of 20,000 to 380,000, the fixing property may be good, but the offset resistance is clearly inferior.

When the molecular weight peak value MA is less than 3,000, blocking resistance becomes poor, and filming or fusion on the photoreceptor tends to occur, and when MA exceeds 20,000, the fixing property becomes poor. there is a possibility. Also,
If the molecular weight peak value MB is less than 380,000, the anti-offset property will be poor, and fused substances will likely be generated in the device during the crushing process, and if it exceeds 1,000,000, the fixing property may be poor. Grindability tends to be poor and productivity also tends to be poor.

The ratio MB/MA of the molecular weight peak value is 30
-150, preferably 30-120, more preferably 30-100.

When MB/MA is less than 30 or exceeds 150, it becomes difficult to achieve both high fixing properties and anti-offset properties.

[0057] When two or more molecular weight peak values exist in the molecular weight region of 3,000 to 20,000, the molecular weight corresponding to the position of the higher peak in the GPC chromatogram is defined as MA.

Similarly, if two or more molecular weight peak values exist in the molecular weight range of 380,000 to 1,000,000, GPC
The molecular weight corresponding to the position of the higher peak in the chromatogram is defined as MB.

When there are two or more molecular weight minimum values in the molecular weight region from 20,000 to 380,000, the molecular weight corresponding to the position of the lower molecular weight minimum value in the GPC chromatogram is determined as Md. shall be.

Area ratio of molecular weight distribution curve SA:SB:Sd
is 1:0.3-0.8:0.35-0.8, preferably SA:SB:Sd is 1:0.3-0.7:0.4
~0.7, more preferably SA:SB:Sd is 1
:0.3-0.6:0.5-0.7. SB is 0.
If it is less than 3, the anti-offset property will decrease, and if it exceeds 0.8, the fixing property will be poor and the crushability will also tend to be poor. If Sd is less than 0.35, the fixing performance and/or anti-offset property will be reduced, and if it exceeds 0.8, the anti-offset property will tend to be poor.

The release agent preferably used in the toner of the present invention has a number average molecular weight of 1000 or less, a weight average molecular weight of 2500 or less, and a ratio of weight average molecular weight/number average molecular weight (M
w/Mn) is 3 or less and the melting point is preferably 60 to 120°C. The mold release agent is preferably contained in an amount of 0.1 to 20% by weight based on the binder resin. More preferably, the number average molecular weight is 400 to 700, the weight average molecular weight is 500 to 1500, and Mw/Mn is 2.5.
or less, and the melting point is 60 to 100°C. The mold release agent is preferably contained in an amount of 1 to 10% by weight based on the binder resin.

If the release agent used in the toner of the present invention does not satisfy this condition, for example, if the melting point exceeds 120°C, the fixing properties will be adversely affected, and if the melting point is below 60°C, the offset resistance and toner has a negative effect on the blocking performance of Furthermore, if the content of the release agent exceeds 20% by weight, it will adversely affect blocking and fixing properties when the toner is left at high temperatures, and if it is less than 0.1% by weight, the toner offset prevention effect will be impaired. tends to be inadequate.

The binder resin used in the toner of the present invention is prepared by mixing a polymer A having a weight average molecular weight of 5,000 to 30,000 and a polymer B having a weight average molecular weight of 400,000 to 1,500,000 in a solvent, and then removing the solvent. Manufactured products are preferred. Preferably, a polymer A having a weight average molecular weight of 7,000 to 25,000 and a polymer B having a weight average molecular weight of 450,000 to 1 million
It is manufactured by mixing these in a solvent and then removing the solvent. Any solvent may be used as long as it dissolves the polymer A and the polymer B, such as toluene, xylene, 2-propanone, and the like.

In the production of the binder resin used in the toner of the present invention, polymer A is produced by a solution polymerization method or suspension polymerization method, and polymer B is produced by a suspension polymerization method or an emulsion polymerization method. is preferred. More preferably, polymer A is produced by a solution polymerization method, and polymer B is produced by a suspension polymerization method.

[0065] In order to produce a binder resin having uniform dispersion, it is preferable to mix Polymer A and Polymer B by mixing in a solvent and then removing the solvent. It is difficult to obtain a binder resin having a uniform dispersion state by a manufacturing method such as heating and melt-mixing using a kneader, and it is difficult to satisfy the fixing properties and anti-offset properties that are the objectives of the present invention. This is undesirable because the fused material is likely to form on the photoreceptor or the pulverized material is likely to be fused to the inner wall of the apparatus during the pulverization process.

If the weight average molecular weight of the polymer A is less than 5,000, the anti-offset properties will be lowered, and the crushability during toner production will also be lowered. If the weight average molecular weight exceeds 30,000, the fixing properties will deteriorate.

When the weight average molecular weight of the polymer B is less than 400,000, it tends to have poor crushability, and furthermore, there is a decrease in offset resistance, a decrease in blocking resistance, and the formation of fused substances on the photoreceptor. Undesirable.

[0068] If the weight average molecular weight exceeds 1,500,000, the pulverizability decreases.

Even if Polymer A and Polymer B are used alone as binder resins for toners, it is difficult to achieve the object of the present invention, and a manufacturing method in which Polymer A and Polymer B are melt-mixed is difficult. Rather, this is preferably achieved by a production method in which the mixture is mixed in a solvent and then the solvent is removed. Polymer B can suitably satisfy contradictory properties such as offset resistance, low-temperature fixing properties, and pulverizability during toner production by the toner production method of the present invention.

[0070] The THF-insoluble content in the present invention refers to the weight percentage of the polymer component (macromolecular polymer or crosslinked polymer) that has become insoluble in the THF solvent in the resin composition of the toner. The THF-insoluble content is measured as follows.

Weigh 0.5 to 1.0 g of toner sample (W1 g), and use a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Co., Ltd.).
) in a Soxhlet extractor and TH as a solvent.
After extraction for 6 hours using 100 to 200 ml of F and evaporating the soluble components extracted with THF,
Vacuum dry at 0°C for several hours, and weigh the amount of THF-soluble resin component (W2g). The weight of insoluble components other than resin components such as magnetic substances or pigments in the toner is assumed to be (W3 g). The THF-insoluble content is calculated from the following formula.

[0072]

[Outside 1]

In the present invention, the molecular weight of the peak and/or shoulder of a chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.

The column was stabilized in a heat chamber at 40°C, and THF was added to the column at this temperature as a solvent.
(Tetrahydrofuran) is flowed at a flow rate of 1 ml per minute, and 50 to 200 μl of a THF sample solution of the resin adjusted to a sample concentration of 0.05 to 0.6% by weight is injected for measurement. When measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithm of a calibration curve prepared using several types of monodispersed polystyrene standard samples and the count number. As a standard polystyrene sample for creating a calibration curve, for example, Pressure Chemical Co. or manufactured by Toyo Soda Kogyo Co., Ltd. with a molecular weight of 6 x 102, 2.
1×103, 4×103, 1.75×104, 5.1×
104, 1.1×105, 3.9×105, 8.6×1
It is appropriate to use at least 10 standard polystyrene samples of 0.05, 2 x 10 6 and 4.48 x 10 6 . An RI (refractive index) detector is used as a detector.

As a column, in order to accurately measure the molecular weight range of 10 3 to 2×10 6 , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, Water
μ-styragel 500,103,1 manufactured by S company
04,105 combination, Showa Denko's shodex
KF-80M, KF-802, 803, 804, 80
5 combination or TSKgel G manufactured by Toyo Soda
1000H, G2000H, G2500H, G3000
H, G4000H, G5000H, G6000H, G7
A combination of 000H and GMH is preferred.

In the Examples described below, the molecular weight distribution of the binder resin was measured under the following conditions.

GPC measurement conditions Equipment: LC-GPC 150C (manufactured by Waters)
Column: KF801 to KF807 (manufactured by Showdex) Column temperature: 28 to 30°C Solvent: Tetrahydrofuran (THF)

The molecular weight distribution of the sample was calculated from the relationship between the logarithm of a calibration curve prepared using a polystyrene standard sample measured under the above conditions and the count number measured under the above conditions.

SA, SB and Sd of the molecular weight distribution curve of the binder resin used in the toner of the present invention are GP
Cut out the chromatogram by C, calculate the weight ratio, and calculate the area ratio.

In the Examples described below, the molecular weight distribution of the mold release agent is measured by GPC (gel permeation chromatography) under the following conditions.

Equipment: LC-GPC 150C (Waters) Column: GMH6 (Toyo Soda) 60cm Column temperature: 140°C Solvent: o-dichlorobenzene

The molecular weight distribution of the sample is calculated from the relationship between the logarithm value and the count number of a calibration curve prepared using a polyethylene standard sample measured under the above conditions.

In the present invention, the melting point of the mold release agent is determined by DSC
Using a differential scanning calorimeter such as -7 (manufactured by Perkin Elmer), the endothermic peak of the sample is measured and taken as the highest melting peak value.

FIG. 5 shows an example of an endothermic peak in DSC.

In the toner of the present invention, the binder resin preferably contains two types of styrene-acrylic copolymer low-temperature softening resin and high-temperature softening resin and a low melting point graft-modified polyolefin mold release agent.

The low temperature softening resin has an Mw of 5.
0x103 to 3.0x104 (preferably 5.0x10
3 to 2.0×104), and the ratio of Mw to Mn (Mw/
Mn) is 3.0 or less, the outflow start temperature in a flow tester is 75 to 90°C, and the softening point is 80°C.
~110°C, the glass transition point (hereinafter referred to as "Tg") is 55 to 70°C (preferably 55 to 65°C), and the high temperature softening resin has an Mw of 4.0 x 105 to 1
．． 5×106, Mw/Mn is 3.0 or less,
The starting point of outflow is 110-160℃, and the softening point is 150℃.
~230°C, and Tg is 55°C or higher.

If the Mw of the low-temperature softening resin is less than 5.0×103, the blocking property of the toner will be significantly deteriorated, storage stability will be impaired, and the phenomenon of toner adhesion to the photoreceptor during development will occur. This tends to have a negative effect on the image. Mw
If it exceeds 3.0×10 4 , it is difficult to achieve low-temperature fixability, and the power consumption required for fixing the toner to the recording material also increases. Mw/Mn of low temperature softening resin is 3.
By setting it to 0 or less, low-temperature fixing properties are improved.

If the flow start temperature of the low-temperature softening resin in a flow tester is less than 75°C, the blocking property of the toner will be significantly deteriorated, while if it exceeds 90°C, the low-temperature fixing property will deteriorate when combined with the high-temperature softening resin. difficult to achieve.

When the softening point of the low-softening resin is less than 80°C, even when combined with a high-temperature softening resin, the toner tends to over-melt during the heat fixing process, causing gloss on the surface of the fixed image and loss of recording material such as transfer paper. Image smearing is likely to occur due to seepage of toner materials, set-off, and spread of molten toner. When the softening point exceeds 110° C., it is difficult to achieve low-temperature fixability, and the power consumption required for fixing the toner to the recording material also increases.

Good low-temperature fixability can be achieved by using the above-mentioned specific low-temperature softening resin.

On the other hand, as a result of intensive research by the present inventors regarding the offset phenomenon, in order to exhibit the low-temperature fixing properties of the low-temperature-softening resin component, the low-temperature-softening resin should be contained in an amount of 50% by weight or more (based on the total amount of the binder resin). (preferably 65% by weight or more, more preferably 70% by weight or more).

It is required that the high temperature softening resin component be added in an extremely small amount to prevent the offset phenomenon.

[0093] It has become clear that a high-temperature softening resin whose molecular weight and melt viscosity characteristics are extremely different from those of the low-temperature softening resin is required as a resin to be combined with the above-mentioned low-temperature softening resin for the purpose of preventing offset. .

In the present invention, the Mw of the high temperature softening resin is 4.
．． If it is less than 0x105, an offset phenomenon is likely to occur if the resin is combined with a low-temperature softening resin at a ratio that enables low-temperature fixing. On the other hand, when Mw exceeds 1.5×10 6 , low-temperature fixability tends to be impaired.

[0095] If the flow start temperature of the high temperature softening resin in a flow tester is less than 110°C or the softening point is less than 150°C, the resin and the low temperature softening resin are combined in a proportion that enables low temperature fixing. If so, an offset phenomenon is likely to occur. On the other hand, if the outflow start temperature exceeds 160°C or the softening point exceeds 230°C, low-temperature fixability tends to be impaired.

[0096] The Tg of the high temperature softening resin is preferably 55°C or higher, more preferably 60 to 70°C, even more preferably 65 to 70°C. This is because the molecular weight of the polymer component decreases due to the scission of polymer chains during melt-kneading during toner production, and therefore, if the Tg is less than 55°C, the toner will fuse to the photoreceptor during development. This is because it is easier to do.

[0097] The ratio of low temperature softening resin and high temperature softening resin in the binder resin is 50:50 to 90:10% by weight.
(preferably 65:35 to 90:10% by weight).

If the proportion of the low temperature softening resin is less than 50% by weight and the proportion of the high temperature softening resin exceeds 50% by weight, it is difficult to achieve low temperature fixability; When the proportion exceeds 90% by weight and is less than 10% by weight of the high temperature softening resin, an offset phenomenon tends to occur and the fixed image is likely to be adversely affected.

[0099] If the proportion of the high temperature softening resin exceeds 50% by weight, the crushability during toner production will be significantly reduced, and the toner production efficiency will likely be reduced.

Another characteristic of the toner of the present invention is that the low-temperature softening resin of the binder resin is obtained by a solution polymerization method, and the high-temperature softening resin is obtained by a suspension polymerization method; is carried out in a solvent in which both can be dissolved.

[0101] Suspension polymerization and emulsion polymerization can be used to obtain high-temperature softening resins with the above-mentioned molecular weight distribution and melt viscosity behavior. However, in emulsion polymerization, it is difficult to avoid residual emulsifiers and the toner This will reduce the characteristics.

It is preferable to synthesize the low-temperature softening resin by a solution polymerization method since it is solution-mixed with the high-temperature softening resin after polymerization.

The low-temperature softening resin and the high-temperature softening resin are mixed by a solution mixing method. Any other mixing will not result in uniform mixing and will have a negative effect on toner properties.

[0104] By carrying out the solution mixing method, it is possible to remove residual monomers through a solvent removal step.

[0105] The measurement of the melting characteristics of the binder resin is shown in Figure 3.
The elevated flow tester shown in (Shimadzu Flow Tester CF)
Sample 3, weighing 1.0 g, was first molded using a pressure molding machine (T-500 type) at a heating rate of 5.0°C/min.
A load of 20 kgf was applied to the plunger 1, and the amount of plunger descent of the flow tester was measured while extruding from the nozzle 4 having a diameter of 1 mm and a length of 1 mm.

[0106] At this time, when the height of the S-curve in the flow tester's plunger descent amount-temperature curve (see flow tester outflow curve in Figure 4) is h, the temperature at h/2 is the softening point, The temperature at which the sample starts flowing out is defined as the temperature at which the sample starts flowing out.

[0107] Tg is determined from the DSC curve during the second temperature rise, as shown in Figure 5, between the midline of the base line (1) before the endothermic peak and the base line (2) after the endothermic peak, and the rising curve. The temperature corresponds to the position of the intersection.

[0108] The method for measuring Tg in the present invention is DSC.
-7 (Perkin Elmer
ASTM (manufactured by ) at a heating rate of 10°C/min.
D3418-82).

The resin composition used as the binder resin of the toner of the present invention is obtained by polymerizing one or more monomers selected from styrenes, acrylic acids, methacrylic acids, and derivatives thereof, and has excellent developing characteristics, charging characteristics, etc. preferred. Examples of monomers that can be used include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, and the like. Acrylic acids, methacrylic acids and their derivatives include acrylics, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, n-tetradecyl acrylate,
Acrylic acid esters such as n-hexadecyl acrylate, lauryl acrylate, cyclohexyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl acrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, Amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxy methacrylate Examples include methacrylic acid esters such as propyl, dimethylaminoethyl methacrylate, glycidyl methacrylate, and stearyl methacrylate.

In addition to the above-mentioned monomers, small amounts of other monomers may be used as long as the objects of the present invention can be achieved. Examples include acrylonitrile, 2-vinylpyridine, 4-vinylpyridine, vinylcarbazole, vinyl methyl ether, butadiene, isoprene, maleic anhydride, maleic acid, maleic acid monoesters, maleic diesters, and vinyl acetate.

The crosslinking agent used in the toner of the present invention includes divinylbenzene, bis(
4-acryloxypolyethoxyphenyl)propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol acrylate, Neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol #200, #400, #600 diacrylate, dipropylene glycol diacrylate,
Examples include polypropylene glycol diacrylate, polyester diacrylate (MANDA Nippon Kayaku), and the above acrylates replaced with methacrylates.

As polyfunctional crosslinking agents, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis(4-methacryloxy, poly ethoxyphenyl)propane, sialyl phthalate, triallyl cyanurate,
Examples include triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diarylchlorendate, and the like.

[0113] These crosslinking agents are preferably not included in order to keep the THF-insoluble content to less than 10% by weight. When included, it is less than 1% by weight, preferably 0.5% by weight or less, more preferably 0.2% by weight based on the binder resin.
Contain less than % by weight.

The binder resin used in the toner of the present invention is synthesized from monomers in the absence or presence of a crosslinking agent and further using a polymerization initiator.

As the polymerization initiator, di-t-butyl peroxide, benzoyl peroxide, lauroyl peroxide, t-butyl peroxylaurate, 2,
2'-Azobisisobutyronitrile, 1,1-bis(t
-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,4-bis(t-butylperoxycarbonyl)cyclohexane, 2,2-bis(t-butylperoxycarbonyl)cyclohexane, 2,2-bis(t-butylperoxycarbonyl)cyclohexane, -butylperoxy)octane, n-butyl 4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, 1,3-bis(t-butylperoxy)- isopropyl)benzene, 2,5-dimethyl-2
,5-di(t-butylperoxy)hexane,2,5-
Dimethyl-2,5-di)t-butylperoxy)hexane-3,2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di-t-butylperoxyisophthalate, 2,2- Bis(4,4-di-t-butylperoxycyclohexyl)propane, di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate, di-t-butylperoxy, hexa Hydroterephthalate, di-t-butyl peroxyazelate, 2,5-dimethyl-2,5-di(t-
butylperoxy)-hexane, diethyl glycol-
Bis(t-butylperoxycarbonate), di-t-
Butylperoxytrimethyladipate, tris(t-
butylperoxy)triazine and vinyltruli(t-butylperoxy)silane.

The above-mentioned polymerization initiators may be used alone or in combination, taking into consideration the amount used, polymerization temperature and half-life.

[0117] The toner used in the present invention has a number average molecular weight (Mn) of 1.0 x 103 or less, a weight average molecular weight (Mw) of 2.5 x 103 or less, and a Mw/M
n is 3.0 or less, and the melting point (mp) is 60 to 120°C
It is preferable to use at least one type of mold release agent. In addition, in the present invention, 0.1
It is preferable to use a mold release agent in an amount of ˜20% by weight (preferably 1-10% by weight).

Examples of release agents preferably used in the toner of the present invention include paraffin wax, low molecular weight polyethylene wax, low molecular weight ethylene-propylene copolymer, low molecular weight polypropylene wax, and aromatic vinyl such as styrene and styrene derivatives. monomer,
Examples include polyolefin wax graft-modified with unsaturated fatty acids or unsaturated fatty acid esters. Among these, graft-modified polyolefin waxes are particularly preferred from the viewpoint of prolonging the life of the developer and machines such as copying machines that use the developer and being free from service and maintenance.

[0119] The graft-modified polyolefin has an Mn of 1
．． 0x103 or less, preferably 400 to 700,
Mw is 2.5 x 103 or less, preferably 700 to 150
0, and Mw/Mn is 3.0 or less, preferably 2.0
or less, and the melting point is 60 to 120°C, preferably 60 to 120°C.
Preferably, the temperature is 100°C.

[0120] As a result, the toner can be heated and fixed on the recording material without offset under low temperature fixing conditions, and therefore power consumption can be reduced.

[0121] As a result of intensive research by the present inventors, it was found that a mold release agent that exhibits good mold release properties at low temperatures is required for a low-temperature melting binder resin that enables low-temperature fixing. It has become clear that the temperature at which moldability is exhibited is correlated with the melting point of the release agent, and that the lower the melting point is, the more advantageous it is to low-temperature fixing. However, when a release agent with a low melting point is used, adverse effects such as deterioration of the blocking properties of the toner and filming of the toner on the carrier when used in a two-component developing method are likely to occur. Therefore, in the present invention, by making the molecular weight distribution of the mold release agent relatively sharp as described above, it is possible to improve the blocking properties, exhibit mold release properties at low temperatures, and have good properties that do not cause the offset phenomenon. It has gained.

However, although low-temperature fixing can be achieved to some extent by combining a low-melting point mold release agent and a binder resin as described above, release in a mixed resin of a low-temperature softening resin and a high-temperature softening resin is difficult. Dispersing molding agents is technically difficult. Insufficient dispersion will adversely affect the developability of the toner.

As a result of further intensive research, the present inventors solved the above-mentioned problems by graft-modifying the dispersion of a release agent in the binder resin with a low melting point polyolefin wax, and the development It has been found that the fixing properties are good and further low temperature fixing properties can be achieved.

The binder resin of the toner of the present invention is preferably obtained by mixing a low-temperature softening resin and a high-temperature softening resin, and it is preferable that both resins are made of the same component.

Examples of the low melting point graft-modified polyolefin mold release agent used in the present invention include aromatic vinyl monomers such as styrene and styrene derivatives, and polyolefin waxes graft-modified with unsaturated fatty acids or unsaturated fatty acid esters.

Examples of the polyolefin wax include polyethylene wax; α- such as propylene, 1-butene, 1-hexene, 1-decene, 4-methyl-1-pentene;
Homopolymers of olefins; copolymers of two or more types of α-olefins; copolymers of ethylene and α-olefins can be mentioned. Furthermore, oxides of polyolefins are also included.

[0127] The unsaturated fatty acids or unsaturated fatty acid esters used to synthesize the graft-modified polyolefin include methacrylic acid; methyl methacrylate;
Ethyl methacrylate, propyl methacrylate, n-
Butyl methacrylate, isobutyl methacrylate, n
-Octyl methacrylate, 2-ethylhexyl methacrylate, rariul methacrylate, staryl methacrylate, dodecyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2,2,2-trifluoro Methacrylates such as ethyl methacrylate, glycidyl methacrylate; acrylic acid; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, lauryl acrylate, stearyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, Phenyl acrylate, 2-chloroethyl acrylate, 2-hydroxyethyl acrylate, cyclohexyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dibutylaminoethyl acrylate, 2-ethoxy acrylate,
Acrylates such as 1,4-butanediol diacrylate; maleic acid, fumaric acid, itaconic acid, citraconic acid, monoethyl maleate, diethyl maleate, monopropyl maleate, dipropyl maleate, monobutyl maleate, dibutyl Malate, di-2-ethylhexyl maleate, monoethyl fumarate, diethyl fumarate, dibutyl fumarate, di-2-ethylhexyl fumarate, monoethyl itaconate, diethyl itaconate, monoethyl citraconate, diethyl citraconate Examples include unsaturated dibasic acid esters such as esters. One or more of these can be used.

[0128] As the aromatic vinyl monomer, styrene,
o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, p-ethylstyrene, p-n-butylstyrene,
Examples include p-tert-butylstyrene, p-n-dodecylstyrene, p-phenylstyrene, and p-chlorostyrene. One or more of these can be used.

[0129] As a method for graft modification, conventionally known methods can be used. For example, a graft-modified polyolefin can be produced by reacting the above-mentioned polyolefin with an aromatic vinyl monomer and an unsaturated fatty acid or an unsaturated fatty acid ester in a molten state or dissolved in a solvent and heated in the presence of a radical initiator in the atmosphere or under pressure. can get. Grafting with an aromatic vinyl monomer and an unsaturated fatty acid or an unsaturated fatty acid ester may be carried out simultaneously or individually.

[0130] Initiators used in the grafting reaction include:
Benzoyl peroxide, dichlorobenzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl perphenylacetate, cumin perpivalate, azobis-isobutyronitrile, dimethyl azoisobutyrate, dicumyl peroxide Oxide etc. can be mentioned.

[0131] The ratio of the grafting agent to the polyolefin is 0.1 to 10 parts by weight per 100 parts by weight of the polyolefin.
It is preferably 0 parts by weight, more preferably 1 to 50 parts by weight. If the amount is less than 0.1 part by weight, the grafting effect will hardly be exhibited, and if it exceeds 100 parts by weight, the polyolefin will lose its originally advantageous properties.

[0132] The weight ratio of aromatic vinyl monomer to unsaturated fatty acid or unsaturated fatty acid ester is 95:5 to 5.
:95 is preferable, more preferably 80:20-20
:80. When there is a large amount of unsaturated fatty acids or unsaturated fatty acid esters, the mold release effect of the polyolefin tends to decrease, and when there is a large amount of aromatic vinyl monomers,
The dispersibility of polyolefin in toner does not improve much.

The amount of the graft-modified polyolefin used in the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the binder resin.
It is 5 to 10 parts by weight. When the amount is less than 0.1 part by weight, it is difficult to exhibit a sufficient mold release effect, and when it is more than 20 parts by weight, the blocking properties of the toner tend to deteriorate.

The graft-modified polyolefin used in the present invention has a melt viscosity of 1 to 250 cp at 160°C.
It is preferably in the range of s. If the speed is less than 1 cps, toner blocking tends to occur;
If it exceeds s, it becomes difficult for the modified polyolefin to ooze out from the toner, making it difficult to exhibit the mold release effect. In the fixing method of the present invention, it is generally preferable to use a release component having a lower melt viscosity as the fixing temperature is lower.

[0135] The melt viscosity referred to in the present invention is a value measured by a B-type rotational viscometer.

The toner used in the present invention has a melting point of 120° C. in an amount that does not adversely affect the fixing properties of the toner.
The mold release agent may contain one or more types of release agents exceeding the above.

The toner of the present invention may contain a charge control agent. As the charge control agent, a conventionally known positive or negative charge control agent is used. Examples of the charge control agent include the following. (1) The following substances can be used to control the toner to be positively charged.

Nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 1627/1983), basic dyes (for example, C.I. Basic Yellow
2 (C.I, 41000), C.I. I. Basic
Yellow 3,C. I. BasicRed 1
(C.I.45160), C.I. I. Basic
Red 9 (C.I.42500), C.I. I. Bas
ic Violet 1 (C.I.42535),
C. I. Basic Violet 3 (C.
I. 42555), C. I. Basic Viole
t 10 (C.I.45170), C. I. Basi
c Violet14 (C.I.42510), C.I.
I. Basic Blue 1 (C.I.4202
5), C. I. Basic Blue3 (C.I.5
1005), C. I. Basic Blue 5 (
C. I. 42140), C. I. Basic Blue
e 7 (C.I.42595), C. I. Basic
Blue 9 (C.I.52015), C.I. I.
Basic Blue24 (C.I.52030),
C. I. Basic Blue25 (C.I.520
25), C. I. Basic Blue 26 (C
．． I. 44025), C. I. Basic Green
n 1 (C.I.42040), C. I. Basic
Green 4 (C.I.42000), lake pigments of these basic dyes (lake-forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten-molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), C. I. S
ovent Black 3 (C.I.261
50), Hansa Yellow G (C.I.11680), C
．． I. MordlantBlack 11,C. I.
Pigment Black 1, benzolmethyl-hexadecyl ammonium chloride, decyl-trimethylammonium chloride or dialkyltin compounds such as dibutyl and dioqual, metal salts of higher fatty acids, inorganic fine powders such as zinc oxide, EDTA, metal complexes of acetylacetone, and amino groups. Polyamine resins such as vinyl polymers containing amino groups and condensation polymers containing amino groups. In particular, from the viewpoint of dispersibility, nigrosine, metal salts of higher fatty acids, and vinyl polymers having amino groups are preferred. (2) The following substances are used to control the negative chargeability of toner.

[0139] Japanese Patent Publication No. 41-20153, No. 42-
No. 27596, No. 44-6397, No. 45-
Metal compounds of monoazo dyes described in JP-A No. 26478, nitrofumic acid and its salts described in JP-A-50-133338, C.I. I. 14645
dyes and pigments such as salicylic acid, naphthoic acid, and dicarboxylic acid described in Japanese Patent Publication No. 55-42752, Japanese Patent Publication No. 58-41508, Japanese Patent Publication No. 58-7384, and Japanese Patent Publication No. 59-7384; Zn, Al, Co
, Cr, Fe metal-containing compounds, sulfonated copper phthalocyanine pigments; nitrile groups, styrene oligomers with halogens introduced, chlorinated paraffins, etc. Particularly from the viewpoint of dispersibility, metal-containing compounds of monoazo dyes; metal-containing compounds of salicylic acid, alkylsalicylic acid, naphthoic acid, or dicarboxylic acid are preferred.

Good results can be obtained with the toner of the present invention even when additives are mixed therein as necessary. Examples of additives include lubricants such as Teflon, zinc stearate, and polyvinylidene fluoride (among which polyvinylidene fluoride is preferred); abrasives such as cerium oxide, silicon carbide, and strontium titanate (among which strontium titanate is preferred); Flowability agents such as colloidal silica and aluminum oxide (
Among them, hydrophobic colloidal silica is preferred); anti-caking agents; and conductivity imparting agents such as carbon black, zinc oxide, antimony oxide, and tin oxide. Further, a small amount of white fine particles and black fine particles having a polarity opposite to that of the toner can be used as a developing property improver.

Furthermore, when the toner of the present invention is used as a two-component developer, it is used in combination with a carrier powder. In this case, the mixing ratio of toner and carrier powder is preferably 0.1 to 50% by weight in terms of toner concentration, more preferably 0.5 to 10% by weight, even more preferably 3 to 5% by weight. It is.

[0142] Known carriers can be used in the present invention. For example, iron powder, ferrite powder,
Examples include magnetic powder such as nickel powder, glass beads, and those whose surfaces are treated with a fluorine-based resin or a silicon-based resin.

Furthermore, the toner of the present invention can further contain a magnetic material and be used as a magnetic toner. In this case, the magnetic material also serves as a coloring agent. The magnetic materials contained in the toner include iron oxides such as magnetite, hematite, and ferrite, or compounds of divalent metals and iron oxides; metals such as iron, cobalt, and nickel, or these metals and aluminum, cobalt, and copper. , alloys with metals such as lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

[0144] These ferromagnetic materials have an average particle size of 0.1 to 2
It is preferably μm, more preferably 0.1 to 0
．． 5 μm, and spherical ones are particularly preferred. The amount of the ferromagnetic material contained in the toner is preferably about 20 to 200 parts by weight per 100 parts by weight of the resin component, and particularly preferably 40 to 180 parts by weight per 100 parts by weight of the resin component. .

[0145] Furthermore, a coloring agent may be added to the toner of the present invention, if necessary.

Pigments or dyes are used as the coloring agent in the toner of the present invention. Examples of pigments include carbon black, aniline black, acetylene black, naphthol yellow, Hansa yellow, rhodamine lake, alizarin lake, red red, phthalocyanine blue, and indanthrene blue. The pigment is used in an amount necessary and sufficient to maintain the optical density of the colored image, and is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 2 to 10 parts by weight, per 100 parts by weight of the resin. good. Dyes include azo dyes, anthraquinone dyes,
Examples include xanthene dyes and methine dyes. It is preferable to use the dye in an amount of 0.1 to 20 parts by weight, more preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the resin.

[0147] To prepare the toner for electrostatic image developer according to the present invention, the resin composition according to the present invention, a mold release agent and a charge control agent, optionally a magnetic material and a pigment as a coloring agent or The dye and additives are thoroughly mixed using a ball mill or other mixer, and then melted, kneaded, and kneaded using a heat kneader such as a heated roll, kneader, or extruder to make the resins compatible with each other. Or disperse or dissolve the dye, cool and solidify, then crush and classify to obtain an average particle size of 3.
There is a method to obtain toner of ~20 μm.

Furthermore, the present invention provides a method for heating and fixing a toner image, which includes: a heating element fixedly supported on a recording material; The present invention also relates to a method of heat fixing using a pressure member that brings the recording material into close contact with the heating body through a film.

Although FIG. 1 shows a configuration diagram of the fixing device of the present invention, the fixing method of the present invention is not limited to this.

In the fixing device shown in FIG. 1, the heating body 11 has a smaller heat capacity than a conventional heating roll and has a linear heating section, and the maximum temperature of the heating section is 100 to 300°C.
It is preferable that

The film 15 located between the heating element 11 and the pressure member 18 is preferably a heat-resistant sheet having a thickness of 1 to 100 μm. These heat-resistant sheets include highly heat-resistant polyester, PET (polyethylene terephthalate), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), and PTF.
Polymer sheets such as E (polytetrafluoroethylene), polyimide, and polyamide, metal sheets such as aluminum, and laminate sheets composed of metal sheets and polymer sheets are used.

[0152] More preferably, the structure of the film is as follows:
These heat-resistant sheets have a release layer and/or a low resistance layer.

[0153] The low heat capacity linear heating element 11 fixedly supported by the device has a thickness of 1.0 mm, a width of 10 mm, and a longitudinal length of 240 m.
The resistive material 13 is coated on an alumina substrate 12 with a width of 1.0 mm, and electricity is applied from both ends in the longitudinal direction. The current is applied in a pulse-like waveform of DC 100V with a period of 20 msec, and pulses are given by changing the pulse width according to the desired temperature and energy release amount controlled by the temperature measuring element 14. The approximate pulse width is 0.5 msec to 5 msec. Heating body 1 whose energy and temperature can be controlled in this way
1, the fixing film 15 moves in the direction of the arrow in the figure. As an example of this fixing film, the thickness is 20 μm.
heat-resistant film (for example, polyimide, polyetherimide, PES, or PFA, at least on the side facing the image)
It is an endless film coated with a release layer of 10 μm in which a conductive material is added to a fluororesin such as TFE or PFA. It is generally preferred that the total thickness be less than 100μ, more preferably less than 40μ. The film is driven by the driving roller 16 and the driven roller 17 and tension to move the film in the direction of the arrow without wrinkles.

[0154] 18 is a pressure roller having a rubber elastic layer with good mold release properties such as silicone rubber, and has a total pressure of 4 to 20 kg.
Pressure is applied to the heating body 11 through the film, and the heating body 11 is rotated in pressure contact with the film. The unfixed toner 20 on the transfer material 19 is guided to the fixing section by the entrance guide 21 and is heated as described above to obtain a fixed image.

[0155] The case where the fixing film is an endless belt has been described above, but the fixing film may also be a film with ends using a sheet feeding shaft and a winding shaft.

The image forming apparatus is applicable to a fixing device of an apparatus that uses toner to form images, such as a copying machine, a printer, or a facsimile machine.

[0157] When the temperature detected by the temperature detection element 14 in the low heat capacity linear heating element 11 is T1, the surface temperature T2 of the film 15 facing the resistance material 13 is about 10 times higher than T1.
~30℃ lower. The film surface temperature T3 at the portion where the film 15 is peeled off from the toner fixing surface is approximately equal to the temperature T2.

[0158] Appropriate methods for supplying electricity to the heating body as this temperature control method include a pulse width modulation method, a frequency modulation method, an AC phase control method, and the like.

[0159]

EXAMPLES The present invention will be specifically explained below using synthesis examples and examples. The numbers in the synthesis examples and examples are parts by weight.

Synthesis Example 1 200 parts of cumene was placed in a reactor and the temperature was raised to reflux temperature. To this, 100 parts of styrene monomer and di-tert-
A compound of 6 parts of butyl peroxide was added dropwise at 135° C. over 4 hours. Furthermore, under reflux of cumene (146℃~15℃)
Solution polymerization was completed at 6° C.) and cumene was removed. The obtained polystyrene is soluble in THF, has a weight average molecular weight of 7800, and a peak molecular weight (MA) of 720.
0, and Tg was 67°C. This is referred to as polymer A-1 of the binder resin related to the toner of the present invention.

Synthesis Examples 2 to 5 Solution polymerization was carried out in the same manner as in Synthesis Example 1 using the monomer composition, polymerization initiator, and solvent shown in Table 1 to obtain binder resin polymer A-2 for the toner of the present invention. ~A-5 was obtained.

[0162]

[Table 1] Synthesis example 6

[0163]

[Table 2] 200 parts of degassed water in which 0.1 part of partially saponified polyvinyl alcohol was dissolved was added to a reactor, and the monomer composition shown in Table 2 was added to form a suspension dispersion. The suspension dispersion was heated to 80° C. under a nitrogen atmosphere. The temperature was maintained for 24 hours to complete the polymerization reaction. After cooling to room temperature, spherical polymer particles produced by the polymerization reaction were filtered out, thoroughly washed with water, dehydrated, and dried to obtain polymer B-1 of the binder resin for the toner of the present invention. The weight average molecular weight was 452,000, the peak molecular weight was 433,000, and the Tg was 57°C. Synthesis Examples 7 to 10 Synthesis Example 7 using the monomer composition and polymerization initiator shown in Table 3
Suspension polymerization was carried out in the same manner as above to obtain binder resin polymers B-2 to B-5 for the toner of the present invention.

[0164]

[Table 3] The above polymers A-1, A-2, A-3, A-4, A-5,
The weight average molecular weight (Mw), Mw/Mn, outflow start point, softening point, and Tg of B-1, B-2, B-3, B-4, and B-5 are shown in Table 4 below.

[0165]

[Table 4] Comparative synthesis example 1

[0166]

[Table 5] Comparative polymer A-6 was obtained in the same manner as in Synthesis Example 1 except that the monomer composition shown in Table 5 was used. Weight average molecular weight is 4
300, the peak molecular weight was 4200, and the Tg was 54°C.

Comparative synthesis example 2

[0168]

[Table 6] Comparative polymer B-6 was obtained in the same manner as Synthesis Example 6 except that the monomer composition shown in Table 6 was used. Weight average molecular weight is 2
17,000, the peak molecular weight is 198,000, and T
g was 59°C.

Next, an example of manufacturing the binder resin for the toner of the present invention will be described.

Production Example 1 68 parts of Polymer A-1 and 32 parts of Polymer B-4 were added to 200 parts of xylene with stirring. Next, it was heated to about 60°C to completely dissolve the added polymers A-1 and B-4. After continued stirring for about 2 hours, the xylene was removed. This is referred to as binder resin 1 for the toner of the present invention.

Production Examples 2 to 10 and Comparative Binder Resin Production Examples 1 to 3 Binder resins 2 to 10 for toners of the present invention and comparative binder resins were produced in the same manner as Production Example 1 except that the polymers shown in Table 7 were used. Binder resins 1 to 3 were obtained.

[0172]

[Table 7] Next, the composition and physical properties of the mold release agent used in the Examples and Comparative Examples are shown in Table 8 below.

[0173]

[Table 8] Example 1

[0174]

[Outside 2]

[0175] The above materials were premixed using a Henschel mixer, and then kneaded for 20 minutes using a two-roll mill heated to 150°C. After cooling the kneaded material and coarsely pulverizing it with a cutter mill,
Finely pulverized using a pulverizer using a jet stream, and further classified using a wind classifier to obtain a volume average particle size of 11.2μ.
A black fine powder (magnetic toner) of m was obtained.

0.4 parts of colloidal silica fine powder was dry mixed with 100 parts of the magnetic toner to obtain a toner having colloidal silica on the surface of the toner particles. This is referred to as toner 1 of the present invention.

The pulverizability of the toner can be expressed as the amount of toner that can be pulverized per unit time, and in the case of Toner 1, it was 16 Kg/hr at an air pressure of 5.6 Kg/cm2, which was very good. No fusion occurred inside the crusher.

[0178] Blocking property is determined by adding approximately 10 g of toner to 1
The sample was placed in a 00 cc plastic cup and left at 50°C for one day, and the change in aggregation degree was examined. The degree of aggregation was measured using a powder tester manufactured by Hosokawa Micron. Products left at room temperature and 50℃
The products left for one day showed almost the same values at 9% by weight and 12% by weight, and the difference (ΔG) was 3%, so it was confirmed that there was no substantial blocking.

Regarding fixing properties, offset properties, wrapping properties, image properties, and durability, Canon copier NP-66
The investigation was conducted using 50 modified machines.

A test was conducted by lowering the set temperature of the fixing device by 5°C.

In particular, the offset property was evaluated by removing the cleaning mechanism of the fixing roller and determining the number of copies it took before the image became smeared or the roller smeared, based on the number of copies that could be made.

[0182] Fixability is determined by fixing the fixed image on silbon paper (len paper).
s cleaning paper “duster”
[Product name]” (OZU paper Co., Ltd.
d. )) was rubbed back and forth 10 times under a load of about 100 g, and the peeling of the fixed image was expressed as a percentage decrease in reflection density (%). The fixed image for evaluation was viewed on the 200th sheet of 200 consecutive sheets.

[0183] The wrapping property was determined by printing three completely black images and checking the appearance of the marks left by the peeling tabs of the fixing roller on the images, and by how much the film relied on the tabs.

As a result, the fixing performance was very good with a decrease rate of 3%, the offset performance was good with no roller stains on the image even after printing 50,000 sheets, and the wrapping performance was also good with no traces caused by the claws on the image. Although it was slightly attached, it was very good.

[0185] In addition, a durability test was carried out on approximately 10,000 sheets using images with an image area ratio of approximately 5%, and the images were good, with slight adhesion to the photoreceptor and filming. There was no effect on the copied image.

The THF-insoluble content of Toner 1 was 4% by weight, the Mw/Mn of the THF-soluble content by GPC was 38.2, the molecular weight peak MA was 7700, and the molecular weight peak MB was 765,000. Yes, MB/MA is 99,
The area ratio of the molecular weight distribution curve SA:SB:Sd is 1:0.3
6:0.60.

Example 2

[0188]

[Outer 3]

[0189] The above materials were premixed using a Henschel mixer, and then kneaded for 20 minutes using a two-roll mill heated to 150°C. After cooling the kneaded material and coarsely pulverizing it with a cutter mill,
Finely pulverized using a pulverizer using a jet stream, and further classified using a wind classifier to obtain a volume average particle size of 8.7 μm.
A fine black powder (magnetic toner) was obtained.

0.4 parts of colloidal silica fine powder was dry mixed with 100 parts of the magnetic toner to obtain a toner having colloidal silica on the surface of the toner particles. This is referred to as toner 2 of the present invention.

[0191] The pulverization property of the toner is determined by the air pressure of 5.6 kg/
It was 5.8 Kg/hr in cm2, which was very good, and no fusion occurred inside the pulverizer.

[0192] Blocking property is determined by adding approximately 10 g of toner to 1
The sample was placed in a 00 cc plastic cup and left at 50°C for one day, and the change in aggregation degree was examined. The products left at room temperature and the products left at 50°C for one day showed almost the same values of 17% by weight and 21% by weight,
Since the difference (ΔG) was 4%, it was confirmed that there was no substantial blocking.

Regarding fixing properties, offset properties, wrapping properties, image properties, and durability, Canon copier NP-48
The investigation was conducted using a modified machine of No. 35 (fixing temperature set at 200° C.).

A test was conducted by lowering the set temperature of the fixing device by 10°C.

In particular, the offset property was evaluated by removing the cleaning mechanism of the fixing roller and determining the number of copies it took to stain the image or stain the roller, based on the number of copies that could be made.

As a result, the fixing performance was very good with a decrease rate of 6%, the offset performance was good with no roller stains on the image even after printing 1,000 sheets, and the winding performance was also good with no traces of nails on the image. Although it was slightly attached, it was very good.

[0197] Furthermore, a durability test was carried out on approximately 30,000 sheets using images with an image area ratio of approximately 5%, and the images were good, with no fusion or filming on the photoreceptor.

The THF-insoluble content of Toner 2 is 2% by weight, the Mw/Mn of the THF-soluble content by GPC is 24.7, the molecular weight peak MA is 14000, and the molecular weight peak MB is 680,000. MB/MA is 48.6, and the area ratio of the molecular weight distribution curve SA:SB:Sd is 1:0.
40:0.59.

Example 3 Using the toner 2 produced in Example 2, an unfixed image was obtained using a modified copying machine FC-5 manufactured by Canon Inc.

[0200] A fixing test for an unfixed image was carried out using an external fixing device shown in FIG. 1, which consists of a pressure member that is in pressure contact with a heating body and brings the recording material into close contact with the heating body through a film. . The material of the fixing film 5 is a release layer of 10 μm made of polyimide film with fluororesin and conductive material added.
A coated endless film 15 was used. As the pressure roller 18, silicone rubber is used, and the nip 3
．． 5 mm, a total pressure of 8 kg between the heating body 11 and the pressure roller 18, and a process speed of 50 mm/sec. The film is driven by a driving roller 16 and a driven roller 17.
The drive and tension caused it to move in the direction of the arrow without wrinkles. The heating element 11 is a linear heating element with a low heat capacity, and provides energy in a pulsed manner to regulate the temperature. The power consumption of the resistance material of the heating element 11 was 150W. Temperature control is FC-5
Tests were conducted at the same temperature as the fuser of the modified machine (fixing temperature set at 180°C) and at a temperature lowered by 15°C. As a result, the fixing performance was reduced by 2%, and even after running on 3,000 sheets, there was no staining on both the image and the fixing film, which was good. Furthermore, the wait time was 3 seconds or less, and the power consumption was significantly lower than that of the hot roller fixing method.

Example 4

[0202]

[Outside 4]

A toner was prepared from the above mixture according to the method of Example 2. 100 parts by weight of this toner and 0 colloidal silica
．． 4 parts by weight, and this is used as toner 3 of the present invention. Approximately 10% by weight of the toner was mixed with iron powder having a particle size of 200 mesh pass to 300 mesh pass to prepare a developer. Only toner was used as a replenisher.

[0204] The crushability of this toner is as follows:
The throughput was 15.2 kg/hr in terms of g/cm2, which was very good. There was no fusion inside the crusher. The blocking property was ΔG=5% and had no problem at all.

[0205] Further, image performance and fixing performance were evaluated using a modified copying machine FC-3 manufactured by Canon. As a result, the image was good and stable even after 1000 sheets of durability. Also, there was no filming or fusion on the drum.

[0206] Further, the set temperature of the fixing device was lowered by 20° C., and the cleaning mechanism of the fixing device was removed, and the above durability was carried out, but the fixing performance was good with a decrease rate of about 5%. Also,
The offset resistance and wrapping resistance were also good.

The THF-insoluble content of Toner 3 is 1.8% by weight, the Mw/Mn of the THF-soluble content by GPC is 29, the molecular weight peak MA is 18,000, and the molecular weight peak MB is 770,000. MB/MA is 43, and the area ratio of the molecular weight distribution curve SA:SB:Sd is 1:0.43
:0.38.

Examples 5 to 8 Toners 4 to 7 of the present invention were obtained in the same manner as in Example 1 except that the binder resin was changed to those shown in Table 9.

Examples 9 to 11 Toners 8 to 10 of the present invention were obtained in the same manner as in Example 2, except that the binder resin and release agent were changed to those shown in Table 9.

Comparative Example 1 Comparative Toner 1 was obtained in the same manner as in Example 2, except that Comparative Binder Resin 1 consisting of only 100 parts of Polymer A-2 was used as the binder resin.

[0211] In the case of this comparative toner 1, the air pressure was 5.
When pulverized at 6 kg/cm2, a large amount of fine toner particles were produced, the particle size distribution was broad, and the productivity was clearly inferior.

[0212] In the same manner as in Example 2, using a modified FC-5 machine, fixing properties, offset properties, wrapping properties, image quality, and durability were examined.

[0213] As a result, in terms of offset property, stains occurred on both the image and the roller after 20 sheets were printed. Regarding the wrapping property, there were clear marks left on the image by the claws, and there were cases where the paper was not ejected from the fixing machine.

[0214] The THF-insoluble content of comparative toner 1 was 0% by weight.
The Mw/Mn of the THF-soluble portion by GPC is 2.
1, and the molecular weight peak MA was 8,900.

Comparative Examples 2 and 3 Comparative toners 2 and 3 were obtained in the same manner as in Example 2, except that the binder resin and release agent were changed to those shown in Table 9. The results are shown in Table 10.

[0216]

[Table 9]

[0217]

[Table 10]

Preparation of Resin 11: 200 parts by weight of xylene was placed in a reactor and heated to reflux temperature. A mixture of 90 parts by weight of styrene monomer, 10 parts by weight of butyl acrylate monomer and 7 parts by weight of di-tert-butyl peroxide was mixed with this, and solution polymerization was completed in 6 hours under reflux of xylene.

[0219] The styrene-butyl acrylate copolymer obtained here (hereinafter referred to as "St-BA copolymer")
The physical properties of the resin were as shown in the low temperature softening resin shown in Resin 11 in Table 11.

On the other hand, 82 parts by weight of styrene monomer, 18 parts by weight of butyl acrylate monomer, 0.3 parts by weight of polyvinyl alcohol, 200 parts by weight of degassed water and 0.11 parts by weight of benzoyl peroxide were mixed, suspended and dispersed. Ta. The above suspension dispersion was heated and kept at a temperature of 78° C. for 24 hours under a nitrogen atmosphere to complete polymerization, and a high temperature softening resin shown in Resin 11 in Table 11 was obtained.

[0221] This dried product of the high temperature softening resin is added to the resin solution of the above-mentioned low temperature softening resin at the end of solution polymerization, completely dissolved in the solvent and mixed, and then the solvent is removed to obtain the resin 11. was manufactured.

Preparation of Resins 12-15 and Comparative Resins 4-6 Resins 12-15 and Comparative Resins 4-6 shown in Table 11 were synthesized and produced in accordance with Resin 11, respectively.

Example 12 Graft-modified polyethylene wax J (Mn is 5.3 x 102 and Mw is 8.0×
102, Mw/Mn is 1.5, and melting point is 93.
After mixing 4 parts by weight of 4 parts by weight (100°C), they were melt-kneaded using a twin-screw kneading extruder, cooled, pulverized using a pneumatic pulverizer, and classified using an air classifier to obtain a black material with a volume average particle diameter of approximately 8.5 μm. A powder (magnetic toner) was obtained. To 100 parts by weight of this magnetic toner, 0.6 parts by weight of hydrophobic colloidal silica powder was added and mixed to obtain toner A having hydrophobic colloidal silica powder on the surface of the toner particles.

[0224] This toner A was produced using a modified copying machine NP-1215 (manufactured by Canon Inc.) in which the fixing device was removed.
An unfixed image was obtained. As the recording material, commercially available copying machine paper Canon New Dry Paper 54 g/m2 paper (Canon Sales Co., Ltd.) was used.

[0225] In the fixing test of the unfixed image, a temperature-variable heat roller external fixing device was used, which used Teflon as the upper roller and silicone rubber as the lower roller, and the pressure between the upper and lower rollers was set at a linear pressure of 0.4 kg/cm with a nip of 4 mm. cm, 100°C to 230°C at a process speed of 45 mm/sec
The temperature was adjusted every 5°C within the temperature range of . The fixed image obtained here was coated with Silbon paper (with a load of 50 g/cm2).
lens cleaning paper
per [product name]” (OZUpaper Co., L
ed. )), the image density reduction rate before and after rubbing was 7%.
Fixing was started at the following temperature. The offset test was evaluated by observing the fixed image and the roller.

[0226] As a result, the fixing start temperature was as low as 120°C, and the non-offset region was 110 to 215°C, indicating that low-temperature fixing was achieved. Furthermore, the anti-blocking properties of the toner were also good. Blocking resistance of toner is 50
Samples left in a dryer for 3 days were evaluated. The results are shown in Table 12.

Examples 13 to 16 In the same manner as in Example 12, toners B to E were prepared using resins 12 to 15 shown in Table 11, and fixing properties were evaluated.

[0228] These are referred to as Examples 13 to 16, and the results are shown in Table 1.
Shown in 3.

Comparative Examples 4 to 6 In the same manner as in Example 12, toners F to H were prepared using comparative binder resins 4 to 6 shown in Table 11, and fixing properties were evaluated.

[0230] These were designated as Comparative Examples 4 to 6, and the results are shown in Table 13.

Comparative Example 7 Toner I was prepared in the same manner as in Example 13, except that 3 parts by weight of Wax 3 (polyethylene wax) having a melting point of 128° C. was used as a release agent, and the fixing properties were evaluated. Table 1 shows the results.
Shown in 3.

Comparative Example 8 Polyethylene wax (Mn4.5×10
Example 12 except that 3 parts by weight of wax 4 (graft-modified polyethylene wax) which had been subjected to the same graft modification treatment as in Example 1 was used in Example 1. Toner J was similarly prepared and evaluated for fixability.

[0233] As is clear from Table 13, Examples 12 to 16
Toners A to E have good low-temperature fixing properties, offset resistance,
While blocking resistance and developability are obtained, toner F of Comparative Example 4 has poor low-temperature fixing properties but poor offset resistance, and toner G of comparative example 5 has poor low-temperature fixing properties. is worsening.

Toner H of Comparative Example 6 did not achieve low-temperature fixability, and Toner I of Comparative Example 7 had problems with low-temperature fixability and developability.

[0235] Toner J of Comparative Example 8 achieved low-temperature fixability, but had poor blocking resistance.

[0236] This revealed that the electrostatic charge developing toner of the present invention has a structure that has excellent low-temperature fixing properties and anti-offset properties, and does not adversely affect anti-blocking properties and developability.

Example 17 Toner A was used as the toner in Example 12 to obtain an unfixed image.

[0238] For the fixing test of unfixed images, an external fixing device as shown in FIG. I used it. As the material of the fixing film 15,
An endless film was used, which was a polyimide film coated with a release layer of 10 μm containing a fluororesin and a conductive material. As the pressure roller 18, silicone rubber is used, the nip is 3.5 mm, and the process speed is 45 mm/se.
I went with c. The film was moved in the direction of the arrow without wrinkles due to the drive and tension of the drive roller 16 and the driven roller 17. The heating element 11 is a linear heating element with a low heat capacity, and provides energy in a pulsed manner to regulate the temperature. The temperature control temperature was 5℃ in the range of 100 to 230℃ as in Example 12.
I went there every now and then. As a result, the fixing start temperature was as low as 120°C, and the non-offset range was 105°C to 215°C, achieving low-temperature fixing. The prevention of wrapping around the fixing member was also good.

Table 12 shows the physical properties of Binder Resins 11 to 15 and Comparative Binder Resins 4 to 6.

[0240]

[Table 11]

[0241]

[Table 12]

[0242]

[Table 13]

[0243]

As described above, according to the present invention, since the toner has excellent fixability and developability at low temperatures, the cost of operating the copying machine is low and it is possible to provide good images.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram schematically showing a specific example of a fixing device used in the fixing method of the present invention.

FIG. 2 is an explanatory diagram of a molecular weight distribution curve determined by GPC.

FIG. 3 is a schematic diagram of an elevated flow tester.

FIG. 4 is a diagram showing a plunger fall amount-temperature curve.

FIG. 5 is a diagram showing a DSC curve for determining Tg.

[Explanation of symbols]

11 Heating body 12 Alumina substrate 13 Resistance material 14 Temperature measurement element 15 Film 16 Drive roller 17 Followed roller 18 Pressure member 19 Transfer material 20 Unfixed toner 21 Entrance guide

Claims (10)

[Claims] 1. A toner for developing electrostatic images having at least a binder resin and a colorant, in which the THF-insoluble content of the binder resin is less than 10% by weight based on the binder resin, and the THF-soluble content of the binder resin is The weight average molecular weight/number average molecular weight (Mw/Mn) in permeation chromatography) is 18 or less, has one molecular weight peak value MA in the molecular weight range of 3,000 to 20,000, and has a molecular weight in the range of 380,000 to 1,000,000. has one molecular weight peak value MB, has a molecular weight minimum value Md between 20,000 and 380,000, and has an MB/MA of 30 to 150.
, where SA is the area of the molecular weight distribution curve from molecular weight 400 to Md, SB is the area of the molecular weight distribution curve from molecular weight Md to 5 million, and a straight line connects the apex of molecular weight peak value MA and the molecular weight peak value MB. When the area surrounded by the molecular weight distribution curve is Sd, SA:SB:
A toner for developing an electrostatic image, characterized in that Sd is 1:0.3 to 0.8:0.35 to 0.8. [Claim 2] The number average molecular weight is 1000 or less,
A mold release agent having a weight average molecular weight of 2500 or less, a weight average molecular weight/number average molecular weight (Mw/Mn) of 3.0 or less, and a melting point of 60 to 120°C is used in a range of 0.1 to 120°C based on the binder resin. The toner for developing an electrostatic image according to claim 1, characterized in that the toner contains 20% by weight. 3. The toner for developing electrostatic images according to claim 2, wherein the mold release agent is a low melting point graft-modified polyolefin mold release agent. Claim 4: The binder resin has a weight average molecular weight of 50.
Polymer A with a weight average molecular weight of 000,000 to 30,000 and a weight average molecular weight of 400,000 to 150
4. The toner for developing an electrostatic image according to claim 1, wherein the toner is produced by mixing 1,000 yen with Polymer B in a solvent and then removing the solvent. 5. A toner for developing electrostatic images comprising at least a binder resin, a low-melting point graft-modified polyolefin release agent, and a colorant, wherein: A) the binder resin is a low-temperature softening resin of a styrene-acrylic copolymer and a high-temperature softening resin; It has two types of softening resin, B)
The weight average molecular weight (Mw) of the low temperature softening resin is 5.0×1
03 to 3.0 x 104, weight average molecular weight/number average molecular weight (Mw/Mn) is 3.0 or less, outflow start point in a flow tester is 75 to 90°C, and softening point is 80 to 110°C. and the glass transition point (Tg) is 55~
70°C, the binder resin contains 50% by weight or more, and C) the high temperature softening resin has a weight average molecular weight (Mw) of 4.0.
×105 to 1.5×106, the weight average molecular weight/number average molecular weight (Mw/Mn) is 3.0 or less, the outflow start point in a flow tester is 110 to 160°C, and the softening point is 150 to The temperature is 230°C, and the glass transition point (T
g) is 55°C or higher, D) the ratio of low temperature softening resin and high temperature softening resin is 50:50 to 90:10 in terms of polymerization ratio, and E) the low temperature softening resin is solution polymerized and high temperature softening F) The low melting point graft modified polyolefin mold release agent has a number average molecular weight (Mn) of 1.0x. 103 or less, the weight average molecular weight (Mw) is 2.5 x 103 or less, and Mw/M
A toner for developing an electrostatic image, wherein n is 3.0 or less, a melting point is 60 to 120°C, and the amount is 0.1 to 20% by weight based on the toner. [Claim 6] Weight average molecular weight (M
w) is 5.0 x 103 to 2.0 x 104, has a glass transition temperature (Tg) of 55 to 65°C, is contained in the binder resin at 65% by weight or more, and is a low temperature softening resin and a high temperature softening resin. The ratio by weight of the resin is 65:35 to 90:
10. The toner for developing an electrostatic image according to claim 5, wherein the toner has a particle size of 10. 7. The binder resin has a THF-insoluble content of less than 10% by weight based on the binder resin, and a weight average molecular weight/number average of the THF-soluble content of the binder resin measured by GPC (gel permeation chromatography). The molecular weight (Mw/Mn) is 18 or less, has one molecular weight peak value MA in the molecular weight range of 3,000 to 20,000, has one molecular weight peak value MB in the molecular weight range of 380,000 to 1,000,000, and has a molecular weight of It has a molecular weight minimum value Md between 20,000 and 380,000, MB/MA is 30 to 150, the area of the molecular weight distribution curve from molecular weight 400 to Md is defined as SA, and the molecular weight distribution ranges from molecular weight Md to 5 million. When the area of the curve is SB and the area surrounded by the straight line connecting the apex of molecular weight peak value MA and the apex of molecular weight peak value MB and the molecular weight distribution curve is Sd, SA:SB:Sd is 1:0.3 to 0. .8: The toner for developing electrostatic images according to claim 5, wherein the toner has a ratio of 0.35 to 0.8. 8. The toner for developing an electrostatic image is produced using a fixedly supported heating body and a pressure member that is in opposing pressure contact with the heating body and brings the recording material into close contact with the heating body through a film.
The toner for developing an electrostatic image according to any one of claims 1 to 7, which is used in a heat fixing method for heat fixing a visible image of the toner onto a recording material. 9. A method of heating and fixing a toner image on a recording material, wherein the toner comprises at least a binder resin and a colorant, and the THF-insoluble content of the binder resin is less than 10% by weight based on the binder resin. , the weight average molecular weight/number average molecular weight (Mw/Mn) of the THF soluble portion of the binder resin in GPC (gel permeation chromatography) is 18 or less, and the molecular weight is 300.
It has one molecular weight peak value MA in the range of 0 to 20,000, and one molecular weight peak value M in the range of molecular weight of 380,000 to 1,000,000.
B, and a minimum molecular weight Md between 20,000 and 380,000.
has a MB/MA of 30 to 150, and a molecular weight of 40
The area of the molecular weight distribution curve from 0 to Md is SA, and the area of the molecular weight distribution curve from molecular weight Md to 5 million is S.
B, and the peak of the molecular weight peak value MA and the molecular weight peak value M
When the area surrounded by the straight line connecting the vertices of B and the molecular weight distribution curve is Sd, SA:SB:Sd is 1:0.3-0
．． 8:0.35 to 0.8, and the toner image is applied to a recording material by pressing a fixedly supported heating element against the heating element and through a film. A heat fixing method comprising heating and fixing the recording material using a pressure member that fixes the recording material to the heating body. 10. A method of heating and fixing a toner image on a recording material, wherein the toner comprises at least a binder resin, a low melting point graft-modified polyolefin release agent, and a colorant, and A) the binder resin is styrene-based. It has two types of acrylic copolymer low temperature softening resin and high temperature softening resin, B)
The weight average molecular weight (Mw) of the low temperature softening resin is 5.0×1
03 to 3.0 x 104, weight average molecular weight/number average molecular weight Mw/Mn) is 3.0 or less, the outflow start point in a flow tester is 75 to 90°C, and the softening point is 80 to 110°C. and the glass transition point (Tg) is 55~
70°C, the binder resin contains 50% by weight or more, and C) the high temperature softening resin has a weight average molecular weight (Mw) of 4.0.
×105 to 1.5×106, the weight average molecular weight/number average molecular weight (Mw/Mn) is 3.0 or less, the outflow start point in a flow tester is 110 to 160°C, and the softening point is 150 to The temperature is 230°C, and the glass transition point (T
g) is 55°C or higher, D) the ratio of low temperature softening resin and high temperature softening resin is 50:50 to 90:10 in terms of polymerization ratio, and E) the low temperature softening resin is solution polymerized and high temperature softening F) The low melting point graft modified polyolefin mold release agent has a number average molecular weight (Mn) of 1.0x. 103 or less, the weight average molecular weight (Mw) is 2.5 x 103 or less, and Mw/M
A toner for developing an electrostatic image, in which n is 3.0 or less, a melting point is 60 to 120°C, and is used in an amount of 0.1 to 20% by weight based on the toner, and the toner image is transferred to a recording material. 1. A heat fixing method characterized in that heat fixing is carried out using a fixedly supported heating body and a pressure member that is in opposing pressure contact with the heating body and fixes the recording material to the heating body through a film.