JPH04199061A - Toner for development of electrostatic image - Google Patents

Abstract

PURPOSE:To make fixation at a low temperature even in a high speed system and prevent outflow of toner from a cleaning member for fixation by setting the dynamic modulus of elasticity and the loss modulus of elasticity in a specific relation. CONSTITUTION:The dynamic modulus of elasticity at 200 deg.C ranges from 1X10<3> to 5X10<4>dyn/cm<2> while the loss modulus of elasticity ranges from 5X10<2> to 5X10<4>dyn/cm<2>, and the former modulus is larger than the latter. Also the two moduli at 100 deg.C both lie under 5X10<6>dyn/cm<2>, and the synthesized curve according to the time vs. temperature conversion law has a point where increase of the dynamic modulus of elasticity caused by increasing frequency is smaller than the increase of the loss modulus of elasticity and at the same time, the dynamic modulus is equal to or larger than the loss modulus. This obtains toner which fixes at a low temperature even in a high speed system and which is free from outflow from the cleaning member for fixation.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a toner used in electrophotography, electrostatic printing, and magnetic recording, and particularly to a toner suitable for hot roller fixing.

[Background technology]

Conventionally, as an electrophotographic method, U.S. Patent No. 2,297°69
Although many methods are known, such as those described in Japanese Patent Publication No. 1, Japanese Patent Publication No. 42-23910, Japanese Patent Publication No. 43-24748, etc., in general, photoconductive substances are used and various means are used. to form an electrical latent image on the photoreceptor, then develop the latent image using toner, transfer the toner image to a transfer material such as paper as necessary, and then apply heat, pressure, or solvent vapor. The image is fixed and a copy is obtained.

Various methods and apparatuses have been developed for the above-mentioned final step of fixing the toner image on a sheet such as paper, but the most common method at present is a compression heating method using a heated roller.

The pressure heating method using a heated roller performs fixing by passing the toner image surface on the fixing sheet while contacting it under pressure with the surface of a heated roller whose surface is made of a material that has releasability for toner. be. 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 come into contact with each other under pressure in a molten state, a portion of the toner image adheres to and transfers to the fixing roller surface, and some of the toner image is transferred again to the next sheet to be fixed. A so-called offset phenomenon may occur, and the sheet to be fixed may be stained. Preventing toner from adhering to the surface of the heat fixing roller is considered to be one of the essential conditions for the heat roller fixed fixing method.

Conventionally, in order to prevent toner from adhering to the surface of the fixing roller, for example, the roller surface was made of a material with excellent release properties, such as silicone rubber or fluorine resin, and the surface was further coated with anti-offset and other materials. In order to prevent fatigue, the roller surface is coated with a thin film of a liquid with good mold releasability, such as silicone oil. However, although this method is extremely effective in preventing toner offset, it also requires a device to supply offset prevention liquid, resulting in problems such as a complicated fixing device. .

Therefore, it is not desirable to prevent offset by supplying an offset-preventing liquid, and rather the development of a toner with high offset resistance over a wide fixing temperature range is currently desired. Therefore, in order to increase the releasability of the toner, a method of adding wax such as low molecular weight polyethylene or polypropylene that melts sufficiently when heated has been used, but while this is effective in preventing offset, it increases the cohesiveness of the toner. , charging characteristics become unstable and durability tends to deteriorate. Therefore, as other methods, various attempts have been made to improve the binder resin.

For example, in order to prevent offset, a method is known in which the glass transition temperature (Tg) and molecular weight of the binder resin in the toner are increased to improve the melt viscoelasticity of the toner. However, when the offset phenomenon is improved by such a method, the fixing performance becomes insufficient, resulting in a problem that the fixing performance at low temperatures required for high-speed copying machines and energy saving, that is, the low-temperature fixing performance is poor.

On the other hand, in order to improve the fixing properties of toner, it is necessary to reduce the viscosity of the toner during melting and increase the adhesive area with the fixing substrate, and for this purpose it is necessary to lower the Tg and molecular weight of the binder resin used. is required.

That is, since low-temperature fixing properties and anti-offset properties have contradictory aspects, it is extremely difficult to develop a toner that satisfies both of these functions.

In order to solve this problem, for example,
Japanese Patent Publication No. 354 discloses a toner made of a vinyl polymer that is moderately crosslinked with the addition of a crosslinking agent and a molecular weight regulator, and Japanese Patent Publication No. 55-6805 discloses a toner containing an α,β unsaturated ethylenic monomer. A toner is disclosed in which the molecular weight distribution is widened so that the ratio of the weight average molecular weight to the number average molecular weight as a constitutional unit is 3.5 to 40, and furthermore, in a vinyl polymer,
Many blend toners and the like that combine Tg1 molecular weight, Kel content, etc. have been proposed.

It is true that toners based on these proposals have a lower fixation limit temperature (
Although the possible fixing temperature range between the lowest fixing temperature (the lowest temperature that can be fixed) and the offset temperature (the temperature at which offset occurs) is widened, if sufficient offset prevention performance is provided, the fixing temperature can still be kept sufficiently low ( unable to
On the other hand, when emphasis is placed on low-temperature fixability, there is a problem in that offset prevention performance becomes insufficient.

Furthermore, JP-A-59-214860 discloses a toner using a thermoplastic resin having a specific modulus of elasticity, but because the modulus of elasticity is too large, this toner still has poor low-temperature fixing properties and low-temperature offset prevention properties. There are problems with this, and the drawback is that the crushability is also poor.

In addition, instead of these vinyl resins, toners made by crosslinking polyester resins, which are said to be essentially superior to vinyl resins in terms of low-temperature fixing properties, and further adding anti-offset agents are also available. This is proposed in the publication No.-208559. Although this product has excellent low-temperature fixing properties and anti-offset properties, it has a problem in terms of production in that it has poor pulverizability.

Furthermore, in JP-A-56-116043, a vinyl monomer is polymerized in the presence of a reactive polyester resin, and the resin is polymerized through crosslinking reaction, addition reaction, and grafting reaction during the polymerization process. Toners using this method have been proposed, and although the pulverizability has been improved, the functions of each resin cannot be fully utilized in terms of low-temperature fixing properties and anti-offset properties.

Furthermore, a toner using a resin simply blended with a polyester resin and two types of vinyl resins with different gel contents (gelation degree of 20% or more and gelation degree of less than 10%) was proposed in JP-A-60-123850. Although this product has good low-temperature fixing properties, it has poor offset prevention properties and
The crushability is still not sufficient. If the proportion of vinyl resin having a gelation degree of 80% or more is increased for the purpose of improving offset resistance, the offset prevention property will improve, but on the contrary, the low temperature fixing property will be significantly lowered. Also, the degree of Kelization is simply 10%
If the amount of vinyl resin contained is less than that, sufficient crushability cannot be achieved.

Furthermore, as a method that satisfies both low-temperature fixing properties and anti-offset properties, it is possible to react a vinyl-based carboxyl group-containing polymer with a metal compound to effect crosslinking.
JP-A-57-178249, JP-A No. 57-17825
It was proposed in Japanese Patent Application Laid-open No. 0, etc., or by reacting a vinyl resin whose essential constituent units are a vinyl monomer and a more specific half-ester compound with a polyvalent metal compound to effect crosslinking. -110155 Publication, 61-11015
This is disclosed in Publication No. 6, etc. Furthermore, JP-A-63-2
No. 14760, No. 63-217362, No. 63-21
7363, etc., it is possible to form a molecular weight distribution divided into two groups, low molecular weight and high molecular weight, and to react the carboxyl group of a unique half-ester compound contained on the low molecular weight side with a polyvalent metal ion. Although various methods have been proposed, the current situation is that none of these methods has been able to satisfy the characteristics required of toners, particularly the low-temperature fixing properties and offset resistance required for high-speed machines.

In this way, it is extremely difficult to achieve high performance in both fixing-related performance (low-temperature fixing properties and anti-offset properties) and crushability. In particular, the crushability during toner production is
This is an important factor in today's trend toward smaller toner particle sizes due to demands for higher quality, higher resolution, and higher fine line reproducibility of copied images, and the crushing process requires a large amount of energy. Improving crushability is also important from the perspective of energy saving. In addition, toner fusion to the inner wall of the crushing device is more likely to occur with toner having good fixing performance, which impairs the crushing efficiency.

As a further aspect, in another copying process, there is a process of cleaning the toner remaining on the photoreceptor after transfer. Today, cleaning using blades (blade cleaning) has become popular in terms of equipment size, weight reduction, and reliability. With the increase in the lifespan of photoconductors, the miniaturization of photoconductor drums, and the increase in speed of systems, the requirements for toners to have resistance to fusion and filming to photoconductors have become more stringent. In particular, amorphous silicon photoreceptors that have recently been put into practical use are extremely durable, and OPC
The lifespan of organic photoreceptors (organic photoreceptors) is also becoming longer, and therefore the various performances required of toners are becoming more sophisticated.

In addition, miniaturization requires the ability to fit each element into a small space. This reduces the space through which cooling air can flow, and the heat sources of the fixing device and exposure system are very close to the toner hopper and cleaner, exposing the toner to a high-temperature atmosphere. Therefore, it has become impossible to put toners into practical use unless they have better anti-blocking properties.

As a method for improving the various drawbacks mentioned above, the applicant of the present application disclosed in JP-A-63-223662 a special resin in which a low molecular weight resin was added during suspension polymerization, but even with this method, For high-speed machines that print more than 80 sheets per minute,
It has been found that sufficient fixing performance cannot yet be obtained, and furthermore, the toner flows out from the cleaning member in contact with the fixing roller, staining the transfer material.

In other words, in high-speed machines that exceed 80 sheets per minute, the number of sheets passed through is enormous, even if the amount of offset per sheet is extremely small, so the amount of offset material to the fixing roller is considerable. This may cause the fuser to malfunction. In order to remove this minute amount of offset material, a fixing cleaning member such as a cleaning roller made of silicone rubber or a web is attached in contact with the fixing roller. Conventional binder resins for toners are designed primarily for low-temperature fixing properties and anti-offset properties.
It is not designed to maintain high melt viscosity up to high temperatures, such as above 200°C.

Therefore, the toner substance adhering to the fuser cleaning member remains at the set temperature of the fuser roller for a long time, resulting in a decrease in melt viscosity, and furthermore, the temperature of the fuser roller exceeds the set temperature of the fuser roller when the copying machine is turned on, etc. When shooting, the fuser roller reaches temperatures in excess of 200° C., and the melt viscosity of the deposited toner material decreases significantly, causing it to transfer again to the fuser roller, resulting in staining of the transfer material.

JP-A-59-38 discloses a method for preventing only staining of the transfer material due to melted toner from the leaning member.
Publication No. 754 proposes to prevent this by increasing elasticity over time in a molten state, but in this method, covalent bonds are formed in a molten state and the elasticity is increased by increasing the crosslink density. Therefore, the melt viscosity increases as well as the elasticity. In such a system, if a copy is made again before cross-linking has progressed to the extent required to prevent stains from the cleaning member, the elasticity of the binder has also increased, resulting in more particles adhering to the fixing cleaning member. The adhesion of the toner substance to the fixing roller increases, making it easier to transfer to the fixing roller.

Furthermore, if left at high temperatures for a long period of time, the degree of crosslinking will become excessively large, resulting in extremely high viscosity and elasticity.
It becomes a hard substance and can damage the fusing roller.

As mentioned above, the various performances required of toners are often contradictory to each other, and it has become increasingly desirable in recent years to satisfy both of them with high performance, and it has become increasingly desirable to satisfy both of them with high performance. Although research has been conducted on comprehensive responses, there is still not enough research.

It has been found that when the toner's elastic modulus has a specific relationship not only with its physical properties but also with its dynamic elastic modulus and loss elastic modulus, better fixing properties and anti-offset properties can be obtained in high-speed machines. This led to the present invention.

[Problems to be Solved by the Invention] An object of the present invention is to provide a toner that solves the above-mentioned problems.

The objects of the present invention are listed below.

SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent toner that can be fixed at a low temperature even in a high-speed system and that does not cause toner to flow out from a cleaning member for fixing.

The purpose of the present invention is to fix at a low temperature, fuse to a photoreceptor,
To provide a toner that does not cause filming even in high-speed systems and even after long-term use.

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner that can be fixed at low temperatures, has excellent anti-blocking properties, and can be used satisfactorily even in high-temperature atmospheres, especially in small machines.

An object of the present invention is to provide a toner suitable for a cleaning method using a plate.

[Means and actions to solve the problem]

The above object of the present invention is to use a toner containing at least a resin, a colorant, and a metal-containing compound at a frequency of 1 x 10-2 to 1H.
z, in the dynamic elastic modulus and loss modulus measured in the temperature range of 100 to 200°C, the dynamic elastic modulus at 200°C is 1
×103~5×10°dyn/Cm', loss modulus is 5
×102 to 5xlO"dyn/crn', the dynamic elastic modulus is larger than the loss modulus, and the dynamic elastic modulus and loss modulus at 100°C are 5 x 104 dyn/cm' or less, In addition, in the composite curve that we wanted to apply to the time-temperature conversion law, the increase in the loss modulus is larger than the increase in the dynamic modulus due to the increase in the elastic modulus as the frequency increases, and the dynamic modulus is the same as the loss modulus. This is achieved by a toner characterized by having dots that are only large.

Furthermore, the dynamic elastic modulus and loss elastic modulus of the toner measured at a temperature of 200° C. and a frequency of 1×10-” Hz are 6.
Dynamic elastic modulus after holding for 0 minutes is 1x103~5xlo'dy
n/crrf and the loss modulus is 5×1O2 to 5×10”d
It is preferable that the dynamic elastic modulus and loss modulus of the toner are within the range of y n / c n'f, and the amount of change over time of the dynamic elastic modulus and loss modulus of the toner measured at a temperature of 200° C. and a frequency of 1×10 −1 Hz is within the range of y n /c n′f. It is also preferable that the amount is less than twice as much.

In addition, JIS K-0070 of the resin used in the present invention
An acid value of 2 to 100 mgKOH/
It is preferable that it is g. Also, the frequency I
The dynamic elastic modulus measured at 2-1Hz and 200°C is
It is preferable that the ratio is 1×102 dyn/crrl' or more, so that good toner viscoelastic properties can be obtained.

Furthermore, it has been found that among the resins used in the present invention, resins having a cycarphoquinol group and a dicarboxyl group derivative group have particularly excellent properties. Furthermore, it is also a preferred embodiment that the vinyl resin containing a carboxylic acid-containing monomer or a carbonic acid derivative monomer as a constituent component of the resin component is 50% by weight or more.

As a particularly preferred resin for the present invention, first, a monomer having a carboxyl group or a dicarboxyl group derivative group is reacted by solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, etc. to produce a polymer. Examples include vinyl resin, polyester resin, epoxy resin, and polyamide resin. Alternatively, a carboxyl group or a dicarboxyl group derivative group can be introduced into the polymer by grafting, block copolymerization, or the like. In addition, if necessary, desolvation operation,
Carphonic acid anhydride can also be incorporated by subjecting it to a heat treatment under reduced pressure. As described above, the glass transition point is 50
℃ or above to form a polymer.

Next, 10 to 50 wt % (preferably 20 to 40 w[%) of the polymer and 0.5 to 20 wt % (preferably 1 to 15 w [%] of a carbonic acid-containing monomer with low water solubility)
t%) to perform a suspension polymerization reaction, and in the molecular weight distribution of the THF-soluble portion by GPC,
Molecular weight 2,000-ioo.

A polymer having at least one peak in the 000 region is produced. This is a polymer in which a portion of the carboxylic acid anhydride is hydrolyzed during suspension polymerization and can contain carbonic acid, dicarboxylic acid, and carbonic acid anhydride. It is believed that these acid components in the polymer interact with each other via the metal-containing compound or its metal ion, which is another component of the present invention, to form various polymer complexes.

Therefore, the toner resin of the present invention contains crosslinks by various polymer complexes having different bonding strengths and strong crosslinks by polymerizable crosslinking agents. By mixing, a toner that exhibits the above-mentioned unique viscoelastic properties is obtained for the first time.
It has excellent blocking resistance, as well as low-temperature fixing and offset resistance.

That is, when a polymer in which a dicarboxylic acid is present on the low molecular weight side is crosslinked via metal ions, it becomes possible to improve the blocking resistance of the toner without increasing the Tg of the polymer. If this method is followed, there is no need to increase Tg to improve blocking resistance, and the elastic modulus in the low temperature region can be kept low, and the dynamic elastic modulus and loss elastic modulus measured at 100 ° C. x 106d yn
/ crrf or less, and low-temperature fixing can be achieved.

Preferably it is 2×10'dyn/crrr' or less.

- When a polymer with a high Tg is used to improve blocking resistance, the dynamic modulus and loss modulus at 100°C exceed 5xlO'dyn/crn', achieving low-temperature fixing. Can not.

Further, the toner of the present invention has a dynamic elastic modulus of 1.5 at 200° C. due to the presence of crosslinks with various bond strengths in the polymer.
X103dyn7'cm' or more can be maintained and has excellent offset resistance. That is, 1xlo3dyn
, /crrr', the softened toner does not have sufficient rubber elasticity, so that the toner tends to offset toward the fixing roller or flow out from the fixing roller cleaning member.

Further, a more preferable range of dynamic elastic modulus at 200°C is I x 103 dyn,/cm" to 5 x 10" dyn
/ cr rn', preferably l X I 03=2 X
I O'dy ny'crrI2. When the dynamic elastic modulus exceeds 5×10 dyn/c, the rubber elasticity is strong at high temperatures, which may have a disadvantageous effect on fixing performance.

In addition, the loss modulus is 5x 102 to 5x 10'dyn
/crn', preferably 5 x 102 to 2 x 104 dyn
/crry', the above-mentioned offset resistance is more effectively achieved. Loss modulus is 5×102dyn/c
When it is less than rrf, the viscosity of the polymer in the toner becomes too low, and even if the toner has rubber-like elasticity with the above-mentioned dynamic elastic modulus, it may not be possible to prevent the toner from flowing out from the fixing cleaning member. be.

If the loss modulus exceeds 5XlO'dyn/crrf, the toner becomes difficult to deform even at high temperatures, so it tends to be difficult to fix the toner to the transfer material sufficiently.

Furthermore, when the dynamic elastic modulus is larger than the loss elastic modulus, the rubber elasticity of the toner acts effectively, making it possible to prevent the toner from flowing out.

Tsumari, dynamic elastic modulus is 1×10°d yn/c
When exceeding rrf, it is possible to prevent offset in which melted toner adheres to the fixing roller, but when the loss modulus is large, it is not possible to prevent toner from flowing out from the fixing device cleaning member. In other words, at high temperatures (200°C), toner outflow can be most effectively prevented if the dynamic elastic modulus is always greater than the loss elastic modulus within the measurement frequency range (lxl, 0"" to IHz). become. Of course, offset is not a problem at all when toner outflow can be prevented.

In conventional toners, the loss modulus of elasticity at high temperatures is greater than or equal to the dynamic modulus of elasticity, so it was not possible to obtain elasticity sufficient to prevent the toner from flowing out.

That is, when the dynamic modulus becomes smaller than the loss modulus,
This is because the elasticity cannot completely prevent the toner from flowing out due to its viscosity.

In addition, in the composite curve according to the time-temperature conversion rule,
The frequency dispersion of the elastic modulus at the reference temperature can be interpreted in the same way as the temperature dispersion at a constant frequency, and the behavior on the low frequency side can be seen as the behavior in the high temperature region, and the behavior on the high frequency side can be seen as the behavior in the low temperature region.

In other words, the change in the elastic modulus as the frequency increases can be seen as a change from a high temperature region to a low temperature region. On the other hand, the dynamic elastic modulus is the part that stores the energy given during a certain deformation and is used for recovery from the deformation, and the loss modulus is the part that irreversibly dissipates the energy given as thermal energy during the deformation. It is a part.

Furthermore, both the dynamic elastic modulus and the loss elastic modulus increase as the temperature decreases, meaning that large amounts of energy are required for deformation.

In order to effectively use energy to deform the toner at low temperatures, it is better for both the dynamic elastic modulus and the loss elastic modulus to be small. Furthermore, unless the dynamic elastic modulus and loss elastic modulus are particularly large, a larger ratio of loss elastic modulus is preferable for fixing at low temperatures because more energy is used for irreversible deformation of the toner. If the dynamic elastic modulus is large, the reversible deformation of the toner consumes the double energy, so the deformed toner returns to its original shape, making fixing at low temperatures inefficient.

That is, when the sum of the dynamic elastic modulus and the loss elastic modulus is the same, a toner exhibiting viscoelastic behavior with a larger loss elastic modulus has better low-temperature fixability.

Furthermore, the smaller the above-mentioned sum is, the less energy is consumed in deforming the toner, which is preferable for low-temperature fixing.

The toner of the present invention has improved offset resistance at high temperatures.
Although the dynamic elastic modulus is large, the contribution of the loss elasticity increases when the elastic modulus increases with a decrease in temperature, and the increase in the loss elastic modulus is larger than the increase in the dynamic elastic modulus. In other words,
In the low temperature region, is the loss modulus the same as the dynamic modulus?
It has a large point and exhibits excellent low-temperature fixing properties. For example, the composite curve is as shown in FIG.

Here, the loss modulus is the same as or larger than the dynamic modulus because the ratio of loss modulus 7/dynamic modulus, that is, the loss tangent tan δ is 09 or more, or the modulus of elasticity measured at 180°C or less is It would be good if it was inside.

Also, in the high temperature section, the dynamic elastic modulus is larger than the loss elastic modulus, which means that the loss tangent at the elastic modulus measured at 200°C is 0.
．． This means that it is less than 9.

In conventional toners, either the dynamic elastic modulus and the loss elastic modulus change at a similar rate (e.g., Figure 2), or the dynamic elastic modulus increases greatly (e.g., Figure 3). . If the dynamic elastic modulus and the loss elastic modulus change at similar rates, it may not be possible to obtain low-temperature fixing performance if emphasis is placed on offset resistance on the high-temperature side, or it may not be possible to prevent toner outflow if emphasis is placed on low-temperature fixing performance. It had become. Furthermore, if the dynamic elastic modulus increases significantly, the fixing performance will be poor, and in addition to this, if the dynamic elastic modulus on the high temperature side is smaller than the loss elastic modulus, sufficient offset resistance will not be obtained. It wasn't there.

In addition, since the toner of the present invention contains crosslinks with various bond strengths in the binder as described above, the dynamic elastic modulus and loss modulus at 200°C are unlikely to change over time.
The dynamic elastic modulus after being kept at ℃ for 60 minutes is lXIO3~5x
lO'dyn/crrr', preferably lxl, 03~
It is within the range of 2xlO"dyn/cm', and the loss modulus is 5XIO2 to 2x10"dyn/crr1
' is preferably within the range. Alternatively, the rate of change in dynamic elastic modulus and loss modulus per 60 minutes when maintained at 200°C is preferably less than 2 times, more preferably within the range of 0.5 to 1.8 times. . As described above, toner is effectively prevented from flowing out from the fixing cleaning member, and furthermore, problems such as damage to the fixing roller do not occur.

If the dynamic elastic modulus exceeds 5 x 104 dyn/crn', the loss elastic modulus exceeds 2 x lO' dyn/crIf, or the rate of change in the elastic modulus is more than double, the fixation will occur when left at high temperatures for a long time. This will cause damage to the rollers. In addition, if the dynamic elastic modulus is less than 1 x 101 dyn/cm', the loss modulus is less than 5 x 102 dyn/crrr', or the rate of change in elastic modulus is less than 0.5 times, the binder resin of the toner may be This tends to cause the toner to disintegrate and cause toner to flow out from the fixing cleaning member.

In the present invention, the molecular weight of the peak and/or shoulder of a chromatogram by GPC (Kölpermeation chromatography) using THF as a solvent is measured under the following conditions.

That is, 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) at a flow rate of 1 ml per minute,
Approximately 100μ of THF sample solution! Inject and measure. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithm value and count number of a calibration curve prepared using several types of monodisperse polystyrene standard samples. For example, standard polystyrene samples for creating a calibration curve include:
Pressure Chemical Co., Toyo Tsudani Gyo Co., Ltd., Showa Denko Co., Ltd. with a molecular weight of 1
It is appropriate to use a standard polystyrene sample of about 07 to 10' and at least about 1O point. Further, an RI (refractive index) detector is used as a detector.

As a column, it is best to combine multiple commercially available polystyrene Kel columns; for example, Showa Denko's 5
hodex GPCKF-801, 802, 803,
Combinations of 804, 805, 806, 800P, w
Ultra Styrunel 500A-TH manufactured by ater
F, 103A-THF, 10'A-THF, 105A-
THF, 10'A-THF combination, or A-To
One example is the combination of the luene series. Furthermore, 5hodexGPCKF-801, 802, 80
Examples include combinations of 3,804,805,806,807,800P.

In addition, the sample is prepared as follows. The sample is placed in THF, left to stand for several hours, shaken thoroughly, mixed well with THF (until the sample no longer coalesces), and left to stand for a further 12 hours or more. At this time, the time of leaving in THF should be 24 hours or more.

After that, sample processing filter (pore size 045~0
For example, Mainyo 11 disk H-25-5 up to 5μm
The GPC sample is obtained by passing it through an Ekiklo Disc 25CR (manufactured by Tosoh Corporation, available from Gelman Science Japan Co., Ltd.). Further, the sample concentration is adjusted so that the resin component is 05 to 5 mg/m (!).

In addition, in the present invention, the content of carbonic acid, especially carphonic acid and its derivatives, in the toner resin has a large effect on the viscoelasticity of the toner,
Acid value measured by a method similar to 070 is 2 to 100 mgK
OH/g, preferably 5 to 70 mgK
OH/g. When the acid value is less than 2 mg K O8, it becomes difficult to obtain desirable rubber elasticity at high temperatures. Further, when the acid value exceeds 100 mg KOH77 g, it is difficult to control the amount of charge, and environmental dependence tends to appear in developability.

In the present invention, the content ratio of carbonic acid, especially sicarphonic acid and its derivatives in the toner resin has a large influence on the viscoelasticity of 1.0%, and the content ratio of carbonic acid, especially sicarphonic acid and its derivatives, in the toner resin has a large effect on the viscoelasticity of 1.
Acid value (A) measured by a method according to 70 and total acid value (B) measured after hydrolyzing the acid anhydride of the vinyl resin
It is obtained by melt-kneading a vinyl resin having a ratio (A, /B) of 0.75 or more, preferably 0.75 to 0.98, together with a metal salt or a metal complex.

When the A/H ratio is less than 0.75, the proportion of acid anhydride becomes too high, the blocking resistance is insufficiently improved, and the viscoelastic properties required in the present invention cannot be obtained.

When the A/B ratio exceeds 0.98, almost no acid anhydride exists, and the charging characteristics of the toner become unstable, which tends to cause problems in image quality.

Note that the total acid value is measured as follows.

2 g of sample resin was dissolved in 30 ml of dioxane, and 10 ml of pyridine and 20 ml of dimethylaminopyridine were added to this.
mg, water 3. 5mj? and heated under reflux for 4 hours while stirring. After cooling, the acid value obtained by neutralization titration with a 1/10 NKOH-THF solution using phenolphthalein as an indicator is defined as the total acid value. l/ION KOH-TH
The F solution is prepared as follows. KOHl, 5g about 3
mf of water and add 200 ml of THF and 3 ml of water to this.
Add 0ml and stir. After standing, if the solution is separated, add a small amount of methanol, or if the solution is cloudy, add a small amount of water to make a homogeneous and transparent solution, and standardize with 1/10N HCf standard solution.

The toner characterized by the present invention is produced by kneading a resin having a dynamic elastic modulus with a constant yield due to crosslinking and entanglement of molecular chains with a high shear, thereby cutting the molecular chains and re-crosslinking. This gives it a dynamic elastic modulus above a certain level. By changing the crosslinking state in this way, the effect on viscoelasticity due to thermal reaction is reduced, making it difficult to change over time.

Further, the crosslinking obtained in this manner has an appropriate loss modulus, so that the viscoelastic properties in the high temperature part and the low temperature part are well balanced, and both fixing properties and anti-offset properties can be maintained. Furthermore, it is difficult to obtain such viscoelastic properties by polymerization alone, which is inconsistent with the improvement of fixing properties and anti-offset properties. This is thought to be due to the fact that the recrosslinking provides appropriate flexibility and regulation of the movement of the molecular chains.

When the dynamic elastic modulus of a resin kneaded under conditions that cut the molecules used in the present invention is measured, it is lower than the dynamic elastic modulus during kneading. On the other hand, if a metal compound is present during kneading, the dynamic elastic modulus is restored. As such an example, FIG. 4 shows the dynamic elastic modulus at 200'C of the resin used in the present invention before and after kneading and of the kneaded product containing a metal compound.

That is, the dynamic elastic modulus that the toner resin originally has is also important, and it is preferable that the dynamic elastic modulus measured at 200° C. .

When the dynamic elastic modulus is 1 x lO'dyn/crrf or less, the dynamic elastic modulus when formed into a toner is 1 x 103 dyn/'c
Even with the configuration of the present invention, it tends to be difficult to obtain I'TT' or more, and sufficient offset resistance performance is not even achieved.

The viscoelastic properties of the resin can be controlled by the types and quantitative ratios of the polymerizable crosslinking monomer, polymerization initiator, resin composition monomers, and polymerization conditions.

Further, it is particularly preferable that the dynamic elastic modulus of the toner, measured at 200 DEG C. 05
If it is less than twice that, deterioration over time may easily occur, and toner may flow out from the fixing cleaning member. This can be controlled by the acid value of the resin and the type and amount of the metal compound.

In conventional toners, even if a resin having sufficient viscoelastic properties is used, when the toner is made into a toner, the viscoelastic properties necessary for the toner are lost, and the toner tends to flow out.

This tendency becomes even stronger when high shear kneading is performed.

Carphonic acid-containing monomers or carboxylic acid derivative monomers used in the present invention include maleic acid, citrachoic acid, dimethylmaleic acid, itaconoic acid, alkenylsuccinic acid, and anhydrides thereof: fumaric acid, methaconic acid. , unsaturated dibasic acids such as methyl fumaric acid, monoesters of the above unsaturated dibasic acids, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and their anhydrides 1 above α, β-
Anhydrides between unsaturated acids, anhydrides with lower fatty acids, alpha, beta unsaturated acids, monomers of these anhydrides: alkenyl malonic acid, alkenyl geltanic acid, alkenyl adipic acid and their anhydrides , monoester;

Among these, monoesters of α,β-unsaturated dibasic acids having structures such as maleic acid, fumaric acid, and succinic acid are particularly preferably used as monomers for obtaining the binder resin of the present invention. Such monomers include, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate, monophenyl maleate, monomethinobefumarate, monoel fumarate, monobutyl fumarate, and monobutyl maleate. Monophenyl: monobutyl n-butenylsuccinate, n-
Monomethyl octenylsuccinate, monoethyl n-butenylmalonate, monomethyl n-dodecenylcurtarate, n
-monobutyl phthynylampinate.

Examples of comonomers for obtaining the binder resin of the present invention include the following.

For example, styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p
-Phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-
Butylstyrene, pn-hequinorstyrene, pn-
Octylstyrene, pn-nonylstyrene, pn-
Styrene and its derivatives such as decylstyrene and pn-dodecylstyrene; ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene; vinylidene chloride, vinylidene chloride, vinyl bromide, Vinyl halides such as vinyl fluoride, vinyl esters such as vinyl acetate, vinyl propionate, and hinyl benzoate: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, Methacrylic acid esters such as n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, Acrylic acid esters such as n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N- N-vinyl compounds such as vinylpyrrolidone; hinylnaphtha.

Phosphorus: Vinyl monomers such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide are used alone or in combination of two or more.

Among these, combinations of monomers that result in styrene copolymers and styrene-acrylic copolymers are preferred.

Further, as the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used.

In order to achieve the object of the present invention, the binder resin used in the present invention needs to be a polymer crosslinked with a crosslinkable monomer as exemplified below.

Aromatic cyhenyl compounds, such as divinylbenzene, divinylnaphthalene, etc.; diacrylate compounds linked with alkyl chains, such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1
, 4-butanediol diacrylate, 1.5-pentanolne acrylate, 1.6-hexanethiolne acrylate, neopentyl glycol diacrylate, and the above compounds in which the acrylate is replaced with methacrylate, containing an ether bond. Diacrylate compounds linked with alkyl chains, such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate,
Polyethylene glycol #400 diacrylate, polyethylene glycol #600 diacrylate, dipropylene glycol diacrylate, and the above compounds in which the acrylate is replaced with methacrylate; diacrylate compounds connected by a chain containing an aromatic group and an ether linkage. such as polyoxyethylene (2) -2,2
-bis(4-hydroxyphenyl)propane diacrylate, polyoxyethylene(4)-2,2-bis(4-
hydroxyphenyl) propane diacrylate, and
In addition, polyester gin acrylate compounds such as MANDA (trade name, manufactured by Nippon Kayaku Co., Ltd.) may be used instead of the acrylate in the above compounds with methacrylate. Examples of polyfunctional crosslinking agents include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and triacrylates in which the acrylates of the above compounds are replaced with methacrylates; Examples include allyl cyanurate and triallyl trimellitate.

These crosslinking agents are used in an amount of 0.0% based on 100% by weight of other monomer components. It is preferable to use about 1 to 5% by weight (more preferably about 0.03 to 3% by weight) of O.

Among these crosslinking monomers, aromatic cyhenyl compounds (particularly divinylbenzene),
Mention may be made of chain diacrylate compounds containing aromatic groups and ether linkages.

The method of synthesizing the binder resin according to the present invention is basically preferably a method of synthesizing two or more types of polymers.

That is, it is a method in which a low molecular weight polymer is dispersed and dissolved in a polymerizable monomer, and the monomers are polymerized to obtain a resin composition. In this case, a composition is formed in which the former and latter polymers are uniformly mixed.

The low molecular weight polymer in the binder resin composition used in the present invention can be obtained by commonly used polymerization methods such as bulk polymerization and solution polymerization.

For example, the following polymers are used. Homopolymers, copolymers, polyesters, polyurethanes, Epoquine resins, polyamides, polyvinyl butyral, rosins, modified rosins, terpene resins, phenolic resins, aliphatic or alicyclic hydrocarbon resins, aromatic resins of the aforementioned vinyl monomers Petroleum resin, haloparaffin, paraffin wax, etc., and a mixture of two or more may be used.

It is sufficient that these polymers contain a carboxyl group or a carboxyl group-inducing group, and when used in a mixture of two or more, it is sufficient that at least one of them contains a carboxyl group or a carboxyl group-inducing group.

Additionally, crafting or block copolymerization can be used to provide these functional groups in the polymer.

In addition, in the bulk polymerization method, it is possible to obtain a low molecular weight polymer by polymerizing at high temperature to accelerate the rate of termination reaction, but there is a problem that it is difficult to control the reaction. On this point, in the solution polymerization method, low molecular weight polymers can be easily obtained under mild conditions by utilizing the difference in chain transfer of radicals depending on the solvent and by adjusting the amount of initiator and reaction temperature. It is preferable to obtain a low molecular weight substance in a resin composition used in

Solvents used in solution polymerization include xylene, toluene,
Cumene, cellosolve acetate, 2-butanone, Hensen, etc. are used. In the case of styrene monomer mixtures, xylene, toluene or cumene are preferred. It is appropriately selected depending on the polymer to be polymerized. The initiator may be tert-butyl peroxide, tert-butyl peroxybenzoate, benzoyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azohis (2°4-methylpaleronitrile), etc. is used at a concentration of 0.05 parts by weight or more (preferably 01 to 15 parts by weight) based on 100 parts by weight of the monomer. The reaction temperature varies depending on the solvent used, the initiator, and the polymer to be polymerized, but
It is best to carry out at a temperature of 70°C to 230°C. In solution polymerization, 30 to 400 parts by weight of monomer per 100 parts by weight of solvent.
Preferably, parts by weight are used.

This low molecular weight polymer is polymerized again together with the monomer that provides the high molecular weight polymer, and emulsion polymerization or suspension polymerization is preferred as the polymerization method for obtaining the high molecular weight component in the highly crosslinked region.

Among these, the emulsion polymerization method uses monomers that are almost insoluble in water (
In this method, monomers are dispersed as small particles in an aqueous phase using an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. In this method, it is easy to control the reaction heat, and because the polymerization phase (oil phase consisting of polymer and monomer) and water phase are separate, the termination reaction rate is low, and as a result, the polymerization rate is high. , a product with a high degree of polymerization can be obtained. Furthermore, the polymerization process is relatively simple, and the polymerization product is fine particles, so it is easy to mix with colorants, charge control agents, and other additives in toner production. Therefore, this method is more advantageous than other methods as a method for producing a binder resin for toner.

However, due to the added emulsifier, the resulting polymer tends to become impure, and operations such as salting out are necessary to remove the N −+"1',", body.To avoid this inconvenience, suspension polymerization is recommended. It's convenient.

On the other hand, in the suspension polymerization method, a monomer containing a low molecular weight polymer is polymerized together with a crosslinking agent in a suspended state, so that the resin composition is formed into a pearl shape, and the crosslinked ring component is formed from the low molecular weight polymer. Including high molecular weight polymers can be obtained in a preferable state in which they are uniformly mixed.

In suspension polymerization, for 100 parts by weight of an aqueous solvent,
It is preferable to use 100 parts by weight or less of the monomer (preferably 10 to 90 parts by weight). Usable dispersants include polyvinyl alcohol, partially saponified polyhinyl alcohol, phosphoric acid, etc., and there are appropriate amounts depending on the amount of monomer relative to the aqueous solvent, but generally it is It is used in an amount of 0.05 to 1 part by weight. The polymerization temperature is suitably 50 to 95°C, but should be appropriately selected depending on the initiator used and the intended polymer. As for the type of initiator, it is possible to use any type of initiator as long as it is insoluble or sparingly soluble in water; for example, benzoyl peroxide, tert-butyl peroxyhexanoate, etc. It is used in an amount of 0.5 to 10 parts by weight.

Further, the metal compounds used in the present invention include metal salts or metal complexes, and those containing the following metal ions can be used. Suitable divalent metal ions include Ba'', Mg2
\CaCa2-1H\5n2-1Pb2\Fe”, Co
2-1Ni2-1Zn2-. In addition, trivalent ions include Ar, S c", Fe', Ce", N
i"', Cr3-1 ¥3- and so on.

Among such metal compounds, organometallic compounds have excellent compatibility and dispersibility with the polymer, and crosslinking by the metal compound proceeds more uniformly in the polymer, giving better results.

Among the organometallic compounds mentioned above, those containing organic compounds with high vaporizability and sublimation properties as ligands and counterions are useful. Among organic compounds that form coordination or counter ions with metal ions, examples of those having the above properties include salicylic acid, salicylamide, salicylamine, salicylaldehyde, salicyrosalicylic acid, ditertiary-butylsalicylic acid, Examples include salicylic acid and its derivatives, such as acetylacetone, propionacetone, β-diketones, such as acetate and low-molecular-weight carbonic acid salts of propionic acid.

It is also possible to impart charge controllability to the toner particles to the metal complex. Examples of such metal complexes include aso metal complexes represented by the following formula CI.

[In the formula, M represents a coordination center metal, Sc with a coordination number of 6, T
i, VXCr, Co, Ni, Mn, Fe, etc. Ar is an aryl group, such as a phenyl group or a naphthyl group, which may have a substituent. Examples of the substituent in this case include a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group. X, X', Y, Y' are -〇-1-CO-1-NH-1-NF! , -(R is 1 carbon number
~4 alkyl group). KO is hydrogen, sodium,
Indicates potassium, ammonium, and aliphatic ammonium.

] Next, specific examples of the complex will be shown.

Complex [I]-6 or the basic organic acid metal complex shown in the following general formula [I[] also provides negative chargeability and can be used in the present invention.

[In the formula, M represents a coordination center metal, and CrS with a coordination number of 6
Examples include Co, Ni, Mn, Fe, and the like. A is E
(having a substituent such as an alkyl group)
; R, R (R represents a hydrogen atom, a C0-C1 alkyl or alkenyl group); Examples of Y include hydrogen, sodium, potassium, ammonium, and aliphatic ammonium. Z is -0- or -C-0-. 1 Next, specific examples of the complex will be shown.

Complex [11]-1 Complex [n] -2 Complex [IT]-3 Complex [11] -4 Complex [■ Cola complex [11]-6 Complex [■] -7 Complex [I[]-8 Complex [11] []-9 Complex [n]-10 These metal complexes can be used alone or in combination of two or more.

The amount of the metal complex added to the toner particles varies depending on the type of toner binder, whether a carrier is used in combination, the pigment that colors the toner, and the reactivity of the metal complex with the binder. 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 1% by weight, based on 100% by weight of the binder, including
~5% by weight.

Furthermore, when the metal salt or metal complex is reacted with the binder during melt-kneading, it has the advantage of being excellent in compatibility with the binder or dispersibility in the binder, and providing stable charging properties as a toner.

In the present invention, it is possible to impart charge control properties to the metal salt or metal complex as a crosslinking component as a toner, but if necessary, a charge control agent may also be used separately. A known negative or positive charge control agent may be used.

Charge control agents known in the art today include the following:

The following substances are used to control the negative chargeability of toner.

For example, organometallic complexes and chelate compounds are effective, including the monoazo metal complexes mentioned above, acetylacetone metal complexes, aromatic hydroxycarphonic acids, and aromatic dicarphonic acid-based metal complexes. Others include aromatic hydroxycarphonic acids, aromatic mono- and polycarphonic acids and their metal salts,
These include anhydrides, esters, and phenol derivatives such as hisphenol.

The following substances are used to control the toner to be positively charged.

Modified products with nigrosine and fatty acid metal salts.

Tributylhensyl ammonium-1-hydroxy-4
- quaternary ammonium salts such as naphthosulfonates, tetrabutylammonium tetrafluorophorate, onium salts such as phosphonium salts which are analogs thereof, and lake pigments thereof, triphenylmethane dyes and lake pigments thereof, ( As a lake agent, metal salts of higher fatty acids such as phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide; dibutyltin oxide, dioctyltin oxide , dicyclohexyltin oxide, and other orkanotin oxides: diocastin oxides, such as siphytylsulforate, dioctyltin phorate, and synchrohexyltin phorate; these alone or two or more types; Can be used in combination. Among these, charge control agents such as nicrosine and quaternary ammonium salts are particularly preferably used.

In the toner of the present invention, it is preferable to add fine silica powder to improve charging stability, developability, fluidity, and durability.

The fine silica powder used in the present invention gives good results when the specific surface area by nitrogen adsorption measured by the BET method is within the range of 30 rn'/g or more (particularly from 50 to 400 rn'/g). The fine silica powder is preferably used in an amount of 0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of toner.

In addition, the fine silica powder used in the present invention may include, if necessary,
Silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents,
It is also preferable that the material be treated with a treatment agent such as a silane coupling agent having a functional group, another organosilicon compound, or a combination of various treatment agents.

Other additives include lubricants such as Teflon, zinc stearate, and polyvinylidene fluoride, with polyvinylidene fluoride being preferred. Alternatively, abrasives such as cerium oxide, silicon carbide, and strontium titanate, among which strontium titanate is preferred. Alternatively, fluidity imparting agents such as titanium oxide and aluminum oxide, among which hydrophobic ones are particularly preferred. A small amount of an anti-caking agent or a conductivity imparting agent such as carbon black, zinc oxide, antimony oxide or tin oxide, or white fine particles and black fine particles of opposite polarity can be used as a developability improving agent.

In addition, in order to improve mold releasability during hot roll fixing, waxy substances such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, carnauba wax, Sasol wax, paraffin wax, etc. are added to 100% by weight of the binder resin. It is also one of the preferred embodiments of the present invention to add about .5 to 10% by weight to the toner.

Further, when the toner of the present invention is used as a two-component developer, it is mixed with carrier powder. In this case, the mixing ratio of toner and carrier powder is 0.1 to 50% by weight, preferably 0.5 to 10% by weight as toner concentration.
More preferably, it is 3 to 5% by weight.

As the vine carrier used in the present invention, all known carriers can be used, such as iron powder, ferrite powder, magnetic powder such as nickel powder, glass beads, etc., and their surfaces are coated with fluorine resin, vinyl Examples include other materials treated with resins such as silicone resins or silicone resins.

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 can also serve as a colorant. The magnetic materials contained in the magnetic toner of the present invention include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and aluminum, cobalt, and aluminum of these metals.
Examples include alloys of metals such as copper, lead, magnesium, tin, zinc, antimony, beryllium, hismuth, cadmium, carunium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

The average particle size of these ferromagnetic materials is preferably about 0.1 to 2 μm, preferably about 0.1 to 0.5 μm, and the amount contained in the toner is about 20 to 200 parts by weight per 100 parts by weight of the resin component. parts, particularly preferably resin component 100
It is preferably 40 to 150 parts by weight.

In addition, the magnetic properties with 10 KOe applied are coercive force 20 to 30.
00e saturation magnetization of 50 to 200 emu/g and residual magnetization of 2 to 20 emu/g are desirable.

Colorants that can be used in the toners of the present invention include any suitable pigments or dyes. Toner colorants are well known and include, for example, pigments such as carhon black, alinin pigment, acetylene black, naphthol yellow, bassa yellow, rhodamine lake, alisarin lake, henkara, phthalocyanine blue, and indanthryfluor. These are used in an amount necessary and sufficient to maintain the optical density of the fixed image, and the addition amount is preferably 1 to 20 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the resin. Further, dyes are also used for the same purpose. For example, azo dyes, anthraquinone dyes, xanthine dyes, methine dyes, etc. 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, per 100 parts by weight of resin.
The amount added in parts by weight is good.

To prepare the toner for developing an electrostatic image according to the present invention, a vinyl resin, a metal salt or a metal complex, and an admixture are used.

Pigments as coloring agents, dyes, magnetic substances, charge control agents, other additives, etc. as necessary, are added to a Hennel mixer,
After thorough mixing using a mixer such as a ball mill, the resins are melted and kneaded using a heat kneading machine such as a heated roll, kneader, or extruder, and the resins are mixed with each other. The toner according to the present invention can be obtained by dispersing or dissolving, cooling and solidifying, and then pulverizing and classifying.

Further, if necessary, desired additives are sufficiently mixed using a kneader such as a Henschel mixer to obtain the toner for developing electrostatic images according to the present invention.

The present invention will be explained below according to specific examples, but the present invention is not limited by these in any way.

〔Example〕

Each of the above components was added dropwise over 4 hours to 200 parts by weight of xylene heated to reflux temperature. Furthermore, under xylene reflux (
Polymerization was completed at 138-144°C) and then heated to 200°C under reduced pressure.
Xylene was removed while raising the temperature to . The obtained copolymer was dissolved in THF, and the main peak of the copolymer was found to have a molecular weight of 11°,000, a Tg of 59.5°C, and a copolymer containing an anhydride derived from maleic acid.

Add 0 partially saponified polyvinyl alcohol to the above mixed solution.
．． 170 parts by weight of water in which 12 parts by weight had been dissolved was added and vigorously stirred to obtain a suspension dispersion having a particle size of 100 μm or less.

The above suspension dispersion was added to a reactor containing 50 parts by weight of water and purged with nitrogen, and suspension polymerization was carried out at a reaction temperature of 80° C. for 8 hours. After the reaction was completed, it was filtered, thoroughly washed with water, and dried to obtain a styrene resin (A).

In addition, when we measured the molecular weight distribution of THF-insoluble components, we found that G
In the CP chart, about 1.7. It had a peak at OOO, and the Tg of the resin was 58°C.

Furthermore, the acid value according to the JIS method is 33.2, and the total acid value is 3.
53, the ratio A/B was 0.94, and most of the maleic anhydride introduced into the low molecular weight resin was converted to cyclophonic acid during suspension polymerization.

Note that the glass transition point Tg of the resin is measured using a differential thermal analysis measuring device,
Using DSC-7 (manufactured by PerkinElmer), ASTM
It was measured according to the D3418-82 method.

In addition, 200℃ walk ≠ ≠ prison ≠ tray, frequency IX1.0-2 ~
The dynamic modulus measured at IHz is shown in Table 2.

The viscoelasticity of the resin is measured using a rheometer (Wakagi Seisakusho IR).
-200 was carried out using an improved model that was able to measure with a parallel plate).

Styrene 765 parts by weight 1 Tert-butyl peroxide 60 parts by weight The above components were used in the same manner as in Synthesis Example 1 to obtain a main peak of 4°900.7.
A copolymer having a temperature of 60.2° C. was obtained.

Resin (B) was obtained by carrying out suspension polymerization in the same manner as in Synthesis Example 1 using the above components. Regarding the physical properties of resin (B), see Table 1.
Shown in Table 2.

Synthesis J Using the above components as in Synthesis Example 1, the main peak was 7°00.
A copolymer with a Tg of 61.5° C. was obtained.

Resin (C) was obtained by carrying out suspension polymerization in the same manner as in Synthesis Example 1 using the above components. Regarding the physical properties of resin (C), see Table 1.
Shown in Table 2.

Synthesis A The above components were added in the same manner as in Synthesis Example 1, and the main peak was 12°1.
00, a copolymer with a Tg of 59.1°C was obtained.

Resin (D) was obtained by carrying out suspension polymerization in the same manner as in Synthesis Example 1 using the above components. Regarding the physical properties of resin (D), see Table 1.
Shown in Table 2.

The main peak was 8°70 using the same ingredients as in Synthesis Example 1.
A copolymer with a Tg of 59.7°C was obtained.

Resin (E) was obtained by carrying out suspension polymerization in the same manner as in Synthesis Example 1 using the above components. Regarding the physical properties of resin (E), see Table 1.
Shown in Table 2.

A copolymer was obtained in the same manner as in Synthesis Example 1. TH copolymer
The molecular weight of the main peak of GPC dissolved in F was 4,500, and the Tg was 60.3°C. Below is 30 parts by weight of the above copolymer! Synthesis Example 1
Suspension polymerization was carried out in the same manner as styrenic resin (Fl
) was obtained.

Various physical properties of the resin (F) are shown in Tables 1 and 2.

Gold” [Example 7 The above components were used in the same manner as in Synthesis Example 1, and the main peak was 6°10.
A copolymer with a Tg of 59.9°C was obtained.

Resin (G) was obtained by carrying out suspension polymerization in the same manner as in Synthesis Example 1 using the above components. Regarding the physical properties of resin (G), see Table 1.
Shown in Table 2.

Table 1 Physical Properties of Resin After premixing the above materials, they were melt-kneaded using a twin-screw kneading extruder set at 110° C. and having a reverse feed shaft in the kneading zone. After cooling the kneaded material, it was coarsely pulverized, finely pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain a black fine powder (toner 1) having a weight average particle size of 8 μm.

The viscoelasticity measurement of this toner was performed using a rheometer (an improved model of Wakagi Seisakusho's IR-200 that can be measured with parallel plates [plate diameter 30φ, measurement plate Ga
p approximately 1 mm]) to determine the frequency dispersion of dynamic viscoelasticity due to sinusoidal vibration.

Measurement temperature is 200℃, 180℃, 160℃, 140℃,
120℃, ioo'c, frequency is 0.01.0゜O2,
0,03,0,05,007,O110,2,0,3,
05,0,7,1,0Hz. Table 3 shows the viscoelastic properties at a temperature of 200°C, and Fig. 5 shows the viscoelastic frequency-dependent composite curve when the viscoelastic properties and loss pressure are set to °C at a temperature of 100°C.

0.6 parts by weight of hydrophobic colloidal silica was added to 100 parts by weight of the above toner.

The image properties, fixing properties, offset properties, etc. of this toner were evaluated using a modified Canon NP-8582 copying machine capable of copying 85 sheets per minute.

As a result of a 500,000 copy test, stable, clear images with no fog were obtained. Also, the image density is 1.34 to 1.
38 and was a high-quality image with high resolution and excellent line reproduction and halftone dot reproduction.

In addition, the image after 500,000 sheets is completely unchanged compared to the initial image, and there is almost no environmental dependence, and there is no filming or fusion on the photoreceptor, and there is no problem with the fixing roller. was not contaminated by copying.

The blocking property was determined by visually observing the degree of aggregation when approximately 10 g of toner was placed in a 100 cc poly cup and left at 50° C. for 3 days.

Evaluation of fixability, offset image quality, and durability was performed according to the following procedure.

The fixing performance was evaluated by leaving the evaluation machine overnight in a low temperature, low humidity environment (15°C, 10%), and making 200 copies in a row after the evaluation machine and its internal fixing device had completely adapted to the low temperature, low humidity environment. An image was taken, and the 200th copy of the image was used for evaluation of fixability. To evaluate the fixability, move the image back and forth on symbol paper once.
The image was rubbed 0 times with a load of about 100 g, and the peeling of the image was evaluated by the rate of decrease in reflection density (%).

The offset property was evaluated by removing the cleaning mechanism of the fixing roller and determining the number of copies it took to smear the image or stain the roller.

In addition, due to dirt on the cleaning wave during continuous copying, the toner that was once removed by the cleaning wave may transfer to the upper roller and contaminate the copy, so in order to evaluate this, After returning the fixing roller cleaning mechanism to its normal state and raising the temperature setting of the fixing device by 5°C, after taking 200 consecutive copies,
Copied images were taken one by one at intervals of 0 seconds for up to 3 minutes, and the occurrence of image staining was examined, and the state of staining of the fixing roller IJ-Ning wave was evaluated.

As for the blocking property, no toner lumps were observed even by visual inspection. The fixability was 7% in terms of density reduction rate, and no offset occurred. Furthermore, there was no reflow of toner from the cleaning mechanism of the fixing device, and there were no scratches on the fixing roller even after durability.

Example 1 ■Eye 2 Toner 2 having a weight average particle size of 12 μm was obtained in the same manner as in Example 1 using the above materials. The viscoelastic properties of this toner are shown in Tables 3 and 4, and the composite curve is shown in FIG.

0.4 parts by weight of hydrophobic colloidal silica was externally added to 100 parts by weight of the above toner.

Table 5 shows the results of the same evaluation as in Example 1 using this toner.

Toner 3 having a weight average particle size of 8 μm was obtained in the same manner as in Example 1 using the above materials. The viscoelastic properties of this toner are shown in Tables 3 and 4, and the composite curve is shown in FIG.

06 parts by weight of hydrophobic colloidal silica was externally added to 100 parts by weight of the above toner.

Table 5 shows the results of the same evaluation as in Example 1 using this toner.

Toner 4 having a weight average particle size of 8 μm was obtained in the same manner as in Example 1 using the above materials. The viscoelastic properties of this toner are shown in Tables 3 and 4, and the composite curve is shown in FIG.

To 100 parts by weight of the above toner, 0.6 parts by weight of hydrophobic colloidal silicone was externally added.

Table 5 shows the results of the same evaluation as in Example 1 using this toner.

Resin (E) 100 parts by weight 1
Propylene copolymer 4 parts by weight Toner 5 having a weight average particle size of 8 μm was obtained in the same manner as in Example 1 using the above materials. The viscoelastic properties of this toner are shown in Tables 3 and 4, and the composite curve is shown in FIG. 9.

0.6 parts by weight of hydrophobic colloidal silica was externally added to 100 parts by weight of the above toner.

Table 5 shows the results of the same evaluation as in Example 1 using this toner. In this example, NP-8582 was modified and an electrophotographic copying machine equipped with a negatively chargeable amorphous silicon photoreceptor was used.

Higame Egami Toner 6 having a weight average particle size of 8 μm was obtained in the same manner as in Example 1 using the above materials. The viscoelastic properties of this toner are shown in Tables 3 and 4, and the composite curve is shown in FIG.

0.6 parts by weight of hydrophobic colloidal silica was externally added to 100 parts by weight of the above toner.

Table 5 shows the results of the same evaluation as in Example 1 using this toner. Since re-crosslinking is not performed, sufficient dynamic elastic modulus cannot be obtained in the high temperature section, resulting in poor offset resistance.

Toner 7 having a weight average particle size of 8 μm was obtained in the same manner as in Example 1 using the above materials. However, the kneading machine uses only a forward feed shaft in the kneading zone, and the set temperature is 150.
℃. The characteristics of this toner are shown in Tables 3 and 4, and the composite curve is shown in FIG.

0.6 parts by weight of hydrophobic colloidal silica was externally added to 100 parts by weight of the above toner.

Table 5 shows the results of the same evaluation as in Example 1 using this toner. Because the molecules are re-crosslinked before they are sufficiently cut, the dynamic elastic modulus is lower than the dynamic elastic modulus at high temperatures even though the glass transition point is low, resulting in poor fixing properties and the glass transition point. Due to this, blocking resistance is also poor.

Table 4 Viscoelastic properties and loss tangent at 100°C Table 5 Evaluation results ◎ Excellent ○: Good △ Acceptable × Not possible [Effects of the invention] Since the present invention is a toner having specific viscoelastic properties, the following It exhibits excellent effects.

(1) It is a toner that fixes at a low temperature and has excellent offset resistance.

(2) It is an excellent toner that does not leak out from the fixing cleaning member.

(3) The toner has excellent fixing properties and blocking resistance.

[Brief explanation of the drawing]

Figures 1 to 3 show schematic diagrams of viscoelastic properties, Figure 4 shows the dynamic elastic modulus of the resin before and after kneading, and Figures 5 to 11 show the reference temperature of each toner at 160°C. This is a viscoelasticity-frequency composite curve when In this figure, only the lines connecting the measurement points are shown. Applicant: Canon Co., Ltd. -1 = 1 ・ \-Ichimata/'

Claims (5)

[Claims] (1) A toner containing at least a resin, a colorant, and a metal-containing compound is heated at a frequency of 1 x 10^-^2 to 1 Hz and a temperature of 1
In the dynamic elastic modulus and loss modulus measured in the range of 00 to 200°C, the dynamic elastic modulus at 200°C is 1 x 10^3
~5×10^4dyn/cm^2, loss modulus is 5×1
The dynamic elastic modulus is within the range of 0^2 to 5 x 10^4 dyn/cm^2, the dynamic elastic modulus is larger than the loss elastic modulus, and the dynamic elastic modulus and loss elastic modulus at 100°C are 5 x 10^6 dyn/cm^2. cm^
2 or less, and in a composite curve according to the time-temperature conversion law, the increase in the loss modulus is larger than the increase in the dynamic modulus due to the increase in the elastic modulus as the frequency increases, and the dynamic modulus is An electrostatic image developing toner characterized by having a point where the loss modulus is equal to or larger than the loss modulus. (2) In the dynamic elastic modulus and loss elastic modulus of the toner measured at a temperature of 200°C and a frequency of 1 x 10^-^1 Hz,
Dynamic elastic modulus after holding for 60 minutes is 1 x 10^3 ~ 5 x 10^
At 4 dyn/cm^2, the loss modulus is 5 x 10^2 ~ 5 x
Claim (1) falling within the range of 10^4dyn/cm^2
The electrostatic image developing toner described in . (3) Claim (1) or (3) wherein the amount of change over time in the dynamic elastic modulus and loss modulus of the toner measured at a temperature of 200° C. and a frequency of 1×10^-^1 Hz is less than twice per 60 minutes. 2) The toner for developing electrostatic images. (4) Claim (1) wherein the resin has an acid value of 2 to 100 mgKOH/g as measured by a method according to JISK-0070.
) to (3). (5) The dynamic elastic modulus of the resin measured at a frequency of 1 x 10^-^2 to 1 Hz and a temperature of 200°C is 1 x 10^2 dy.
The toner for electrostatic image development according to any one of claims (1) to (4), which has a particle size of n/cm^2 or more.