JP3210244B2 - Electrostatic image developing toner, image forming method and process cartridge - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known as described in Japanese Patent Publication No. JP-A-Heisei, 43-24878 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. Forming and then developing the latent image with toner,
After transferring the toner image to a transfer material such as paper as necessary,
This is for obtaining a copy fixed by heating, pressure, heating and pressurizing, or solvent vapor, and the toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

In recent years, such copying apparatuses have begun to be used not only as office work copying machines for simply copying original documents, but also as printers as personal computer outputs or personal copying machines for individuals. .

[0004] Therefore, smaller, lighter, faster, and more reliable devices have been strictly pursued, and machines have become simpler in various aspects. As a result, the performance required of the toner has become higher, and if the performance of the toner cannot be improved, a better machine cannot be realized.

For example, various methods and apparatuses have been developed for fixing a toner image to a sheet such as paper. For example, there are a pressure heating method using a heat roller, and a heat fixing method in which a heating member is brought into close contact with a heating member via a film.

In the heating method using a heating roller or a film, the toner is fixed by allowing the toner image surface of the sheet to be fixed to pass through the surface of the heat roller or the film formed of a material having a releasable property to the toner. Is performed. In this method, since the surface of the heat roller or the film comes into contact with the toner image of the sheet to be fixed, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. Very good in electrophotographic copiers. However, in the above method, a part of the toner image adheres to and transfers to the fixing roller or film surface because the heat roller or the film surface and the toner image come into contact in a molten state, and the toner image re-transfers to the next fixing sheet. A so-called offset phenomenon occurs, and the sheet to be fixed may be stained. Preventing the toner from adhering to the heat fixing roller and the film surface is one of the essential conditions of the heat fixing method.

Conventionally, for the purpose of preventing toner from adhering to the surface of the fixing roller, for example, the surface of the roller is formed of a material having excellent releasability with respect to the toner, such as silicone rubber or a fluorometer resin, and the surface of the roller is prevented from being offset. In order to prevent the roller surface from being fatigued, the roller surface is coated with a thin film of a liquid having good releasability such as silicone oil. Although this method is extremely effective in preventing toner offset, it has a problem that a fixing device is required because a device for supplying an anti-offset liquid is required.

[0008] This is in the opposite direction of miniaturization and weight reduction, and moreover, silicone oil and the like may evaporate due to heat and contaminate the inside of the machine. Therefore, instead of using a silicone oil supply device, instead of supplying the anti-offset liquid during heating from the toner, a method of adding a release agent such as low molecular weight polyethylene or low molecular weight polypropylene to the toner is proposed. Have been. If a large amount of such an additive is added in order to obtain a sufficient effect, filming on a photoreceptor or contamination of the surface of a toner carrier such as a carrier or a sleeve will cause deterioration of an image and pose a practical problem. Therefore, a small amount of release agent is added to the toner to such an extent that the image is not deteriorated, and a small amount of release oil is supplied or the offset toner is cleaned by a roll-up type device using a member such as a web. It has been used together.

However, in view of recent demands for miniaturization, weight reduction, and high reliability, it is necessary and preferable to remove even these auxiliary devices. Therefore, it cannot be coped with without further improvement in performance such as toner fixing property and anti-offset property, and it is difficult to realize this without further improvement of the binder resin and the release agent of the toner.

It is known that a wax is contained in a toner as a release agent. For example, JP-A-52-330
No. 4, JP-A-52-3305, JP-A-57-3305.
A technique such as 52574 is disclosed.

[0011] These waxes are used to improve the offset resistance of the toner at low and high temperatures. However, while these properties are improved, blocking resistance is deteriorated and developability is deteriorated.

Further, as a toner containing two or more types of wax in order to exert the effect of adding wax from a low temperature region to a high temperature region, for example, Japanese Patent Publication No.
3305, JP-A-58-215659, JP-A-62-100775, JP-A-4-12467.
No. 6, JP-A-4-299357, 4-362.
Japanese Unexamined Patent Publication No. 953, Japanese Unexamined Patent Publication No. 5-197192 and the like have been disclosed.

However, even with these toners, not all performances can be satisfied, and some problems have arisen. For example, high-temperature offset resistance and developability are excellent, but low-temperature fixability is just one step away, or low-temperature offset resistance and low-temperature fixability are excellent, but blocking resistance is slightly inferior and developability decreases. And the offset resistance at low and high temperatures is not compatible.Blotch occurs due to uneven toner coating due to free wax components, causing image defects and fogging on the image. Was happening.

The waxes contained in these toners have a wax component which merely exists in a wide or fluctuating temperature range with respect to an endothermic peak at the time of temperature rise of a DSC curve measured by a differential scanning calorimeter. However, it contained many components that were insufficient to satisfy the above-mentioned performance, or degraded or had little effect.

[0015]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above problems.

That is, an object of the present invention is to provide a toner for developing an electrostatic charge image, an image forming method, and a process cartridge which are excellent in low-temperature fixing property and anti-offset property and have a wide fixing temperature range.

It is a further object of the present invention to provide a toner for developing electrostatic images, an image forming method and a process cartridge which have excellent blocking resistance and do not deteriorate developability.

It is a further object of the present invention to provide a toner for developing an electrostatic image, an image forming method, and a process cartridge which do not cause fusing on a photosensitive member.

Still another object of the present invention is to provide a toner for developing an electrostatic charge image, an image forming method and a process cartridge, which reduce the amount of free wax components and does not cause blotting due to poor toner coat uniformity on a toner carrier of a developing device. To provide.

It is a further object of the present invention to provide a toner for developing an electrostatic image without fogging on an image, an image forming method and a process cartridge.

[0021]

SUMMARY OF THE INVENTION The present invention relates to a toner for developing an electrostatic image containing at least a binder resin and a wax, the endothermic peak of the DSC curve of the wax measured by a differential scanning calorimeter when the temperature is raised. The minimum onset temperature of the endothermic peak is 50 ° C. or more,
0 has at least one endothermic peak each temperature region of the temperature range and 90 to 150 ° C. in ° C., P ₁ when the maximum endothermic peak at each temperature range was P _1, P ₂ and P ₂
Is 15 ° C. or more, and the GP
Respect chromatogram as measured by C, the wax component is a weight average molecular weight which constitutes the endothermic peak P ₁ (M
w) and the number average molecular weight (Mn) ratio Mw / Mn is 1.7.
Or less, it is to achieve the above object by wherein the wax component constituting the endothermic peak P ₂ is the ratio Mw / Mn is 5 or less.

Further, in a DSC curve of the wax measured by a differential scanning calorimeter, an endothermic peak at the time of temperature rise,
What achieves the above object by having an onset temperature at a start point of an endothermic peak in a temperature range of 90 to 150 ° C. higher than an onset temperature at an end point of an endothermic peak in a temperature range of 60 to 90 ° C. It is.

Further, in the endothermic peak at the time of temperature rise in the DSC curve of the wax measured by the differential scanning calorimeter,
The minimum onset temperature of the endothermic peak is 50 ° C. or higher, and has at least one endothermic peak in each of a temperature range of 60 to 90 ° C. and a temperature range of 100 to 150 ° C., and a maximum endothermic peak in each temperature range. the is intended to achieve the object by the peak temperature difference between P ₁ and P ₂ when the P _1, P ₂ is characterized in that at 20 ° C. or higher.

Further, in a DSC curve of the wax measured by a differential scanning calorimeter, an endothermic peak at the time of temperature rise,
What achieves the above object by having an onset temperature at a start point of an endothermic peak in a temperature range of 100 to 150 ° C. higher than an onset temperature at an end point of an endothermic peak in a temperature range of 60 to 90 ° C. It is.

Further, in a DSC curve of the wax measured by a differential scanning calorimeter, an endothermic peak at the time of temperature rise,
It is intended to achieve the object by wherein the difference between the peak temperature of the peak temperature and said maximum endothermic peak P ₂ of said maximum endothermic peak P ₁ is 20 ° C. or higher.

Further, in a DSC curve of the wax measured by a differential scanning calorimeter, the endothermic peak at the time of temperature rise is as follows:
In which the difference between the peak temperature of the peak temperature and said maximum endothermic peak P ₂ of said maximum endothermic peak P ₁ is to achieve the object by wherein a is 25 ° C. or higher.

Further, in the endothermic peak at the time of temperature rise of the DSC curve measured by the differential scanning calorimeter of the wax,
It is intended to achieve the object by wherein the difference between the peak temperature of the peak temperature and said maximum endothermic peak P ₂ of said maximum endothermic peak P ₁ is 30 ° C. or higher.

Further, the present invention relates to a toner for developing an electrostatic image containing at least a binder resin and a wax, which has an endothermic peak at a temperature rise of 65 to 65 in a DSC curve of the toner measured by a differential scanning calorimeter. has at least one endothermic peak each temperature region of the temperature range and 95 to 130 ° C. in 85 ° C., P ₃ and the peak temperature of P ₄ when the maximum endothermic peak was P _3, P ₄ at each temperature region The difference is 50 ° C. or less, the Tg of the toner is 50 to 65 ° C., and the binder resin has a molecular weight of 3 in a molecular weight distribution determined by gel permeation chromatography (GPC).
× is intended to achieve the object by further comprising a respective peak 10 3 ^{to 5} × 10 ⁴ region and molecular weight ¹⁰⁵ or more regions.

Further, at the endothermic peak at the time of temperature rise of the DSC curve of the toner measured by a differential scanning calorimeter, 6
It has at least one endothermic peak in the temperature range of 5 to 85 ° C. and 100 to 130 ° C., and the maximum endothermic peak in each temperature range is P ₃ , P _4
3 and the peak temperature difference of P ₄ is not less 50 ° C. or less, in which Tg of the toner to achieve the object by being a 50-65 ° C..

Further, the present invention provides a step of applying a voltage to the latent image holding member to charge the latent image holding member, a step of forming an electrostatic latent image on the charged latent image holding member, and a step of forming a toner image. An image forming method comprising a step of developing an electrostatic latent image formed on a holding member with a toner carried on a toner carrying member, wherein the toner contains at least a binder resin and a wax, and the wax In the endothermic peak at the time of temperature rise of the DSC curve measured by the differential scanning calorimeter, the minimum onset temperature of the endothermic peak is 50 ° C. or more,
When at least one endothermic peak is present in each of a temperature range of 60 to 90 ° C. and a temperature range of 90 to 150 ° C., and the maximum endothermic peaks in each temperature range are P ₁ and P ₂ , P
₁ and peak temperature difference between P ₂ is at 15 ℃ or more, with respect chromatogram as measured by GPC of the wax,
The ratio Mw / Mn of the wax component forming the endothermic peak _{P 1} is the weight average molecular weight (Mw) to number average molecular weight (Mn)
There is 1.7 or less, by the wax component constituting the endothermic peak P ₂ is and a ratio Mw / Mn is 5 or less, is to achieve the above object.

Further, the present invention provides a step of applying a voltage to the latent image holding member to charge the latent image holding member, a step of forming an electrostatic latent image on the charged latent image holding member, and a step of forming the latent image to form a toner image. An image forming method comprising a step of developing an electrostatic latent image formed on a holding member with a toner carried on a toner carrying member, wherein the toner contains at least a binder resin and wax, and In the endothermic peak at the time of temperature rise of the DSC curve measured by the differential scanning calorimeter, 65
Has at least one endothermic peak each temperature region of the temperature range and 95 to 130 ° C. of to 85 ° C., the peak of the _{P 3} and _{P 4} when the maximum endothermic peak was _P 3, _{P 4} at each temperature region The temperature difference is 50 ° C. or less, and the T
g is 50-65 ° C., the binder resin, the molecular weight distribution by gel-Mei chromatography (GPC), the molecular weight 3 × ¹⁰ 3 to 5 × respectively 10 ⁴ region and molecular weight ¹⁰⁵ or more regions The object is achieved by having a peak.

Further, according to the present invention, in a process cartridge detachable from the main body of the image forming apparatus, the process cartridge is held by a latent image holding member for holding an electrostatic latent image and the latent image holding member. Developing means for developing the electrostatic latent image, the developing means comprising a toner containing at least a binder resin and a wax, a toner container containing the toner, and a toner contained in the toner container Having a toner carrier for carrying and transporting the wax, and having a DS measured by a differential scanning calorimeter of the wax.
In the endothermic peak at the time of temperature rise of the C curve, the minimum onset temperature of the endothermic peak is 50 ° C. or more, and 60 to 90 ° C.
Has at least one endothermic peak each temperature region of the temperature range and 90 to 150 ° C., the peak temperature difference between P ₁ and P ₂ when the maximum endothermic peak was P _1, P ₂ at the respective temperature regions and at 15 ℃ or more, with respect chromatogram as measured by GPC of the wax, the wax component is a weight average molecular weight which constitutes the endothermic peak P ₁ (Mw)
When the number ratio Mw / Mn of the average molecular weight (Mn) of 1.7 or less, the object by wherein the wax component constituting the endothermic peak P ₂ is the ratio Mw / Mn is 5 or less Is to achieve.

Further, the present invention relates to a process cartridge detachably mountable to an image forming apparatus main body, wherein the process cartridge is held by a latent image holding member for holding an electrostatic latent image and the latent image holding member. Developing means for developing the electrostatic latent image, the developing means comprising a toner containing at least a binder resin and a wax, a toner container containing the toner, and a toner contained in the toner container Having a toner carrier for carrying and transporting the toner, the DSC of which is measured by a differential scanning calorimeter.
In the endothermic peak at the time of temperature rise of the curve, the curve has at least one endothermic peak in each of a temperature region of 65 to 85 ° C and a temperature region of 95 to 130 ° C, and the maximum endothermic peak in each temperature region is P ₃ , P peak temperature difference between _{P 3} and _{P 4 when 4} and the is at 50 ° C. or less, Tg of the toner is from 50 to 6
A 5 ° C., the binder resin, the molecular weight distribution by gel-Mei chromatography (GPC), have a molecular weight 3 ^× 10 3 ~5 × 10 ^4, respectively peak in the region and molecular weight ¹⁰⁵ or more regions of the The above object is achieved by the features described above.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Further, the present invention will be described in detail.

In the present invention, by analyzing the data of the DSC curve measured by the differential scanning calorimeter of the wax, an endothermic peak accompanying the transition and melting of the wax is observed, especially at the time of raising the temperature, and heat is applied to the wax. You can see the change when given.

The wax contained in the toner of the present invention is:
It has at least one endothermic peak in the temperature range of 60 to 90 ° C. and 90 to 150 ° C., and the maximum endothermic peaks in each temperature range are P ₁ and P _2, and P ₁
And the peak temperature difference between P ₂ and 15 ° C. or more,
By wax component constituting the said maximum endothermic peak P ₁ is relatively melted at a low temperature of temperature range, give a plasticizing effect to the binder resin, improving the low-temperature offset property and low-temperature fixability. Further, by the wax component constituting the said maximum endothermic peak P ₂ is melted at a relatively high temperature of the temperature range, the release effect appeared good hot offset resistance can be obtained.

When the minimum onset temperature of the endothermic peak is 50 ° C. or higher, an excessive plasticizing effect on the low molecular weight component of the binder resin is suppressed, so that the blocking resistance can be guaranteed. .

When the maximum endothermic peak P ₁ is less than 60 ° C. or the minimum onset temperature of the endothermic peak is less than 50 ° C., the wax melting onset temperature becomes too low, and the plasticizing effect starts from a very low temperature. And the developability deteriorates.

[0039] If said maximum endothermic peak P ₁ is higher than 90 ° C. is not obtained a sufficient plasticizing effect to the binder resin can not be obtained good low-temperature fixability.

If the maximum endothermic peak P ₂ does not exist at 100 ° C. or higher, the wax melts quickly,
High temperature offset resistance at high temperatures cannot be satisfied.

If the maximum endothermic peak P ₂ does not exist at 90 ° C. or higher, the wax melts quickly, so that high-temperature offset resistance at high temperatures cannot be satisfied.

When the maximum endothermic peak P ₂ exceeds 150 ° C., the melting temperature of the wax is too high, so that a sufficient releasing effect cannot be exerted in a operable temperature range of a fixing device such as a copying machine. The high temperature offset resistance is inferior.

When the difference between the peak temperature of the maximum endothermic peak P _{1 and} the peak temperature of the maximum endothermic peak P ₂ is less than 15 ° C., the wax component in the melting temperature range that contributes to low-temperature fixability and high-temperature offset resistance. Interact and cannot effectively exert both performances.

Further, the above-mentioned wax is preferably 6
It is preferable to have at least one endothermic peak in each of a temperature range of 0 to 90 ° C. and a temperature range of 95 to 150 ° C., and more preferably a temperature range of 60 to 90 ° C.
It is preferable to have at least one endothermic peak in the temperature range of ~ 150 ° C, more preferably 65 ~ 150 ° C.
It is preferable to have at least one endothermic peak in each of a temperature range of 85 ° C. and a temperature range of 105 to 130 ° C.
As a result, both the fixing property and the developing property can be achieved, and good images can be continuously obtained.

Preferably, the difference between the peak temperature of the maximum endothermic peak P _{1 and} the peak temperature of the maximum endothermic peak P ₂ is 20.
C. or higher, more preferably 25 ° C. or higher. Thereby, an excessive plasticizing effect of the wax component of the endothermic peak including the maximum endothermic peak P ₁ on the wax component of the endothermic peak including the maximum endothermic peak P ₂ can be suppressed, and the latitude for preventing fusion on the photoreceptor can be reduced. Can be further expanded.

[0046] More preferably, the endothermic peak during the temperature increase of the DSC curve measured by a differential scanning calorimeter of wax, the endothermic peak temperature range of 60 to 90 ° C. containing said maximum endothermic peak P ₁ of the end point Onsetsuto may be onset temperature of the starting point of the endothermic peak temperature range of 90 to 150 ° C. containing said maximum endothermic peak P ₂ is higher than the temperature, more preferably comprises a said maximum endothermic peak P ₁ sixty to nine
0 onset temperature of the starting point of the endothermic peak temperature range of 100 to 150 ° C. containing said maximum endothermic peak P ₂ than the onset temperature of the end point of the endothermic peak temperature range of ° C. higher is better. As a result, the amount of wax components in the melting temperature range that does not significantly contribute to the performance of both the low-temperature fixing property and the high-temperature offset resistance is reduced, and more wax components are present in the melting temperature range in which each performance is most exhibited. As a result, the amount of free wax components is reduced, the uniformity of the toner coat on the toner carrier of the developing device is impaired, and the phenomenon of so-called blotching, which results in a partially uneven toner coat, is less likely to occur.

60 to 90 ° C. including the maximum endothermic peak P ₁
The onset temperature of the end point of the endothermic peak temperature region, if the outermost endothermic peak temperature range of 90 to 150 ° C. containing large endothermic peak P ₂ above onset temperature of the starting point, the low-temperature fixability and high-temperature offset resistance Since the proportion of the wax component in the melting temperature range that does not greatly contribute to any of the above performances increases, both performances cannot be remarkably improved.

Further, if a large amount of wax is contained in order to improve both performances, a defect occurs on an image due to the occurrence of blotches.

Particularly preferably, the difference between the peak temperature of the maximum endothermic peak P _{1 and} the peak temperature of the maximum endothermic peak P ₂ is at least 25 ° C., more preferably at least 30 ° C. This further clarifies the functional separation of the wax component, so that low-temperature fixability and high-temperature offset resistance can be compatible without inconsistency, and fogging on an image is eliminated.

The wax contained in the toner of the present invention is
Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; or block copolymers thereof; carnauba wax; Waxes mainly containing fatty acid esters such as sasol wax and montanic acid ester wax; and those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax. Further, saturated straight-chain fatty acids such as palmitic acid, stearic acid, montanic acid, and long-chain alkyl carboxylic acids having a longer-chain alkyl group; unsaturated fatty acids such as brandinic acid, eleostearic acid, and barinaric acid Saturated alcohols such as stearin alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, seryl alcohol, melisyl alcohol, or long-chain alkyl alcohols having a longer-chain alkyl group; polyhydric alcohols such as sorbitol; Fatty acid amides such as acid amide, oleic acid amide, lauric acid amide; saturated fatty acids such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide Unsaturated fatty acid amides such as samides, ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N, N'-dioleyladipamide, N, N'-dioleylsebacic acid amide; m-xylene bis Aromatic bisamides such as stearic acid amide and N, N 'distearyl isophthalic acid amide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metallic soaps); Waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; obtained by hydrogenation of vegetable oils and fats Has a hydroxyl group Such that methyl ester compounds.

The wax preferably used is a low-molecular-weight alkylene polymer obtained by subjecting an alkylene to radical polymerization under high pressure or polymerized under low pressure using a Ziegler catalyst or other catalyst, or an alkylene obtained by thermally decomposing a high-molecular-weight alkylene polymer. Polymers, low-molecular-weight alkylene polymers produced as by-products when polymerizing alkylene polymers are separated and purified, from the distillation residue of hydrocarbons obtained by the Atage method from synthesis gas consisting of carbon monoxide and hydrogen, or hydrogenated from these A wax obtained by extracting and separating a specific component from a synthetic hydrocarbon or the like obtained by the above method may be used, and an antioxidant may be added. Alternatively, it is a linear alcohol, fatty acid, acid amide, ester or montan derivative. It is also preferable that impurities such as fatty acids have been removed in advance.

Among them, preferred are those obtained by polymerizing an olefin such as ethylene using a Ziegler catalyst or another catalyst, by-products at this time, such as Fischer-Tropsch wax having a carbon number of several thousand, especially up to about 1,000. Those having a hydrocarbon as a base are preferred. Further, a long-chain alkyl alcohol having a hydroxyl group at the terminal having several hundred carbon atoms, particularly up to about one hundred carbon atoms, is also preferable. Further, those obtained by adding an alkylene oxide to an alcohol are also preferably used.

From these waxes, the waxes are subjected to press sweating, solvent method, vacuum distillation, supercritical gas extraction, fractional crystallization (for example, melt liquid crystal precipitation and crystal filtration), etc., to obtain waxes having different molecular weights. The fractionated wax whose molecular weight distribution was sharpened was obtained by a differential scanning calorimeter (DS).
It is more preferable because the endothermic peak at the time of temperature rise in the C curve becomes sharp, and the proportion of components in the necessary melting behavior range increases. Among them, the use of two or more kinds of the waxes separated in this way, the low-temperature fixing property, the blocking resistance and the high-temperature offset resistance, the wax component of the melting behavior range necessary to improve these properties in a well-balanced manner. It is particularly preferable because it can be contained in the toner without waste.

In order to incorporate the wax into the toner according to the present invention, the wax, the binder resin and other additives are sufficiently mixed by a mixer such as a ball mill and then heated by a heating roll, kneader, extruder or the like. Melting using a kneader,
After kneading and kneading, the resins are mutually dissolved, and after cooling and solidification, pulverization is performed.

When two or more kinds of waxes are to be contained, the waxes are melted and mixed in advance while stirring at a temperature not lower than the wax melting temperature, cooled, solidified and then pulverized.

The binder resin is dissolved in a solvent, the temperature of the resin solution is raised, wax is added and mixed with stirring, and after removing the solvent and drying, pulverizing is performed. And the like. Preferably, the method is good in terms of the dispersibility of the wax in the toner, and more preferably, the method is excellent in terms of production stability.

When the toner of the present invention contains two or more kinds of the wax, the wax is compared with respect to an endothermic peak at the time of temperature rise in a DSC curve of the wax measured by a differential scanning calorimeter. At least one kind is, for example, 0.1 to 15 parts by weight (preferably 0.5 to 10 parts by weight) of a wax having an endothermic peak in a low temperature region of 40 to 100 ° C., and at least one kind is, for example, 90 to 160 ° C. It is preferable to contain 0.1 to 12 parts by weight (preferably 0.5 to 10 parts by weight) of a wax having an endothermic peak in a high temperature region.

In addition, the wax in the other temperature range is added to 0.1%.
1-10 parts by weight (preferably 0.5-7 parts by weight) may be contained.

Thus, the low-temperature fixability and the offset resistance performance can be effectively improved without impairing the blocking resistance.

In the toner of the present invention, the total content of these waxes is 0.2 to 100 parts by weight of the binder resin.
It is effective to use at 20 to 20 parts by weight, preferably 0.5 to 10 parts by weight.

The wax which can be contained in the toner of the present invention is:
In the endothermic peak at the time of temperature rise of the DSC curve measured by the differential scanning calorimeter of the wax, the maximum endothermic peak P
₁ (H ₁ ) and the maximum endothermic peak P ₂ (H
₃ ) and the height of the minimum value (H ₂ ) between the two peaks, H ₁ : H ₂ : H ₃ = (0-0.5) :( 0.1-10.
0) is preferably satisfied (an example of Embodiment 9 of the present invention is shown in FIG. 3 as a specific example). If the maximum endothermic peak P ₂ of the height (H ₃₎ is 0.1 to 1.5 is particularly preferred. If the height (H ₃ ) of the maximum endothermic peak P ₂ is less than 0.1, the effect of releasing the wax is less likely to be exhibited.
Offset resistance is impaired. On the other hand, when the height (H ₃ ) of the maximum endothermic peak P ₂ exceeds 10.0, the content of the low-temperature component effective for the plasticizing effect is relatively reduced, and the low-temperature fixability is poor. The height of the minimum value between the two peaks (H ₂ )
Is more than 0.5, the amount of wax components not effectively contributing to low-temperature fixability and offset resistance increases as a whole, and the effect is reduced.

In the DSC measurement in the present invention, it is preferable to use a high-precision internal heating type input compensation type differential scanning calorimeter in view of the measurement principle. For example, DSC-7 manufactured by PerkinElmer can be used.

The measuring method is as described in ASTM D3418-82.
Perform according to. The DSC curve used in the present invention is obtained by raising and lowering the temperature once, taking a pre-history, and then setting the temperature rate to 10 ° C./m.
In, a DSC curve measured when the temperature is raised is used. The definition of each temperature is defined as follows (heat is taken in the plus direction. Examples of the first and ninth embodiments of the present invention are shown in FIGS. 1 and 2, respectively).

<Temperature at all endothermic peaks> Minimum onset temperature of endothermic peak (S ₁ -OP) The temperature at the intersection of the tangent to the base line and the base line at the point where the differential value of the curve at the time of temperature increase is maximum. Lowest temperature in.

<60 to 90 ° C. including the maximum endothermic peak P ₁
Temperature at the endothermic peak in the temperature range of ( ₁ )> Peak temperature of maximum endothermic peak (P ₁ P) Peak top temperature of the maximum endothermic peak in the temperature range of 60 to 90 ° C. when the temperature is raised.

The onset temperature at the end point of the endothermic peak (E
_1- OP) The temperature at the intersection of the tangent to the curve and the base line at the point where the differential value of the curve at the time of temperature rise is finally minimized.

[0067] <90 to 150, including the maximum heat absorption peak P ₂
Each temperature at endothermic peak in temperature range of ° C.> Peak temperature of maximum endothermic peak (P ₂ P) Peak top temperature of maximum endothermic peak in a temperature range of 90 to 150 ° C. when temperature is raised.

The onset temperature at the start of the endothermic peak (S
_2- OP) The temperature at the intersection of the tangent of the curve and the baseline at the point where the differential value of the curve at the time of temperature rise is first maximized.

The wax contained in the toner of the present invention is
With respect to the chromatogram of the wax measured by GPC (gel permeation chromatography), the wax component constituting the maximum endothermic peak P ₁ was Mn of 1
00-2,000, Mw / Mn is 2.0 or less (preferably 1.7 or less, more preferably 1.5 or less), and the wax component constituting the maximum endothermic peak P _2, Mn is 20
0 to 8000, and Mw / Mn of 7 or less (preferably 5 or less, more preferably 3 or less), the molecular weight distribution of each wax component is sharper, so that low-temperature fixability, blocking resistance and offset resistance are achieved. It does not contain any unnecessary components for effectively improving the properties, and can satisfy the object of the present invention.

In the present invention, the molecular weight distribution of the wax is G
It is measured by a PC under the following conditions.

Apparatus: GPC-150C (Waters) Column: GMH-HT 30 cm double (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (added with 0.1% ionol) Flow rate: 1 0.0 ml / min sample: 0.4 ml of 0.15% sample injected

Measurement is performed under the above conditions, and the molecular weight of the sample is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. In addition, Mark-Hou
It is calculated by converting to polyethylene using a conversion formula derived from the wink viscosity formula.

As described above, the present invention can also be achieved by the following electrostatic image developing toner. That is, in the toner for developing an electrostatic image containing at least a binder resin and a wax component, a temperature range of 65 to 85 ° C. is used in an endothermic peak at the time of temperature rise of a DSC curve measured by a differential scanning calorimeter of the toner. It has at least one endothermic peak in a temperature range of 95 to 130 ° C, and preferably has at least one endothermic peak in a temperature range of 65 to 85 ° C and a temperature range of 100 to 130 ° C. The maximum endothermic peak in the region is P ₃ , P
By peak temperature difference between P ₃ and P _{4 when 4} and the it is 50 ° C. or less, developing property can be obtained with good fixation. Further, the Tg of the toner is 50 to 65 ° C, preferably 50 to 60 ° C.
By doing so, it is possible to ensure blocking resistance while ensuring good fixing properties.

When the maximum endothermic peak P ₃ is less than 65 ° C. or the Tg of the toner is less than 50 ° C., the toner undergoes a plastic change from a relatively low temperature for a long period of time, causing deterioration in blocking resistance and developability. Cheap.

If the maximum endothermic peak P ₃ exceeds 85 ° C. or the Tg of the toner exceeds 65 ° C., the temperature at which the composition of the toner starts to change becomes high, and good low-temperature fixability cannot be obtained.

When the maximum endothermic peak P ₄ does not exist at 95 ° C. or higher, the wax component in the toner melts before the temperature becomes relatively high, and a sufficient releasing effect cannot be obtained at the high temperature.

When the maximum endothermic peak P ₄ exceeds 130 ° C., the wax is not melted to the extent that the releasing effect can be exhibited near the high temperature offset start temperature of the toner, and the high temperature offset resistance is improved. It doesn't matter.

When the peak temperature difference between the maximum endothermic peak P ₃ and the maximum endothermic peak P ₄ is 50 ° C. or more, it is difficult to achieve both the plasticizing effect and the releasing effect of the wax component in the toner, and the low-temperature fixing property Further, it is impossible to provide a toner satisfying both the blocking resistance and the high-temperature offset resistance at the same time.

The DSC measurement of the toner is based on the above-described wax, and the definition of each temperature is defined as follows (the positive direction is assumed to be endothermic. As a specific example, an example of Example 9 of the present invention is shown in FIG. 4). Shown).

<65 to 85 ° C. including the maximum endothermic peak P ₃
Each temperature at endothermic peak in temperature range of (1)> Peak temperature of maximum endothermic peak (P ₃ P) Peak top temperature of maximum endothermic peak in a temperature range of 65 to 85 ° C. when temperature is raised.

<100 to 13 including the maximum endothermic peak P ₄
Each temperature in endothermic peak in temperature range of 0 ° C.> Peak temperature of maximum endothermic peak (P ₄ P) Peak top temperature of maximum endothermic peak in a temperature range of 95 to 130 ° C. at the time of temperature rise.

<Temperature at all endothermic peaks> Tg (glass transition point temperature) of toner In the DSC curve at the time of temperature rise, the temperature at the intersection of the DSC curve and the line connecting the midpoint of the baseline before and after the specific heat change appears. .

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

For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene and their substituted products; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene Copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Styrene such as vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer -Based copolymer; polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin , Xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin and the like can be used. Preferred binders include styrene copolymers or polyester resins.

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

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

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

The method for synthesizing the binder resin may be any of a bulk polymerization method, a solution polymerization method, a suspension polymerization method and an emulsion polymerization method.

In the bulk polymerization method, a polymer having a low molecular weight can be obtained by increasing the termination reaction rate by polymerizing at a high temperature, but there is a problem that the reaction is difficult to control.
In the solution polymerization method, a low molecular weight polymer 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 the initiator and the reaction temperature. It is preferable when a low molecular weight compound is obtained in the composition.

As the solvent used in the solution polymerization, xylene, toluene, cumene, cellosolve acetate, isopropyl alcohol, benzene and the like are used. In the case of a styrene monomer mixture, xylene, toluene or cumene is preferred. It is appropriately selected depending on the polymer to be polymerized.

The reaction temperature depends on the solvent used, the initiator and the polymer to be polymerized.
It is better to carry out at 0 ° C. In solution polymerization, solvent 100
It is preferable to carry out with 30 parts by weight to 400 parts by weight of the monomer based on parts by weight.

Further, it is preferable to mix another polymer in the solution at the end of the polymerization, and several kinds of polymers can be mixed well.

Further, as a polymerization method for obtaining a high molecular weight component or a gel component, an emulsion polymerization method or a suspension polymerization method is preferable.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, it is easy to control the heat of reaction, and since the phase in which the polymerization is carried out (the oil phase composed of the polymer and the monomer) and the aqueous phase are different, the termination reaction rate is small, and as a result, the polymerization rate is large. , With a high degree of polymerization.
Further, the reason is that the polymerization process is relatively simple, and that the polymerization product is fine particles, so that it is easy to mix with the colorant, the charge control agent, and other additives in the production of the toner. This is advantageous as compared with other methods as a method for producing a binder resin for a toner.

However, the resulting polymer tends to be impure due to the added emulsifier, and an operation such as salting out is required to take out the polymer. Therefore, suspension polymerization is a simple method.

In the suspension polymerization, 100 parts by weight or less of the monomer (preferably 1 part by weight) is added to 100 parts by weight of the aqueous solvent.
(0 to 90 parts by weight). Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, and the like. There is an appropriate amount in terms of the amount of a monomer relative to an aqueous solvent, and generally 0.05 to 1 based on 100 parts by weight of an aqueous solvent. Used in parts by weight. The polymerization temperature is suitably from 50 to 95 ° C, but should be appropriately selected depending on the initiator used and the intended polymer. As the type of initiator, any initiator that is insoluble or hardly soluble in water can be used.

The initiators used include t-butylperoxy-2-ethylhexanoate, cumin perpivalate, t-butylperoxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, -T-butyl peroxide, t
-Butylcumyl peroxide, dicumyl peroxide, 2,2'-azobisisobutyronitrile, 2,2 '
-Azobis (2-methylbutyronitrile), 2,2'-
Azobis (2,4-dimethylvaleronitrile), 2,
2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 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-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, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane,
G-tert-butyldiperoxyisophthalate, 2,2-
Bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate, di-t-butylperoxyhexahydro Terephthalate, di-t-butylperoxyazelate, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexane, diethylene glycol-bis (t-butylperoxycarbonate), di-t-butylperoxytrimethyladipate, tris (t-butylperoxy) triazine, Vinyl tris (t-butylperoxy) silane and the like can be mentioned, and these can be used alone or in combination.

The amount used is 0.05 parts by weight or more (preferably 0.1 to 15 parts by weight) with respect to 100 parts by weight of the monomer.

The composition of the polyester resin used in the present invention is as follows.

Examples of the dihydric alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, and 1,5-pentanediol. , 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-
Hexanediol, hydrogenated bisphenol A, and bisphenol represented by formula (A) and derivatives thereof;

[0101]

[Outside 1] (Wherein R is an ethylene or propylene group, x,
y is an integer of 0 or more, and the average value of x + y is 0 to 10. )

Diols represented by the formula (B):

[0103]

[Outside 2] (Wherein R ′ is —CH ₂ CH ₂ — or

[0104]

[Outside 3] Where x 'and y' are integers of 0 or more, and x '
The average value of + y 'is 0 to 10. ).

As the divalent acid component, for example, phthalic acid,
Benzenedicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides and lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides and lower alkyl esters; n- Alkenyl succinic acids or alkyl succinic acids such as dodecenyl succinic acid, n-dodecyl succinic acid, or anhydrides and lower alkyl esters thereof; fumaric acid, maleic acid, citraconic acid, unsaturated dicarboxylic acids such as itaconic acid or anhydrides, lower acids And dicarboxylic acids such as alkyl esters; and derivatives thereof.

It is preferable to use a trivalent or higher valent alcohol component which also functions as a crosslinking component and a trivalent or higher valent acid component in combination.

The polyhydric alcohol component having three or more valences includes
For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol,
1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,
3,5-trihydroxybenzene and the like.

The polyvalent carboxylic acid component having three or more valences in the present invention includes, for example, trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid,
2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,2
5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-
Octanetetracarboxylic acid, empol trimer acid, and anhydrides and lower alkyl esters thereof;

[0109]

[Outside 4] (Wherein X is an alkylene group or alkenylene group having 5 to 30 carbon atoms having at least one side chain having 3 or more carbon atoms), such as tetracarboxylic acids, and anhydrides and lower alkyl esters thereof. And polyvalent carboxylic acids and derivatives thereof.

The alcohol component used in the present invention is 40 to 60 mol%, preferably 45 to 55 mol%.
%, 60 to 40 mol% as an acid component, preferably 5%
It is preferably from 5 to 45 mol%.

It is also preferable that the content of the trivalent or higher polyvalent component is 1 to 60 mol% of all components.

From the viewpoints of developability, fixability, durability and cleaning properties, a styrene-unsaturated carboxylic acid derivative copolymer,
Polyester resins, block copolymers thereof, grafted products thereof, and furthermore, mixtures of styrene copolymers and polyester resins are preferred. The binder resin used in the toner of the present invention preferably has a Tg (glass transition point) of 50 to 50.
70 ° C.

The binder resin used in the toner of the present invention has a molecular weight distribution of 10 ⁵ as measured by GPC.
It is preferable to have a peak in the above region, and 3 ×
It is preferable to have a peak in the region of 10 ^{3 to} 5 × 10 ^{4 from} the viewpoint of fixability and durability.

In the case of a positively chargeable toner, a styrene-acryl copolymer, a styrene-methacryl-acryl copolymer, a styrene-methacryl copolymer, a styrene-butadiene copolymer, a polyester resin, Block copolymers, grafted products, and blend resins are preferable. In the case of a negatively chargeable toner, a styrene-acryl copolymer, a styrene-methacryl-acryl copolymer, a styrene-methacryl copolymer, Copolymer with maleic acid monoester, polyester resin, and block copolymers thereof, grafted product,
Blend resins are preferred in terms of developability.

In the case of the heat fixing toner, when a styrene copolymer is used as the binder resin, the effect of the wax is sufficiently exerted and the deterioration of the blocking resistance and the developing property, which are the adverse effects of the plastic effect, are prevented. Therefore, the following toners are preferable.

The molecular weight distribution of the toner measured by GPC (gel permeation chromatography) was 3 × 10
^{3 to} 5 × 10 ⁴ area, preferably 3 × 10 ^{3 to} 3 × 1
0 ⁴ areas, particularly preferably at least one peak in the region of ^{5 × 10 3 ~2 × 10 4} (P 1) that is present, it is possible to obtain good fixing properties, developability, blocking resistance . If it is less than 3 × 10 ³ , good blocking resistance cannot be obtained, and if it exceeds 5 × 10 ⁴ , good fixability cannot be obtained. The 10 ⁵ or more regions, preferably at least one peak (P ₂₎ is present in a region of ^{3 × 10 5 ~5 × 10 6} , 3 × 10 5 ~2 × 10 6 regions 10 ⁵ or more regions of the Is particularly preferable, and good high-temperature offset resistance, blocking resistance, and developability can be obtained. The larger the peak molecular weight is, the stronger the high-temperature offset becomes. However, when there is a region peak of 5 × 10 ⁶ or more, there is no problem with a hot roll to which pressure can be applied, but when pressure cannot be applied, The elasticity increases and the fixing property is affected. Therefore, in the heat fixing at a relatively low pressure used in a medium-to-low speed machine, a peak exists in a region of 3 × 10 ⁵ to 2 × 10 ⁶ , and it is preferable that this is the maximum peak in a region of 10 ⁵ or more.

Further, the component in the region of 10 ⁵ or less is 50% or more, preferably 60 to 90%, particularly preferably 65 to 8%.
5%. Within this range, good fixability is exhibited. If it is less than 50%, not only the sufficient fixing property cannot be obtained but also the pulverizability becomes inferior. On the other hand, if it exceeds 90%, it tends to be weak against the adverse effect of the plasticization effect due to the addition of wax.

When a polyester resin is used, the molecular weight distribution of the toner by GPC is from 3 × 10 ³ to 3 × 10 ³ .
1.5 × 10 ⁴ area, preferably 4 × 10 ^{3 to} 1.2
× 10 ⁴ region, particularly preferably 5 × 10 ³ to 1 × 10
It is preferable that the main peak exists in the region of No. ⁴ . Further, it is preferable that at least one peak or shoulder exists in the region of 1.5 × 10 ⁴ or more, or that the region of 5 × 10 ⁴ or more accounts for 5% or more. Also Mw / M
It is also preferable that n is 10 or more.

When the main peak is less than 3 × 10 ³ , the effect of the plastic effect due to the addition of the wax tends to be adversely affected, and the blocking resistance and the developing property are liable to be reduced. If the main peak exceeds 1.5 × 10 ⁴ , good fixability cannot be obtained. When the peak or shoulder is present in the region of 1.5 × 10 ⁴ or more, when the region of 5 × 10 ⁴ or more is 5% or more, or when Mw / Mn is 10 or more, the plastic effect due to the addition of the wax is reduced. The adverse effects can be suppressed.

In the present invention, the molecular weight distribution of the chromatogram of the toner by GPC is measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40 ° C., THF (tetrahydrofuran) as a solvent was flowed through the column at this temperature at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution was injected. Measure. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is used.
It is appropriate to use about 0 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
As the column, a plurality of commercially available polystyrene gel columns are preferably combined, and for example, showex GPC KF-801, 802, 80 manufactured by Showa Denko KK
3,804,805,806,807,800P or TSKgelG1000H (H
_{XL), G2000H (H XL)} , G3000H (H XL),
_{G4000H (H XL), G5000H (} H XL), G60
00H (H _XL ), G7000H (H _XL ), TSKgua
rdcolumn can be mentioned.

The sample is prepared as follows.

After placing the sample in THF and leaving it to stand for several hours, it is shaken sufficiently, mixed well with THF (until the sample is no longer united), and left still for 12 hours or more. Then T
The time of leaving in HF is set to 24 hours or more.
After that, the sample processing filter (pore size 0.45
0.5 μm, for example, Myshoridisk H-25
-5, manufactured by Tosoh Corp., and manufactured by Ekiclodisc 25CR manufactured by Germanic Science Japan) can be used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

In the toner according to the present invention, in addition to the above-mentioned binder resin component, the following compounds may be contained at a ratio smaller than the content of the binder resin component. For example, silicone resin, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, rosin, modified rosin,
Examples include terpene resins, phenolic resins, and copolymers of two or more α-olefins.

The toner of the present invention preferably contains a charge control agent.

The following substances control the toner to be positively charged.

Modified products such as nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate;
And onium salts such as phosphonium salts, which are analogs thereof, and their lake pigments, triphenylmethane dyes, and these lake pigments (as the lake-forming agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid) , Lauric acid, gallic acid, ferricyanide, ferrocyanide), metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin borate Diorganotin borates; guanidine compounds, imidazole compounds; These can be used alone or in combination of two or more. Among these, a triphenylmethane compound and a quaternary ammonium salt whose counter ion is not halogen are preferably used. The general formula (1)

[0128]

[Outside 5] [R ₁ : H, CH ₃ R ₂ , R ₃ : a substituted or unsubstituted alkyl group (preferably C ₁ -C ₄ )], a homopolymer of a monomer: styrene, acrylate, methacryl described above A copolymer with a polymerizable monomer such as an acid ester can be used as a positive charge control agent. In this case, these charge control agents also act as (all or part of) the binder resin.

Particularly, a compound represented by the following general formula (2) is preferable in the constitution of the present invention.

[0130]

[Outside 6] [Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different and are each a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl. Represents a group. R ⁷ , R ⁸ and R ⁹ each represent a hydrogen atom, a halogen atom, which may be the same or different,
Represents an alkyl group or an alkoxy group. A ^- is an anion such as sulfate ion, nitrate ion, borate ion, phosphate ion, hydroxide ion, organic sulfate ion, organic sulfonate ion, organic phosphate ion, carboxylate ion, organic borate ion, and tetrafluoroborate. Is shown).

The following substances control the toner to be negatively charged.

For example, organic metal complexes and chelate compounds are effective, and examples thereof include monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid-based metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

Further, an azo metal complex represented by the following general formula (3) is preferable.

[0134]

[Outside 7] [Wherein, M represents a coordination center metal, and Sc, Ti, V,
Examples thereof include Cr, Co, Ni, Mn, and Fe. 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 -O-, -CO-,-
NH- and -NR- (R is an alkyl group having 1 to 4 carbon atoms).

[0135]

[Outside 8] Represents hydrogen, sodium, potassium, ammonium, aliphatic ammonium or none. ]

In particular, the central metal is preferably Fe or Cr, the substituent is preferably a halogen, an alkyl group or an anilide group, and the counter ion is preferably hydrogen, alkali metal, ammonium or aliphatic ammonium.
Also, a mixture of complex salts having different counter ions is preferably used.

Alternatively, a basic organic acid metal complex represented by the following general formula (4) also gives negative chargeability and can be used in the present invention.

[0138]

[Outside 9]

In particular, as the central metal, Fe, Cr, Si,
Zn and Al are preferred, and the substituent is preferably an alkyl group, an anilide group, an aryl group or a halogen, and the counter ion is preferably hydrogen, ammonium or aliphatic ammonium.

As a method for incorporating the charge control agent into the toner, there are a method of adding it inside the toner and a method of adding it externally. The use amount of these charge control agents is determined by the type of the binder resin, the presence or absence of other additives, the toner manufacturing method including the dispersion method, and is not limited to a specific one. It is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the binder resin.

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

The fine silica powder used in the present invention is BE
The specific surface area by nitrogen adsorption measured by the T method is 20 m ² / g
Good results are obtained within the above range (especially 30 to 400 m ² / g). It is preferable to use 0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight of silica fine powder with respect to 100 parts by weight of the toner.

The silica fine powder has a silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, a silane coupling agent, and a functional group, if necessary, for the purpose of hydrophobization, charge control, and the like. It is also preferable that the treatment is performed with a treating agent such as a silane coupling agent or another organosilicon compound, or in combination with various treating agents.

It is also preferable to add the following inorganic powder in order to improve developability and durability. Magnesium, zinc, aluminum, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin,
Metal oxides such as antimony; composite metal oxides such as calcium titanate, magnesium titanate and strontium titanate; metal salts such as calcium carbonate, magnesium carbonate and aluminum carbonate; clay minerals such as kaolin;
Phosphate compounds such as apatite; silicon compounds such as silicon carbide and silicon nitride; and carbon powders such as carbon black and graphite. Of these, zinc oxide, aluminum oxide, cobalt oxide, manganese dioxide, strontium titanate, and magnesium titanate are preferred.

Further, the following lubricant powder can be added. Fluoro resins such as Teflon and polyvinylidene fluoride; fluorinated compounds such as carbon fluoride; fatty acid metal salts such as zinc stearate; fatty acid derivatives such as fatty acids and fatty acid esters; molybdenum sulfide, amino acids and amino acid derivatives.

The toner of the present invention can be used as a two-component developer in combination with a carrier. When the toner is used in the two-component developing method, any conventionally known carriers can be used. Specifically, particles having an average particle size of 20 to 300 [mu] m, such as metals such as iron, nickel, cobalt, manganese, chromium, and rare earths, and their alloys and oxides, whose surface is oxidized or not oxidized, are used.

Further, those obtained by adhering or coating a substance such as a styrene resin, an acrylic resin, a silicone resin, a fluorine resin, or a polyester resin on the surface of the carrier particles are preferably used.

The toner of the present invention can be used as a magnetic toner by further containing a magnetic material. In this case, the magnetic material can also serve as a colorant. In the present invention,
Examples of the magnetic material contained in the magnetic toner include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; or aluminum, cobalt, copper, lead, magnesium, tin, zinc, and antimony of these metals. , Beryllium, bismuth, cadmium,
Examples include alloys of metals such as calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

These ferromagnetic substances preferably have an average particle diameter of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount contained in the toner is preferably about 20 to 200 parts by weight, particularly preferably 40 to 150 parts by weight, per 100 parts by weight of the resin component.

The coloring agent that can be used in the toner of the present invention includes any suitable pigment or dye. As a colorant of the toner, for example, carbon black as a pigment,
Examples include aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengalara, phthalocyanine blue, and indanthrene blue. These are used in an amount necessary and sufficient to maintain the optical density of the fixed image, and 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, per 100 parts by weight of the resin.
Good addition amount by weight. A dye is further used for the same purpose. For example, azo dyes, anthraquinone dyes,
There are xanthene dyes and methine dyes, and 0.1 to 20 parts by weight, preferably 0.3 to 1 part by weight, per 100 parts by weight of the resin.
The addition amount of 0 parts by weight is good.

To prepare the toner for developing an electrostatic image according to the present invention, a binder resin, a wax, a metal salt or a metal complex, a pigment or dye as a colorant, a magnetic material, a charge control agent if necessary, While the other additives, etc. were thoroughly mixed by a mixer such as a Henschel mixer or a ball mill, and then heated and kneaded using a hot kneader such as a heating roll, kneader, or extruder, the resins were mixed with each other. Disperse or dissolve metal compounds, pigments, dyes, magnetic materials,
After solidification by cooling, pulverization and classification are performed to obtain the toner according to the present invention.

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

The particle size distribution can be measured by various methods. In the present invention, the particle size distribution was measured using a Coulter counter multisizer.

That is, a Coulter counter Multisizer II (manufactured by Coulter) was used as a measuring device, and an interface (manufactured by Nikkaki) for outputting the number distribution and volume distribution and a CX-1 personal computer (manufactured by Canon) were connected. Then, a 1% NaCl aqueous solution is prepared using a special grade or primary grade sodium chloride as an electrolytic solution. As a measurement method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and the measurement sample is further diluted with 2 to 50 ml.
Add 20 mg. The electrolytic solution in which the sample is suspended is subjected to dispersion treatment for about 1 to 3 minutes by an ultrasonic disperser, and when measuring the toner particle size as an aperture by the Multisizer II of the Coulter counter, a 100 μm aperture is used. Measure. The volume and number of the toner were measured, and the volume distribution and the number distribution were calculated. Then, the weight-based weight average diameter determined from the volume distribution according to the present invention is determined from the volume distribution.

Next, the image forming method of the present invention will be described with reference to the schematic structure of a general electrophotographic apparatus using a drum type photosensitive member shown in FIG.

In the figure, reference numeral 1 denotes a drum type photosensitive member as a latent image holding member, which is driven to rotate around an axis 1a in a direction of an arrow at a predetermined peripheral speed. The photoreceptor 1 receives a uniform charge of a predetermined positive or negative potential on its peripheral surface by a primary charging corona charger 2 as a primary charging means during the rotation process, and then forms a latent image (not shown) in an exposure unit 3. By means of light image exposure L
(Slit exposure, laser beam scanning exposure, etc.). As a result, an electrostatic latent image corresponding to the exposure image is sequentially formed on the peripheral surface of the photoconductor.

The electrostatic latent image is then subjected to toner development by the developing means 4 so that the toner-developed image is transferred from the photoreceptor 1 to the transfer means 5 by a transfer corona charger 5 as a transfer means. Meanwhile, the transfer material P is sequentially transferred onto the surface of the transfer material P fed in synchronization with the rotation of the photoconductor 1.

The transfer material P having undergone the image transfer is separated from the photoreceptor surface and introduced into the image fixing means 8 where the image is fixed and printed out of the apparatus as a copy.

The surface of the photoreceptor 1 after the image transfer is cleaned by the cleaning means 6 to remove the untransferred toner, and is further subjected to a static elimination treatment by the pre-exposure means 7 to be used repeatedly for image formation. You.

As the primary charging means 2 of the photoreceptor 1, a contact charging means such as a roller charger for charging by contacting the photoreceptor can be used instead of the corona charger for primary charging. The use of the contact charging means is preferable because the amount of ozone generated at the time of charging can be suppressed, so that it is not necessary to use an ozone filter.

Further, the transfer device 5 can also use a contact transfer means such as a roller transfer charger for transferring the image by contacting the photosensitive member via a transfer material, instead of the transfer corona charger. Since the amount of ozone generated during transfer can be suppressed, it is not necessary to use an ozone filter, which is preferable.

FIG. 6 shows a specific example of the process cartridge of the present invention.

In the following description of the process cartridge, components having the same functions as those of the components of the image forming apparatus described with reference to FIG. 5 will be described using the same reference numerals as those in FIG.

In the process cartridge of the present invention, at least the developing means and the latent image holding member are generally made into a cartridge, and are attached to and detached from an image forming apparatus main body (for example, a copying machine, a laser beam printer, a facsimile machine). It is configured to be possible.

In the embodiment shown in FIG.
A process cartridge C integrally includes a drum-shaped latent image holding member (photosensitive drum) 1, a cleaning unit 6 having a cleaning blade 61, and a corona charging unit 2 as a primary charging unit.

In the present embodiment, the developing means 4 has an elasticity regulating blade 41 as a toner layer thickness regulating means and a one-component developer 43 having a toner in a toner container 42. At the time of development, an electric field is formed between the photosensitive drum 1 and a developing sleeve 44 as a toner carrier by a developing bias voltage from a bias applying unit, and a developing process is performed. The distance between the photosensitive drum 1 and the developing sleeve 44 is very important for suitably executing the developing step.

In the above description, the embodiment in which the four components of the developing means 4, the latent image holding member 1, the cleaning means 6, and the primary charging means 2 are integrally formed as a cartridge has been described. It is sufficient that at least two components of the image forming apparatus and the latent image holding member are integrally formed into a cartridge, and the three components of a developing unit, a latent image holding unit and a cleaning unit, a developing unit, a latent image holding unit and It is also possible to integrally form a cartridge by adding three components of the primary charging means or other components.

In FIG. 5, when the electrophotographic apparatus is used as a copier or a printer, the light image exposure L is a light reflected from or transmitted from the original, or a read signal of the original, and is converted into a signal. It is performed by scanning, driving an LED array, driving a liquid crystal shutter array, or the like.

When used as a facsimile printer, the light image exposure L is an exposure for printing received data. FIG. 7 is a block diagram showing an example of this case.

The controller 11 controls the image reading section 10 and the printer 19. The whole controller 11 is CP
It is controlled by U17. The read data from the image reading unit is transmitted to the partner station through the transmission circuit 13. Data received from the partner station is sent to the printer 19 through the receiving circuit 12. Predetermined image data is stored in the image memory. The printer controller 18 is the printer 1
9 is controlled. 14 is a telephone.

The image received from the line 15 (image information from a remote terminal connected via the line) is demodulated by the receiving circuit 12, and then the CPU 17 performs a decoding process on the image information and sequentially executes the image memory 16 Is stored in Then, when the image of at least one page is stored in the memory 16,
The image of the page is recorded. The CPU 17 is a memory 1
6, one page of image information is read out and the combined one-page image information is sent to the printer controller 18. The printer controller 18 receives 1
When the image information of the page is received, the printer 19 is controlled to record the image information of the page.

The CPU 17 receives the next page during recording by the printer 19.

As described above, image reception and recording are performed.

[0174]

The present invention will be described below with reference to specific examples.

First, the wax used in the present invention will be described.

Using a Ziegler catalyst, ethylene was polymerized at a low pressure to obtain wax A having a relatively low molecular weight, and wax B having a somewhat sharp molecular weight distribution by fractional crystallization.
I got Using wax A, wax C having a sharp molecular weight distribution was obtained by vacuum distillation. Also,
Ethylene was polymerized at a low pressure using a Ziegler catalyst to obtain wax D having a higher molecular weight than wax A obtained by the same polymerization, and waxes E and F whose molecular weight distribution was somewhat sharpened by fractional crystallization. Using wax D, waxes G and H whose molecular weight distribution was sharpened by a vacuum distillation method were obtained. Wax K having a sharp molecular weight distribution was obtained from a mixture of wax A and wax D by a vacuum distillation method.

Using wax 135 ° (manufactured by Nippon Oil Co., Ltd.) and Viscol 660P (manufactured by Sanyo Chemical Co., Ltd.) as wax whose molecular weight distribution was sharpened by vacuum distillation, wax I was obtained from paraffin wax 135 °. Wax J was obtained from Viscol 660P. These physical properties are shown in Table 1.

Next, the binder resin used in the present invention will be described.

(Resin Synthesis Example 1) 200 parts by weight of xylene was charged into a four-necked flask equipped with a nitrogen gas inlet tube, a condenser, a stirrer, and a thermometer, stirred under a stream of nitrogen gas, kept at 140 ° C. A mixture of 16 parts by weight of n-butyl acrylate, and 2 parts by weight of di-t-butyl peroxide (DTBP) as an initiator was dropped by using a continuous dropping apparatus over 4 hours to carry out polymerization. Solvent was used to obtain Polymer A. The molecular weight distribution of the polymer A was determined by GP
When measured at C, the molecular weight has a maximum value of 12,000,
Mw / Mn was 2.2.

(Resin Synthesis Example 2) In the polymerization apparatus of Resin Synthesis Example 1, 80 parts by weight of styrene and 20 parts by weight of n-butyl acrylate were added to 300 parts by weight of a 0.1% aqueous solution of polyvinyl alcohol.
Parts by weight, 2,2-bis (4,4-di-t-
A mixture of 0.2 parts by weight of butylperoxycyclohexyl) propane was charged and polymerization was carried out at a polymerization temperature of 90 ° C. for 24 hours. Thereafter, the mixture was cooled, washed with water, and dried to obtain a polymer B. When the molecular weight distribution of the polymer B was measured by GPC, it had a maximum value at a molecular weight of 780,000, and Mw / Mn was 3.8.
Met.

The polymer A and the polymer B were mixed in a solution at a weight ratio of 75:25 to obtain a binder resin 1 of a styrene-acrylate copolymer.

Example 1 100 parts by weight of binder resin 1 80 parts by weight of iron tetroxide 2 parts by weight of triphenylmethane dye 4 parts by weight of wax B 2 parts by weight of wax E

After the above materials were premixed, they were kneaded with a twin screw extruder set at 130 ° C. The obtained kneaded material is cooled, coarsely pulverized by a cutter mill, and then finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder is subjected to a multi-divided classifier utilizing the Coanda effect. The toner 1 having a weight average particle size of 7.8 μm was obtained. 100 parts by weight of this toner and 0.6 part by weight of positively charged hydrophobic colloidal silica fine powder were mixed (externally added) to obtain a toner having colloidal silica fine powder on the surface of toner particles as a developer. Table 2 shows the physical properties when the waxes B and E were mixed at a ratio of 2: 1 and Table 3 shows the physical properties of the toner. Further, the toner was subjected to a fixing property test, an offset resistance test, a blocking resistance test, and an image output test.

As a result, good low-temperature fixability and low
Good offset resistance at high temperatures was obtained. In addition, there were no problems in blocking resistance, image density stability, fusion to a photoreceptor, blotching, and fogging on an image. Table 4 shows the results.

The test method for evaluating the toner is as follows.

Fixing property and offset resistance test An electrophotographic copying machine NP4 was used as the image forming apparatus shown in FIG.
The above-mentioned developer was charged into a modified machine of 835 (manufactured by Canon Inc.) from which the fixing device was removed to obtain an unfixed image. On the other hand, the fixing device removed from the NP4835 was modified into a temperature-variable heat roller external fixing device, and a fixing test and an anti-offset test of an unfixed image were performed using the fixing device.

The nip of the external fixing device was set to 5.5 mm, the process speed was set to 200 mm / s,
The temperature is controlled every 5 ° C. in a temperature range of 0 ° C., and an unfixed image is fixed at each temperature.
The paper was rubbed with a silbon paper weighted with m ² , and the fixing temperature at which the image density reduction rate before and after the rubbing was 10% or less was defined as the fixing start temperature.

The offset is defined as a low-temperature offset-free starting point at which the image is no longer stained by unfixed toner visually, and the offset disappears at a fixing device temperature higher than the temperature at which the image density reduction rate before and after rubbing is 10% or less. The temperature was taken as the fixing start temperature, the temperature was raised, and the highest temperature without offset was taken as the high-temperature offset-free end point.

Image Output Test Electrophotographic copier NP4 as the image forming apparatus shown in FIG.
835 (manufactured by Canon Inc.) on an A4 size transfer paper with an A4 size image area ratio of 6%
Zero images were formed, and the image density and fog were evaluated from the copy image, and the toner fusion was evaluated from the state on the photoconductor and the copy image. In addition, blotting was evaluated based on the state of the toner coat on the toner carrier and the copy image during image output.

(Image Density Stability) There is no density unevenness on the image, and the density is stable and good. ○ There is no density unevenness on the image, but there is a slight decrease in density. △ Density unevenness on the image was slight, and density was reduced. C: Density unevenness and density decrease on the image are remarkable.

(Fog) な い Not observed at all. ○ It appears faintly in a part of the image, but there is no practical problem. △ Faintly appears on the entire surface of the image. × Appears markedly on the entire surface of the image.

(Toner fusion) ◎ Not observed at all. ○ Slightly visible on the photoreceptor, but not visible on the image. Δ: Seen on the photoreceptor and faintly appear on the image. C: Notable on the image.

(Blotch) ら れ Not observed at all. ○ Slightly visible on the toner carrier, but not visible on the image. C: Appears on the toner carrier and appears faintly on the image. C: Notable on the image.

Blocking Resistance Test Approximately 10 g of the developer was placed in a 100 cc glass
After leaving it at 3 ° C. for 3 days, it was visually evaluated.凝集 No aggregates were observed. ○ Aggregates can be seen but easily collapse. △ Aggregates are seen, but collapse when shaken. X: Aggregates can be grasped and do not collapse easily.

Example 2 The procedure of Example 1 was repeated except that 4 parts by weight of the wax B and 2 parts by weight of the wax E were melt-mixed with stirring, solidified by cooling, and then pulverized. The toner 2 was prepared and evaluated. The results are shown in Table 4, and the physical properties of the toner are shown in Table 3.

<Example 3> In Example 1, 100 parts by weight of binder resin 1 was dissolved in a xylene solvent instead of the binder resin and wax, and the temperature of the resin solution was increased. Toner 3 was prepared and evaluated in the same manner as in Example 1 except that a wax-containing binder resin, which was mixed with 2 parts by weight of wax E and 2 parts by weight of wax E, and was subjected to solvent removal and drying, was used. Was. Table 4 shows the results.
Table 3 shows the physical properties of the toner.

Example 4 Toner 4 was prepared and evaluated in the same manner as in Example 1, except that 4 parts by weight of wax C and 2 parts by weight of wax E were used. The results are shown in Table 4, the physical properties when waxes C and E were mixed at a ratio of 2: 1 are shown in Table 2, and the physical properties of the toner are shown in Table 3.

Example 5 Toner 5 was prepared and evaluated in the same manner as in Example 1 except that 4 parts by weight of wax B and 2 parts by weight of wax G were used. The results are shown in Table 4, the physical properties when waxes B and G were mixed at a ratio of 2: 1 are shown in Table 2, and the physical properties of the toner are shown in Table 3.

Example 6 Toner 6 was prepared and evaluated in the same manner as in Example 1, except that 4 parts by weight of wax C and 2 parts by weight of wax G were used. The results are shown in Table 4, the physical properties when waxes C and G were mixed at a ratio of 2: 1 are shown in Table 2, and the physical properties of the toner are shown in Table 3.

Example 7 Toner 7 was prepared and evaluated in the same manner as in Example 1, except that 4 parts by weight of wax C and 2 parts by weight of wax F were used. The results are shown in Table 4, the physical properties when waxes C and F were mixed at a ratio of 2: 1 are shown in Table 2, and the physical properties of the toner are shown in Table 3.

Example 8 Toner 8 was prepared and evaluated in the same manner as in Example 1, except that 4 parts by weight of wax I and 2 parts by weight of wax J were used. The results are shown in Table 4, the physical properties when waxes I and J were mixed at a ratio of 2: 1 are shown in Table 2, and the physical properties of the toner are shown in Table 3.

Example 9 Toner 9 was prepared and evaluated in the same manner as in Example 1, except that 4 parts by weight of wax C and 2 parts by weight of wax H were used. The results are shown in Table 4, the physical properties when waxes C and H were mixed at a ratio of 2: 1 are shown in Table 2, and the physical properties of the toner are shown in Table 3.

Example 10 Toner 10 was prepared and evaluated in the same manner as in Example 1, except that 4 parts by weight of wax C and 2 parts by weight of wax K were used. The results are shown in Table 4, the physical properties when the waxes C and K were mixed at a ratio of 2: 1 are shown in Table 2, and the physical properties of the toner are shown in Table 3.

Comparative Example 1 A toner 11 was prepared and evaluated in the same manner as in Example 1 except that only 4 parts by weight of the wax A was used. The toner 11 was evaluated for blocking resistance, high temperature offset resistance, and image density. The stability was remarkably inferior. The results are shown in Table 4, and the physical properties of the toner are shown in Table 3.

Comparative Example 2 A toner 12 was prepared and evaluated in the same manner as in Example 1 except that only 4 parts by weight of the wax D was used. Fusing, blotching, and fogging on the image. The results are shown in Table 4, and the physical properties of the toner are shown in Table 3.

Comparative Example 3 Paraffin Wax 135 °
A toner 13 was prepared and evaluated in the same manner as in Example 1, except that 3 parts by weight (manufactured by Nippon Oil Co., Ltd.) and 10 parts by weight of Viscol 660P (manufactured by Sanyo Chemical Industries; low molecular weight polypropylene wax) were used. However, the blocking resistance was remarkably poor, and the image density stability was poor. The results are shown in Table 4, the physical properties when 135 ° and 660P were mixed at a ratio of 3:10 are shown in Table 2, and the physical properties of the toner are shown in Table 3.

Comparative Example 4 Except that 3 parts by weight of Viscol 550P and 2 parts by weight of Biscol 660P (manufactured by Sanyo Chemical Industries; low molecular weight polypropylene wax) were used.
The toner 14 was prepared and evaluated in the same manner as in Example 1. As a result, the low-temperature fixability was remarkably poor. Table 4 shows the results
Table 2 shows the physical properties when 550P and 660P were mixed at a ratio of 3: 2, and Table 3 shows the physical properties of the toner.

Comparative Example 5 A toner 15 was prepared and evaluated in the same manner as in Example 1 except that no wax was used. The toner 15 was remarkably inferior in low-temperature fixability and high-temperature offset resistance. . The results are shown in Table 4, and the physical properties of the toner are shown in Table 3.

[0209]

[Table 1]

[0210]

[Table 2]

[0211]

[Table 3]

[0212]

[Table 4]

[0213]

According to the present invention, by using the above-mentioned wax, it is possible to provide a toner having a wide fixing temperature range and excellent low-temperature fixing property and offset resistance.

Further, the present invention can provide a toner which is excellent in blocking resistance and does not deteriorate developability.

Further, the present invention can provide a toner which does not fuse to a photoreceptor, does not generate blotches, and has no fog on an image.

[Brief description of the drawings]

FIG. 1 is a view showing an endothermic peak portion of a DSC curve at the time of temperature rise when waxes B and E are mixed at a ratio of 2: 1 in toner 1 (Example 1) of the present invention.

FIG. 2 is a view showing an endothermic peak portion of a DSC curve at the time of temperature rise when waxes C and H are mixed at a ratio of 2: 1 in a toner 9 (Example 9) of the present invention.

FIG. 3 is a view showing an endothermic peak portion of a DSC curve at the time of temperature rise when waxes C and H are mixed at a ratio of 2: 1 in the toner 9 (Example 9) of the present invention.

FIG. 4 shows the DS of the toner 9 of the present invention (Example 9) when the temperature is raised.
It is a figure which shows the endothermic peak part of a C curve.

FIG. 5 is a diagram showing a schematic configuration of an image forming apparatus for explaining an image forming method of the present invention.

FIG. 6 is a view showing a specific example for explaining the process cartridge of the present invention.

FIG. 7 is a block diagram illustrating a case where the image forming method of the present invention is applied to a printer of a facsimile machine.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Latent image holder 1a axis 2 Charging means 3 Exposure part 4 Developing means 5 Transfer means 6 Cleaning means 7 Pre-exposure means 8 Image fixing means 10 Image reading part 11 Controller 12 Receiving circuit 13 Transmitting circuit 14 Telephone 15 Line 16 Memory 17 CPU 18 Printer Controller 19 Printer 41 Toner Layer Thickness Control Means 42 Toner Container 43 Developer 44 Toner Carrier C Process Cartridge L Light Image Exposure P Transfer Material

──────────────────────────────────────────────────続 き Continuation of the front page (72) The inventor, Manabu Oono 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-63-125950 (JP, A) JP-A-6 JP-A-194872 (JP, A) JP-A-6-332228 (JP, A) JP-A-60-252366 (JP, A) JP-A-6-130714 (JP, A) JP-A-7-77830 (JP, A) JP, 5-197192 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08

Claims (13)

(57) [Claims] 1. A toner for developing an electrostatic image containing at least a binder resin and a wax, wherein a minimum onset of an endothermic peak in a heat-absorbing peak of a DSC curve of the wax measured by a differential scanning calorimeter is obtained. The temperature is 50 ° C. or higher, and has at least one endothermic peak in each of a temperature range of 60 to 90 ° C. and a temperature range of 90 to 150 ° C., and the maximum endothermic peaks in each temperature range are P ₁ and P _2. the peak temperature difference between P ₁ and P ₂ when is at 15 ℃ above, in the chromatogram measured by GPC of the wax
Regarding the wax component constituting the endothermic peak P ₁ is the weight
Ratio M between weight average molecular weight (Mw) and number average molecular weight (Mn)
w / Mn is 1.7 or less, constitute the endothermic peak _{P 2}
A ratio of Mw / Mn of the wax component to be used is 5 or less . 2. An endothermic peak at the time of temperature rise of a DSC curve of the wax measured by a differential scanning calorimeter,
The electrostatic charge image according to claim 1, wherein the onset temperature at the start point of the endothermic peak in the temperature region of 90 to 150C is higher than the onset temperature at the end point of the endothermic peak in the temperature region of ~ 90C. Development toner. 3. An endothermic peak at the time of temperature rise in a DSC curve of the wax measured by a differential scanning calorimeter, wherein the lowest onset temperature of the endothermic peak is 50 ° C. or more, and
It has at least one endothermic peak in each of a temperature range of 0 to 90 ° C. and a temperature range of 100 to 150 ° C. When the maximum endothermic peaks in each temperature range are P ₁ and P ₂ , P
₁ and an electrostatic image developing toner according to claim 1, wherein the peak temperature difference P ₂ is 20 ° C. or higher. 4. An endothermic peak at the time of temperature rise of a DSC curve of the wax measured by a differential scanning calorimeter,
4. The onset temperature at the starting point of the endothermic peak in the temperature range of 100 to 150 [deg.] C. is higher than the onset temperature of the end point of the endothermic peak in the temperature range of ~ 90 [deg.] C.
3. The toner for developing an electrostatic image according to item 1. 5. An endothermic peak at the time of temperature rise in a DSC curve of the wax measured by a differential scanning calorimeter, wherein the peak temperature of the maximum endothermic peak P _{1 and} the maximum endothermic peak P ₂
The toner for developing an electrostatic charge image according to claim 1, wherein the difference between the peak temperatures is 20 ° C. or more. 6. The endothermic peak during heating in DSC curve measured by a differential scanning calorimeter of the wax, said maximum endothermic peak P ₁ of the peak temperature and said maximum endothermic peak P ₂
The toner for developing an electrostatic image according to claim 1, wherein the difference between the peak temperatures is 25 ° C. or more. 7. The endothermic peak during heating in DSC curve measured by a differential scanning calorimeter of the wax, said maximum endothermic peak P ₁ of the peak temperature and said maximum endothermic peak P ₂
The toner for developing an electrostatic charge image according to claim 1, wherein the difference between the peak temperatures is 30 ° C. or more. 8. An electrostatic image developing toner containing at least a binder resin and a wax, wherein the toner has a temperature of 65 to 85 ° C. in an endothermic peak at the time of temperature rise of a DSC curve measured by a differential scanning calorimeter. has at least one endothermic peak each temperature region of the area and the 95 to 130 ° C., the peak temperature difference between P ₃ and P ₄ when the maximum endothermic peak was P _3, P ₄ at each temperature range 50 ° C. And the Tg of the toner is 50 to 65 ° C.
, And the binder resin is gel-Mei Activation chromatography
In the molecular weight distribution by (GPC), the molecular weight was 3 × 10
³ to 5 × 10 ⁴ region and molecular weight ¹⁰⁵ or more of that in the area
A toner for developing an electrostatic image, wherein each toner has a peak . 9. An endothermic peak at the time of temperature rise of a DSC curve of the toner measured by a differential scanning calorimeter, from 65 to 65.
Has at least one endothermic peak each temperature region of the temperature range and the 100 to 130 ° C. in 85 ° C., P ₃ and the peak temperature of P ₄ when the maximum endothermic peak was P _3, P ₄ at each temperature region The difference is 50 ° C. or less, and the T
The toner for developing an electrostatic image according to claim 8, wherein g is 50 to 65C. 10. A step of applying a voltage to the latent image holding member to charge it, a step of forming an electrostatic latent image on the charged latent image holding member, and forming a latent image on the latent image holding member to form a toner image. An image forming method including a step of developing the formed electrostatic latent image with a toner carried on a toner carrier, wherein the toner contains at least a binder resin and a wax, and the differential scanning calorimeter of the wax In the endothermic peak at the time of temperature rise of the DSC curve measured by the above, the minimum onset temperature of the endothermic peak is 50 ° C. or more, and
0 has at least one endothermic peak each temperature region of the temperature range and 90 to 150 ° C. in ° C., P ₁ when the maximum endothermic peak at each temperature range was P _1, P ₂ and P ₂
Is 15 ° C. or more, and the GP
With respect to the chromatogram measured by C, the endothermic peak
Wax component is a weight average molecular weight constituting the over click P ₁ (M
w) and the number average molecular weight (Mn) ratio Mw / Mn is 1.7.
Or less, the wax component constituting the endothermic peak P ₂
Wherein the ratio Mw / Mn is 5 or less . 11. A step of applying a voltage to the latent image holding member to charge it, a step of forming an electrostatic latent image on the charged latent image holding member, and forming a latent image on the latent image holding member to form a toner image. An image forming method including a step of developing the formed electrostatic latent image with a toner carried on a toner carrier, wherein the toner contains at least a binder resin and wax, and a differential scanning calorimeter of the toner. D measured by
In the endothermic peak at the time of temperature rise in the SC curve, 65 to 85 ° C
Has at least one endothermic peak each temperature region of the temperature range and 95 to 130 ° C., the peak temperature difference between P ₃ and P ₄ when the maximum endothermic peak was P _3, P ₄ at each temperature region 50 ° C. or less, and the Tg of the toner is 50
６５65 ° C., and the binder resin is a gel permeation chromatography
In the molecular weight distribution by (GPC), the molecular weight was 3 × 10
³ to 5 × 10 ⁴ region and molecular weight ¹⁰⁵ or more of that in the area
An image forming method, wherein each image has a peak . 12. A process cartridge detachably mountable to an image forming apparatus main body, wherein the process cartridge includes a latent image holding member for holding an electrostatic latent image and the electrostatic latent image held on the latent image holding member. Developing means for developing an image, the developing means carrying at least a toner containing a binder resin and wax, a toner container containing the toner, and a toner contained in the toner container; Having a toner carrier for conveying, the endothermic peak at the time of temperature rise of a DSC curve measured by a differential scanning calorimeter of the wax, the minimum onset temperature of the endothermic peak is 50 ° C. or more, Temperature range of 60-90 ° C and 90-150 ° C
Has at least one endothermic peak in each temperature region, and the maximum endothermic peak in each temperature region is P ₁ , P
Peak temperature difference between _{P 1} and _{P 2} when the ₂ Ah at 15 ℃ or higher
And the chromatogram of the wax measured by GPC.
The wax component constituting the endothermic peak P ₁
Is the difference between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
The ratio Mw / Mn is 1.7 or less, the endothermic peak _{P 2}
A process cartridge wherein the constituent wax component has a ratio Mw / Mn of 5 or less . 13. A process cartridge detachable from an image forming apparatus main body, wherein the process cartridge includes a latent image holding member for holding an electrostatic latent image and the electrostatic latent image held on the latent image holding member. Developing means for developing an image, the developing means carrying at least a toner containing a binder resin and wax, a toner container containing the toner, and a toner contained in the toner container; It has a toner carrier for conveyance, and has a temperature range of 65 to 85 ° C. and a temperature range of 95 to 130 ° C. in an endothermic peak at the time of temperature rise of a DSC curve of the toner measured by a differential scanning calorimeter. Each has at least one endothermic peak,
Peak temperature difference between P ₃ and P ₄ when the maximum endothermic peak was P _3, P ₄ at each temperature region is at 50 ° C. or less,
The toner has a Tg of 50 to 65 ° C., and the binder resin is formed by gel permeation chromatography.
In the molecular weight distribution by (GPC), the molecular weight was 3 × 10
^{3 to} 5 × 10 ⁴ or more region and molecular weight of 10 ⁵ or more region
Wherein each of the process cartridges has a peak .