JP3342229B2 - Wax composition used for electrostatic image developing toner, method for producing the same, and electrostatic image developing toner containing the wax composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wax composition used for an electrostatic image developing toner used in electrophotography, electrostatic recording, and magnetic recording, a method for producing the same, and the wax composition. Related to toner.

[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,
The toner is fixed by heating, pressure, heat and pressure, or solvent vapor to obtain a copy, 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] For this reason, smaller, lighter, faster, and more reliable devices have been strictly pursued, and machines have become simpler in various respects. 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 compression 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 sheet to be fixed. A so-called offset phenomenon occurs, and the sheet to be fixed may be stained. Preventing toner from adhering to the heat fixing roller or 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 a 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 fluorine-based resin, and the surface of the roller is further prevented from offsetting. 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 to miniaturization and weight reduction, and moreover, silicon oil and the like may evaporate due to heat and contaminate the inside of the machine. Therefore, instead of using a silicon oil supply unit, 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 has been proposed. Proposed. 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 downsizing, weight reduction, and high reliability, it is necessary and preferable to remove even these auxiliary devices. Therefore, if there is no further performance improvement such as toner fixing and offset,
This is difficult to achieve without further improvements in the binder resin and 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 for improving the fixing performance of the toner, particularly the offset resistance. However, while these performances are improved, the blocking resistance is deteriorated, and a problem occurs in matching with the image forming means, thereby deteriorating the developability and the like.

Further, there is disclosed a technique in which two or more kinds of waxes are added to a toner from a low temperature range to a high temperature range at the time of fixing in order to exert the effect of further adding the wax. For example, JP-B-52-3305, JP-A-58-215659, JP-A-62-10075, JP-A-4-124676, and 299357
JP, 362953, JP-A-5-19719
A technique such as Japanese Patent Publication No. 2 is disclosed.

However, none of these toners can satisfy all the toner performances, and some problems have occurred. For example, there are disadvantages such as excellent high-temperature offset resistance and developability but poor low-temperature fixability, excellent low-temperature offset resistance but poor blocking resistance, and further causing a decrease in developability. In addition, when a plurality of wax components are used, the dispersion in the toner becomes non-uniform, which causes poor charging of the toner, poor conveyance on the developing device or the developing sleeve, and uneven coating, and causes fog or blotch on the image. Image defects occurred.

On the other hand, the effect of the wax composition on toner productivity cannot be ignored. For example, when a wax having a relatively low melting point is used, since the binder resin is plasticized, the mechanical strength of the toner decreases and the pulverization efficiency increases, but the amount of fine powder having a desired particle size or less increases. It falls into a so-called over-pulverized state, the yield at the time of classification decreases, and as a result, the production efficiency deteriorates. On the other hand, when a wax having a relatively high melting point is used, the pulverization efficiency deteriorates, and the dispersibility becomes difficult when melt-kneading the toner. If the kneading state is strengthened to improve the dispersibility, new problems such as molecular breakage of the binder resin occur.

As a result of our intensive studies, the waxes contained in these toners were found to have a differential scanning calorimeter (DSC).
In the peak at the time of temperature rise of the DSC curve measured by the formula (1), the wax component is simply widely distributed or the wax component is present in a biased temperature range. Not reached,
Or it turned out that it contains many components which deteriorate.

The various properties required for the above-mentioned toners are often reciprocal to each other, and it is increasingly desired in recent years to satisfy them with high performance. Under such circumstances, the role of the wax composition as a toner constituent material plays a large role, and high functionality is required. However, there is not yet enough comprehensive response to comprehensively address the above issues.

[0017]

SUMMARY OF THE INVENTION An object of the present invention is to solve and improve the above problems.

That is, an object of the present invention is to provide a wax composition used for obtaining a toner for developing an electrostatic image having an excellent low-temperature fixing property and offset resistance and a wide fixing temperature range, and a method for producing the same. is there.

Further, the present invention has excellent blocking resistance,
An object of the present invention is to provide a wax composition used for obtaining a toner for developing an electrostatic image without deteriorating developability and a method for producing the same.

A further object of the present invention is to provide a wax composition used for obtaining a toner for developing an electrostatic image, which realizes a high-quality image and does not adversely affect the photoreceptor and the developer carrier, and a method for producing the same. To provide.

It is a further object of the present invention to provide a wax composition capable of improving the production efficiency of a toner for developing an electrostatic image, and a method for producing the same.

A main object of the present invention is to provide a wax composition used in an electrostatic image developing toner and a method for producing the same, which can achieve the above objects at a high level without contradiction. It is a further object of the present invention to provide a toner for developing an electrostatic image containing the above wax composition.

[0023]

The present invention relates to a wax composition used in a toner for developing an electrostatic image, wherein the wax composition comprises two or more waxes having different melting points (low melting point wax). / High melting point wax) as a main component, and a differential scanning calorimeter (DSC) of the wax composition.
Of the endothermic peak at the time of temperature rise of the DSC curve measured by
To, high melting point wax of the DSC curve obtained during the first heating
Maximum endothermic peak (P ₂ ′) attributed to
Heat of fusion (ΔHa) and the maximum endothermic peak at the second heating
The heat of fusion (ΔHb) exhibited by (P ₂ ) is given by the following equation (1):

[0024]

(Equation 4) Is satisfied, the endothermic peak at the time of the second temperature rise of the DSC curve is satisfied.
Respect chromatography click, is (a) a low melting point wax component, the maximum endotherm at 60 to 90 ° C.
Has a peak (P _1), including said maximum endothermic peak (P ₁₎
If the onset temperature at the start of the endothermic peak is
Ri, (b) a high melting point wax component has a maximum in the 100 to 150 ° C.
It has an endothermic peak (P _2), (c) the maximum endothermic peak of the low melting point wax component (P ₁₎
And a maximum endothermic peak (P ₂ ) of the high melting point wax component satisfies the relationship of (P ₂ peak temperature) − (P ₁ peak temperature) ≧ 20.
The present invention relates to a wax composition used in the present invention.

[0025]

Further, the present invention provides a method of mixing a low-melting wax component, a high-melting wax component and, if necessary, a third component by heating and melting without a solvent to obtain a uniform wax melt.
The present invention relates to a method for producing a wax composition used in a toner for developing electrostatic images, wherein the wax composition is obtained by cooling and solidifying at a cooling rate of 1 to 20 ° C./sec. Also,
The present invention relates to a toner for developing an electrostatic image, comprising at least a binder resin and the above wax composition.

Hereinafter, the present invention will be described in detail.

In the present invention, the low-melting-point wax component and the high-melting-point wax component, and further, the thermal properties of the wax composition after the melt blending, which are measured by a differential scanning calorimeter (DSC), are precisely specified, whereby the toner has a low temperature. A good balance between fixing ability and offset resistance, developing characteristics, preservation and matching with image forming apparatus, and further improvement of toner production efficiency,
Moreover, it can be achieved to a high degree.

The wax composition of the present invention has a DSC curve 2
Regarding the endothermic peak at the time of the second temperature increase, the maximum endothermic peak (P ₁ ) attributed to the low melting point wax component at 60 to 90 ° C. and 1
It has a maximum endothermic peak (P ₂ ) attributed to the high melting point wax component at 00 to 150 ° C., and calculates the difference between the peak temperature of the maximum endothermic peak (P ₁ ) and the peak temperature of the maximum endothermic peak (P ₂ ). By setting the temperature to 20 ° C. or higher, the low melting point wax component melts from a relatively low temperature range, thereby plasticizing the surrounding binder resin and high melting point wax, and improving low temperature offset resistance and low temperature fixability. At the same time, the high melting point wax component is melted in a relatively high temperature range, so that a releasing effect is exhibited and good high-temperature offset resistance is obtained. Therefore, a wider fixing area can be obtained as compared with the case where these wax components are used alone.

Further, by setting the onset temperature of the starting point of the endothermic peak including the maximum endothermic peak (P ₁ ) to 50 ° C. or more, the plasticization of the binder resin can be appropriately suppressed, so that the low-temperature fixability is impaired. In addition, the blocking resistance is maintained without causing the problem, and the excessive pulverization phenomenon caused by the insufficient strength of the toner is prevented, and the production efficiency is improved.

When the maximum endothermic peak (P ₁ ) exceeds 90 ° C. or when the maximum endothermic peak (P ₂ ) is less than 100 ° C., a high degree of low-temperature fixing property and anti-offset property is achieved similarly to the conventional wax. Can not.

The maximum endothermic peak (P ₂ ) is 150
When the temperature exceeds ℃, the melting temperature of the wax is too high, so that not only the sufficient releasing effect cannot be exerted in the operable temperature range of the fixing device such as a copying machine, but also the low-temperature fixing property is hindered, and the production of toner is inhibited. This leads to a decrease in efficiency. Further, the compatibility with the low-melting-point wax component is also deteriorated, which is a factor that hinders the matching with the image forming apparatus.

When the difference between the maximum endothermic peak (P ₁ ) and the peak temperature of the maximum endothermic peak (P ₂ ) is less than 20 ° C.,
The wax component contributing to low-temperature fixability and high-temperature offset resistance is hardly balanced in the melting temperature range, and it is not possible to effectively extract both performances. 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 preferably 40 ° C. or more. More preferably, it is 60 ° C. or higher.

Further, the wax composition of the present invention comprises a DSC
Regarding the endothermic peak at the time of the second temperature rise of the curve, (end point temperature of the end point of the endothermic peak including the maximum endothermic peak (P ₁ )) <(on of the start point of the endothermic peak including the maximum endothermic peak (P ₂ )) (Set temperature). This makes it possible to reduce the amount of the wax component that does not contribute to the improvement of the toner characteristics, and each of the wax components effectively acts on the heat energy received from the fixing device, thereby securing a sufficient fixing area. Further, the cause of image defects such as deterioration of the fluidity of the toner and poor charging of the toner due to the addition of the wax is removed, and as a result, a high-quality image can be obtained for a long period of time.

By the way, in the wax composition of the present invention, the above-mentioned various properties required for the toner are remarkably improved by controlling the interaction between the low melting point wax component and the high melting point wax component. The interaction between such wax components is measured by a differential scanning calorimeter (DSC).
First maximum endothermic peak of the high melting point wax component during heating prior to removing the front history SC curve (P ₂ ') the heat of fusion exhibits (ΔHa) and second heating time of said maximum endothermic peak (P ₂₎ Can be estimated by comparing the heat of fusion (ΔHb) given by That is, as the interaction that forms a partially compatible state between the wax components becomes stronger,
The ratio of each heat of fusion (ΔHb / ΔHa) shows a large value, and conversely approaches 1 as it weakens. The wax composition of the present invention

[0036]

(Equation 5) It is preferable to be controlled so that ΔHb
When / ΔHa is less than 1.2, no interaction between the wax components occurs, and when it exceeds 10, most of the high melting point wax component remains compatible with the low melting point wax component. Since it exists in a state, the effect of adding the high melting point wax component partially disappears.

Furthermore wax composition of the present invention, with respect to an endothermic peak of the second temperature Nukutoki the DSC curve, the height of said maximum endothermic peak (P ₁₎ (h ₁₎ and said maximum endothermic peak (P ₂₎
Of h ₁ between the height (h ₃₎ the minimum value of the height between the both peaks _{(h 2): h 2:} h 3 = 1: (0~0.5) :( 0.1~1 .
It is preferable that the relationship of 5) is satisfied.

When the height (h ₃ ) of the maximum endothermic peak (P ₂ ) is less than 0.1 or more than 1.5, the low melting point wax component and the high melting point wax component in the wax composition It becomes difficult to express the plasticizing effect and the releasing effect in a well-balanced manner, and it is not possible to highly satisfy the above-mentioned various properties required of the toner. Further, by setting the ratio of the minimum value (h ₂ ) of the height between the two peaks to 0.5 or less, the heat energy received from the fixing device can be efficiently used, and the fixing device can be sensitive to a temperature change. Therefore, it is possible to secure a sufficiently wide fixing area and eliminate fixing unevenness.

In the present invention, a differential scanning calorimeter (DSC)
DSC measurement by measuring the wax composition and the exchange of heat between the low-melting wax component and the high-melting wax component in the wax composition, and observing its behavior. It is preferable to measure with an input compensation type differential scanning calorimeter. 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 includes a DSC curve at the first temperature increase obtained when the temperature is raised from around room temperature to 200 ° C. at a rate of 10 ° C./min, and a 200 ° C.
After removing the previous history by lowering the temperature to 20 ° C., the DSC curve at the second temperature increase obtained when the temperature is similarly increased is used.

The respective temperatures exhibited by the wax composition precisely specified in the present invention are defined as follows.

<Each temperature related to the endothermic peak including the maximum endothermic peak (P ₁ ) attributed to the low-melting-point wax component> In the DSC curve obtained when the peak temperature of the maximum endothermic peak (P ₁ ) is increased , 60 to 90 ° C. Peak top temperature of the peak showing the maximum endothermic peak in the temperature range of (Corresponding to P ₁ P in FIG. 2)

The temperature at the intersection of the tangent of the curve and the baseline at the point where the differential value of the DSC curve obtained when the onset temperature rises at the start point of the endothermic peak first becomes maximum. (Corresponding to S ₁ -OP in FIG. 2)

The temperature at the intersection between the tangent of the curve and the baseline at the point where the differential value of the DSC curve obtained at the time of the temperature rise at the end point of the end point of the endothermic peak is the last. (Corresponding to E ₁ -OP in FIG. 2)

<Each temperature related to the endothermic peak including the maximum endothermic peak (P ₂ ) attributed to the high melting point wax component> In the DSC curve obtained when the peak temperature of the maximum endothermic peak (P ₂ ) rises , 100 to 150
Peak top temperature of the peak showing the maximum endothermic peak in the temperature range of ° C. (Corresponding to P ₂ P in FIG. 2)

The temperature at the intersection of the tangent of the curve and the baseline at the point where the differential value of the DSC curve obtained when the onset temperature of the start point of the endothermic peak rises first becomes the maximum. (Corresponding to S ₂ -OP in FIG. 2)

Heat of fusion exhibited by the maximum endothermic peak (P ₂ ′)
(ΔHa) and melting at the maximum endothermic peak (P ₂ )
Heat (ΔHb) In the DSC curve obtained at the first heating, the maximum endothermic peak is determined from the minimum value between the endothermic peak including the maximum endothermic peak (P ₁ ′) and the endothermic peak including the maximum endothermic peak (P ₂ ′). A tangent is drawn to the end point of the endothermic peak containing (P ₂ ′), and the endothermic amount per unit weight of the wax composition determined from the DSC curve and the portion surrounded by the tangent is the maximum endothermic peak (P ₂ ′). Heat of fusion (ΔHa)
(FIG. 1). Further, the heat of fusion (ΔHb) at which the maximum endothermic peak (P ₂ ) at the time of the second temperature rise is defined in the same manner.

In the wax composition of the present invention, the weight ratio of the low melting point wax component to the high melting point wax component is 1/1.
The ratio may be 9 to 9/1, preferably 1/9 to 8/1.
And more preferably 1/7 to 7/1. If each wax component is to be used outside the range of the use ratio described above, all characteristics required for the toner, such as low-temperature fixability and offset resistance, as well as blocking resistance and developability, must be satisfied. Not only becomes difficult, but when the use ratio of the low melting point wax component is high, the production efficiency is reduced due to the over-crushing phenomenon during the production of the toner, or conversely, when the use ratio of the high melting point wax component is high. However, the dispersibility of the wax composition in the toner deteriorates, which hinders matching with the image forming apparatus.

Further, the wax composition of the present invention comprises, besides the low-melting wax component and the high-melting wax component, other third
One or more wax components can be contained for fine adjustment of low-temperature fixing property, blocking resistance and offset resistance, the content is 20% by weight or less based on the total amount of wax, and the melting point is 60 to 100%. The temperature may be 140 ° C.

In the method for producing a wax composition of the present invention,
A low-melting wax component, a high-melting wax component and, if necessary, a third component are heated and melt-mixed in the absence of a solvent to form a uniform wax melt, and then cooled at a cooling rate of 1 to 20 ° C./sec. Solidifying to obtain a wax composition for a toner.

In the method for producing a wax composition of the present invention, each wax component is heated and melt-mixed without a solvent. When a solvent is used at the time of melt mixing, the amount of the solvent cannot be sufficiently reduced under the above-described cooling conditions, phase separation of the wax component by the remaining solvent is promoted, and the composition of the wax composition becomes non-uniform. As a result, unevenness in toner fixability may occur,
This may cause the developing property and the matching with the image forming apparatus, and may cause an unpleasant odor at the time of fixing the toner by heating. Further, if the heating and drying are performed for a long time to reduce the residual solvent, not only is the production uneconomical, but also the phase separation of the wax component proceeds as described above, and a free component is generated, which is not preferable.

In the production method of the present invention, cooling conditions are important because they affect the state of each wax component. That is, if the cooling rate is less than 1 ° C./sec, phase separation of the wax component proceeds as described above, which is not preferable. Also,
If the cooling rate exceeds 20 ° C./sec, the effect of adding the high melting point wax component partially disappears because most of the low melting point wax and the high melting point wax component remain in a state of being dissolved. Further, since the wax component is plasticized, a problem occurs in storage stability.

As a specific example of the production method of the present invention, the above-mentioned wax components are dry-mixed with a Hensiel mixer or the like, and then melted, kneaded and kneaded using a kneading device such as an extruder to be mutually compatible. A kneading method of pulverizing after cooling and solidifying, after heating and melting the wax component to form a uniform wax melt, discharging and atomizing the wax melt into a tank at least at atmospheric pressure or below, or an air stream,
A spray-drying method for cooling and the like can be mentioned. Among them, a spray drying method is particularly preferable from the viewpoint of dispersibility of the wax component.

The wax component used in the wax composition of the present invention includes aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, and the like.
Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes mainly containing fatty acid esters such as carnauba wax, sasol wax, montanic acid ester wax, and deacidification Fatty acid esters such as carnauba wax are partially or entirely deoxidized. Further, unsaturated straight-chain fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a longer-chain alkyl group, and 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, linole Fatty acid amides such as acid amide, oleic acid amide, lauric acid amide, and saturated fatty acids such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide Suamido, ethylene bis-oleic acid amide, hexamethylene bis-oleic acid amide, N, N'-dioleyl adipic acid amide, N, N '
Unsaturated fatty acid amides, such as dioleyl sebacamide, m-xylene bisstearic acid amide, N,
Aromatic bisamides such as 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 grafted with hydrogen-based wax using vinyl monomers such as styrene and acrylic acid, and partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols, and hydrogenation of vegetable oils and fats The resulting methyl ester compound having a hydroxyl group is exemplified.

In the present invention, the low-melting wax component preferably used is a hydrocarbon having a long-chain alkyl group with few branches. Specifically, for example, radical polymerization of alkylene under high pressure or polymerization of Zylene under low pressure with a Ziegler catalyst is used. Hydrogenated alkylene polymer obtained from the distillation residue of hydrocarbons obtained by the Age method from a synthesis gas consisting of an alkylene polymer obtained by pyrolyzing a high molecular weight alkylene polymer, carbon monoxide, and hydrogen, or hydrogenating them. Waxes such as synthetic hydrocarbons obtained by the above method are preferred. Further, those obtained by separating a hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation or a separation crystallization method are more preferably used. Hydrocarbons as bases are metal oxide catalysts (often two or more types).
Synthesized by the reaction of carbon monoxide and hydrogen using, for example, the Zintole method, the hydrochol method (using a fluidized catalyst bed), or the Aage method using a large amount of waxy hydrocarbons (using a fixed catalyst bed). Is obtained by

The long-chain alkyl group may be partially substituted with a hydroxyl group and a sensitive group derived from the hydroxyl group, such as a carboxyl group, an ester group, an ethoxy group, and a sulfonyl group. The long-chain alkyl alcohol is obtained, for example, by the following production method. That is, ethylene is polymerized using a Ziegler catalyst, and after the polymerization is completed, it is oxidized to generate an alkoxide of the catalyst metal and polyethylene. Thereafter, hydrolysis is performed to obtain a long-chain alkyl alcohol. The long-chain alkyl alcohol thus obtained has a small number of branches and a small molecular weight distribution, and is in accordance with the object of the present invention.

The high-melting-point wax component preferably used in the present invention comprises a hydrocarbon having a long-chain alkyl group with few branches. Specifically, for example, radical polymerization of alkylene under high pressure or polymerization of Zylene under low pressure with a Ziegler catalyst is used. Hydrogenated alkylene polymer obtained from the distillation residue of hydrocarbons obtained by the Age method from a synthesis gas consisting of an alkylene polymer obtained by pyrolyzing a high molecular weight alkylene polymer, carbon monoxide, and hydrogen, or hydrogenating them. Waxes such as synthetic hydrocarbons obtained by the above method are preferred.

The long-chain alkyl group may be partially substituted with a hydroxyl group and a functional group derived from the hydroxyl group, such as a carboxyl group, an ester group, an ethoxy group, and a sulfonyl group. The long-chain alkyl alcohol is obtained, for example, by the following production method. That is, ethylene is polymerized using a Ziegler catalyst, and after the polymerization is completed, it is oxidized to generate an alkoxide of the catalyst metal and polyethylene. Thereafter, hydrolysis is performed to obtain a long-chain alkyl alcohol. The long-chain alkyl alcohol thus obtained has a small number of branches and a small molecular weight distribution, and is in accordance with the object of the present invention.

The low melting point wax preferably used in the present invention has a weight average molecular weight (Mw) of 300 to 1000, preferably 350 to 900, and Mw / Mn of 2.8 or less. Preferably 2.
It is the case where it is 3 or less, most preferably 1.5 or less.
Further, the high melting point wax has a molecular weight of 500 to 15,000, preferably 650 to 10000, and Mw / Mn is 3.0 or less, preferably 2.5 or less, and most preferably 1 or less. .5 or less. By specifying the molecular weight distribution of each wax component, the interaction between the wax components is rapidly developed, and the above-mentioned various properties required of the toner are greatly improved.

In the present invention, the molecular weight distribution of the low-melting wax component and the high-melting wax component, and the molecular weight distribution of the wax composition of the present invention are determined by gel permeation chromatography (G
PC) under the following conditions.

Apparatus: GPC-150C (Waters) Column: GMH-HT 30 cm 2 columns (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (0.1% ionol added) Flow rate: 1.0 ml / min Sample: 0.4 ml of 0.15% sample is injected

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.

An antioxidant may be added to the wax composition of the present invention, if necessary. As the antioxidant, known compounds such as a phenol compound, an amine compound, a sulfur compound and a phosphorus compound can be used. These compounds are used at 0.5% by weight or less. If used in an amount exceeding 0.5% by weight, problems may occur in the offset resistance and blocking resistance of the toner, and the charging characteristics of the toner and the matching with the image forming apparatus may be impaired. Further, it may cause an unpleasant odor at the time of heat fixing, which is not preferable.

The combination of the low melting point wax and the high melting point wax preferably used in the present invention includes, for example, the following combinations.

(1) Combination of low-melting hydrocarbon wax and high-melting hydrocarbon wax: The low-melting hydrocarbon wax is a long-chain alkyl group having few branches, and has a melting point of 70 to 90 ° C.
The weight average molecular weight is 400 to 700, and Mw / Mn is 2.0 or less.

The high melting point hydrocarbon wax is a long-chain alkyl group having few branches, and has a melting point of 95 to 130 ° C., a weight average molecular weight of 800 to 2500, and Mw / Mn = 5.0 or less.

(2) Combination of low-melting hydrocarbon wax and high-melting-point substituted alkyl wax: The low-melting wax used is the same as the low-melting hydrocarbon wax shown in (1) above.

The high-melting-point substituted alkyl-based wax has a long-chain alkyl group with few branches, a substituent other than a hydrogen atom at the terminal or in a part of the molecule, and the substituent is a hydroxyl group and / or a carboxyl group. And an alkyl group having a substituent is contained in an amount of 50% by weight or more of the total wax.
Melting point 95-130 ° C, weight average molecular weight 800-500
0, Mw / Mn = 2.0 or less.

(3) Combination of low-melting-point substituted alkyl-based wax and high-melting-point hydrocarbon wax: The low-melting-point substituted alkyl-based wax has a long-chain alkyl group with few branches, and a terminal or a part of the molecule other than a hydrogen atom. Wherein the substituent is a hydroxyl group and / or a carboxyl group, and the alkyl group having the substituent is contained in 40% by weight or more of the total wax. Melting point 70-90 ° C, weight average molecular weight 40
0 to 700, Mw / Mn = 2.0 or less.

As the high melting point hydrocarbon wax, the same high melting point hydrocarbon wax as described in the above (1) can be used.

(4) Combination of low-melting-point substituted alkyl-based wax and high-melting-point-substituted alkyl-based wax: The low-melting-point substituted alkyl-based wax may be the same as the low-melting-point alkyl-based wax described in (3) above.

As the high melting point substituted alkyl-based wax, the same high melting point substituted alkyl-based wax shown in the above (2) can be used.

The wax composition of the present invention can contain 1 to 20 parts by weight with respect to 100 parts by weight of a binder resin in the production of a toner, and can be compared with waxes known in the art today. Since the low-melting-point wax component and the high-melting-point wax component are functionally separated, it is easy to adjust the amount of addition and to disperse the wax.

The wax composition of the present invention can be added to a toner by various methods. In general, the pulverized wax composition is added to a toner constituent material such as a binder resin or a magnetic material by stirring and mixing with a Henschel mixer or the like, and then melt-kneaded. Further, as another preferable method of adding the wax composition, there is a method of heating and dissolving the binder resin in an organic solvent, thereafter adding the wax composition, and evaporating the solvent to dryness. There is a method in which the binder resin is heated and melted without using the wax composition and the wax composition is added. Another preferred method of adding the wax composition is a method of adding the wax composition in a binder resin synthesis step or a polymerization step of a polymerization toner. Also,
Another preferable method of adding the wax composition is a method of directly adding the wax composition to the surface of the toner. After preparing a toner classified product, the wax composition finely pulverized to 1 μm or less is dry-processed with a Henschel mixer or the like. It is a method of mixing. In this case, it is selected by either a batch mixing method with a known additive added to the toner for other purposes, or a two-stage mixing method of mixing the wax composition and then mixing the additive. .

The wax composition of the present invention can be used in combination with a known binder resin, but is preferably used for a polyester resin and a vinyl resin.

The polyester resin to which the wax composition of the present invention is preferably used is as follows.

The composition of the polyester resin is 4% of all components.
5 to 55 mol% is an alcohol component, and 55 to 45 mol%.
mol% is the acid component.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and a bisphenol derivative represented by the formula (a);

[0079]

Embedded image

Diols represented by the formula (b):

[0081]

Embedded image And the like.

The divalent carboxylic acid containing 50 mol% or more of the total acid component includes benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydrides thereof; succinic acid, adipic acid, sebacine Alkyl dicarboxylic acids such as acid and azelaic acid or anhydrides thereof, and succinic acid or anhydrides further substituted with an alkyl group having 6 to 18 carbon atoms; non-succinic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid; Saturated dicarboxylic acids or anhydrides thereof are exemplified.

Further, polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, and oxyalkylene ethers of novolak type phenol resins; trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and anhydrides thereof And the like.

The particularly preferred alcohol component of the polyester resin in the practice of the present invention is a bisphenol derivative represented by the above formula (A), and the preferred acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, or succinic acid. , N-dodecenyl succinic acid, or anhydrides thereof, and dicarboxylic acids such as fumaric acid, maleic acid, and maleic anhydride. Preferred examples of the crosslinking component include trimellitic anhydride, benzophenonetetracarboxylic acid, pentaerythritol, and oxyalkylene ether of a novolak type phenol resin.

The polyester resin thus obtained has a glass transition temperature of 40 to 90 ° C., preferably 45 to 85 ° C., and a number average molecular weight (Mn) of 1,000 to 50,000.
Preferably from 1,500 to 20,000, more preferably from 2,500 to 10,000, weight average molecular weight (Mw)
3,000 to 3,000,000, preferably 10,000
00 to 2,500,000, more preferably 40,0
00 to 2,000,000.

[0086] Examples of the vinyl monomer for producing the vinyl resin include the following.

For example, styrene, o-methylstyrene, m
-Methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
styrene and its derivatives such as p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene; ethylene; Ethylenically unsaturated monoolefins such as propylene, butylene and isobutylene; unsaturated polyenes such as butadiene;
Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl ester acids such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid α-methylene aliphatic monomers such as n-butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Carboxylic esters;
Methyl acrylate, ethyl acrylate, acrylic acid n-
Butyl, isobutyl acrylate, propyl acrylate,
Acrylic esters such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N
N- such as vinylindole and N-vinylpyrrolidone
Vinyl compounds; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; esters of the above-mentioned α, β-unsaturated acids and diesters of dibasic acids.

Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride and alkenyl succinic anhydride Unsaturated dibasic acid anhydrides such as those; methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, methyl itaconate Half esters of unsaturated dibasic acids such as half ester, methyl alkenyl succinate half ester, methyl fumarate half ester and methyl half mesaconic acid; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; Acid, methacrylic acid, crotonic acid, such as cinnamic acid alpha, beta-unsaturated acid; crotonic acid anhydride, such as alpha of cinnamic acid anhydride, beta-unsaturated acid anhydride, the alpha, beta
-Anhydrides of unsaturated acids and lower fatty acids; and monomers having a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides and monoesters thereof.

Also, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Monomers having a hydroxyl group such as (hydroxy-1-methylhexyl) styrene are exemplified.

The glass transition temperature of this vinyl resin is 45
-80 ° C, preferably 55-70 ° C, and a number average molecular weight (Mn) of 2,500-50,000, preferably 3,000-20,000, and a weight average molecular weight (M
It is preferred that w) is from 10,000 to 1,500,000, preferably from 25,000 to 150,000.

The development characteristics of the toner can be improved by adding a charge control agent to the wax composition of the present invention in advance. That is, good chargeability can be obtained by increasing the dispersibility of the charge control agent in the wax composition. This also makes it possible to reduce the amount of the charge control agent used, and at the same time improves the durability of the toner. On the other hand, by adding the charge control agent to the wax composition, the wax composition is protected from deterioration due to oxidation and the like, and can maintain a predetermined performance for a long period of time. Also, no special storage equipment is required.

The charge control agent is the same as the wax composition 100
1 to 200 parts by weight, preferably 1 to 15 parts by weight based on parts by weight
It is preferred to use 0 parts by weight.

The charge control agents known in the art today include the following:

For example, organic metal complexes and chelate compounds are effective. Examples thereof include a monoazo metal complex, an aromatic hydroxycarboxylic acid, a metal complex, and an aromatic dicarboxylic acid-based metal complex. Others include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides,
Examples include esters and phenol derivatives of bisphenol.

When the wax composition of the present invention is used in a magnetic toner, the wax composition may be previously mixed with magnetic particles. In this case, the wax composition and the magnetic particles are mixed with a wheel-type kneader. Alternatively, the magnetic particles are preferably kneaded by compression, shearing and spatula using a grinder to coat the surface of the magnetic particles with the wax composition. By coating the surface of the magnetic particles with the wax composition, the compatibility with the binder resin in the toner is improved, and the dispersibility is improved. Thereby, matching with the image forming apparatus is improved. In this case, the wax composition comprises:
It is preferable to use 1 to 30 parts by weight based on 100 parts by weight of the magnetic particles.

[0096] Magnetic materials for magnetic particles known in the art today include the following. For example, iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides; Fe, Co, N
i, or these metals and Al, C
o, Cu, Pb, Mg, Ni, Sn, Zn, Sb, B
alloys with metals such as e, Bi, Cd, Ca, Mn, Se, Ti, W and V, and mixtures thereof.

The magnetic particles have an average particle size of 0.1 to 2
about 10 μm, the magnetic characteristics when a 10K Oersted is applied show a coercive force of 20 to 150 Oersted saturation magnetization of 50 to 200 e
mu / g (preferably 50 to 100 emu / g) and a residual magnetization of 2 to 20 emu / g are desirable.

The wax composition of the present invention improves the color development of the toner by adding a coloring agent such as a pigment and / or a dye in advance. Particularly when used in a full-color toner, not only good sharpness can be obtained by increasing the dispersibility of the colorant, but also the uniformity of development unevenness due to the action of the low melting point wax component and the high melting point wax component. As a result, a high quality image can be obtained because a good image and a uniform image surface with good fixability can be obtained. In this case, the coloring agent is used in an amount of 10 to 30 parts by weight based on 100 parts by weight of the wax composition.
It is preferable to use 0 parts by weight, preferably 20 to 200 parts by weight.

Colorants for toner are well known, and include, for example, carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow,
Rhodamine lake, Alizarin lake, Bengala, phthalocyanine blue, indanthrene blue, titanium white and the like. Examples of the dye include an azo dye, an anthraquinone dye, a xanthene dye, and a methine dye.

[0100]

The present invention will be described below by way of examples.

[Production Examples 1 to 6 and Comparative Production Examples 1 to 5 of Wax Compositions] A low-melting-point wax component and a high-melting-point wax component were weighed, preliminarily mixed uniformly with a Henschel mixer, and then heated and melted to obtain a uniform mixture. A wax melt was obtained. This was converted into an EHP-604 system (nozzle pressure: 1 kg / m ² ) manufactured by Nippon Devilbiss Co., Ltd. with a spray gun of a spray drier (manufactured by Mitsubishi Kakoki), and discharged and atomized in an air stream to obtain a spherical wax composition. The cooling rate of the wax composition was adjusted by the temperature at the inlet and the outlet and the pressure difference.
The obtained spherical wax composition was pulverized to obtain wax compositions (A) to (F) for toner of the present invention and wax compositions (a) to (e) for comparison.

Table 1 shows the contents of the low-melting wax component and the high-melting wax component used in the above Production Examples and Comparative Production Examples, and the obtained wax compositions (A) to (F).
And the manufacturing conditions (a) to (e) and the differential scanning calorimeter (D
Table 2 summarizes the measurement results of SC).

Example 1 Binder resin 100 parts by weight [Styrene-butyl acrylate-divinylbenzene copolymer produced by solution polymerization method] Mw = 200,000, Tg = 59 ° C.] Fine magnetic powder 100 parts by weight Negatively chargeable charge control agent 2 parts by weight [azo dye-based iron complex] Wax composition 7 parts by weight [Wax composition obtained in Production Example 1 above] Thing (A)]

After the above materials were premixed with a Henschel mixer, they were heated to 110 ° C. and melt-kneaded with a twin-screw extruder. After cooling, the kneaded product was coarsely pulverized with a hammer mill and further finely pulverized with a jet mill, and the obtained pulverized product was subjected to air classification to obtain a classified product (I) having a weight average diameter of 6.5 μm.

<Evaluation of Toner Productivity> At this time, the number% of fine powder having a particle diameter of 4.00 μm or less in the above-mentioned pulverized material was used as a measure of productivity, and the influence of the wax composition was evaluated.

The particle size distribution can be measured by various methods. In the present invention, the particle size distribution was measured using a 100 μm aperture on a Coulter Counter Multisizer II (manufactured by Coulter).

◎: Very good (less than 20% by number) ：: Good (more than 20% by number and less than 25% by number) △: Practical (25% by number or more, less than 35% by number) ×: Not practical (35% by number) %that's all)

Examples 2 to 5 and Comparative Examples 1 to 4 The wax compositions (B) to (E) of the present invention obtained in the above Production Examples and the waxes (9 ), (10), and the classified waxes (d) and (e) obtained in Comparative Production Examples, except that the classified waxes (II) to (V) and Comparative classified products (i) to (iv) were obtained.

Example 6 100 parts by weight of binder resin [terephthalic acid (15 mol), fumaric acid (18 mol), trimellitic anhydride (16 mol), propoxy adduct of bisphenol (28 mol), and ethoxy adduct of bisphenol ( Non-linear polyester obtained by polycondensation of 20 mol). Mw = 40000, Tg = 62 ° C.] Magnetic fine powder 90 parts by weight Negatively chargeable charge control agent 2 parts by weight [Salicylic acid-based iron complex] Wax composition 7 parts by weight [Wax composition obtained in Production Example 6 above ( F)]

A classified product (VI) was obtained in the same manner as in Example 1 except that the above-mentioned materials were used.

[Comparative Example 5] As a wax composition, 4.7 parts by weight of wax (3) shown in Table 1 and wax (7)
Was changed to 2.3 parts by weight in the same manner as in Example 6 to obtain a comparative classified product (v).

[Comparative Examples 6 to 8] Comparative wax compositions (a) to (x) obtained in the above comparative production examples as wax compositions.
Except that each of (c) was used, comparative classified products (vi) to (viii) were obtained in the same manner as in Example 6.

1.2 parts by weight of hydrophobic oil-treated silica fine powder (BET
(Specific surface area: 300 m ² / g) was dry-mixed with a Henschel mixer to obtain toners (I) to (VI) and comparative toners (i) to (viii).

Next, the image forming apparatus used in the embodiment will be described. In this example, a commercially available laser beam printer LBP-SX (manufactured by Canon) and a cartridge for the printer were reset and modified for use.

The printer was modified under the following conditions. That is, 600d due to the modification of the laser unit
After the pi machine, an electrostatic latent image is formed by temporarily charging at −600 V, a gap (300 m μm) is set in a non-contact manner between the photosensitive drum and the developer layer on the developing sleeve (magnet inclusion), and an AC bias (f = 1800 Hz, Vpp = 1300 V) and a DC bias V _DC = −450 V) were applied to the developing sleeve. The rotation speed of the fixing device was 36 mm / sec, and the temperature of the fixing device was 130 ° C.

The printer cartridge is shown in FIG.
Modified as shown in That is, a commercially available toner cartridge for a laser beam printer LBP-8II (manufactured by Canon) was modified as shown in FIG. Attach an elastic blade made of urethane rubber.
It was set to 0 g / cm, and each of the toners was filled.

Under the above set conditions, the room temperature and the normal humidity (25 ° C., 6
0% RH) and a high-temperature and high-humidity (30 ° C., 80% RH) environment at a printout speed of 6 sheets (A4 size) / minute while replenishing the toner according to the present invention and the comparative toner. A printout test was performed on 10,000 continuous sheets, and the obtained images were evaluated for the following items. At the same time, matching between the used image forming apparatus and the toner was also evaluated.

[Evaluation of Printout Image] (1) Image Density The image density was evaluated by maintaining the image density at the end of printing 3000 sheets of ordinary paper for copying machines (75 g / m ² ).
The image density was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth Co., Ltd.) with respect to a printout image of a white background portion having a document density of 0.00.

◎ (excellent): 1.40 or more ○ (good): 1.35 or more and less than 1.40 Δ (acceptable): 1.00 or more and less than 1.35 × (impossible): less than 1.00

(2) Dot Reproducibility The pattern shown in FIG. 4 was printed out, and the dot reproducibility was evaluated.

A: very good (less than 2 defects / 100
○: Good (3-5 defects / 100 defects) △: Normal (6-10 defects / 100 defects) ×: Bad (11 or more defects / 100 defects)

(3) Image fog The fog density (%) was calculated from the difference between the whiteness of the white background portion of the printout image measured by the “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper. Image fog was evaluated.

A: Very good (less than 1.5%) A: Good (1.5% or more, less than 2.5%) C: Normal (2.5% or more, less than 4.0%) X: Bad (4% or more)

(4) Fixing Property The fixing property was evaluated by applying a load of 50 g / cm ² , rubbing the fixed image with soft thin paper, and decreasing the image density before and after rubbing (%).

◎ (excellent): 5% or less ○ (good): 5% or less, less than 10% Δ (acceptable): 10% or more, less than 20% × (impossible): 20% or more

(5) Offset Resistance The offset resistance was evaluated by printing out a sample image having an image area ratio of about 5% and evaluating the degree of stain on the image after 3000 sheets.

◎: very good (not generated) ：: good (almost no occurrence) △: normal ×: worse than △

[Evaluation of Image Forming Apparatus Matching] (1) Matching with Developing Sleeve After the printout test was completed, the state of fixation of the residual toner on the surface of the developing sleeve and the effect on the printout image were visually evaluated.

◎: very good (not generated) ：: good (almost no occurrence) Δ: practical (there is sticking, but there is little effect on the image) ×: impractical (many sticking, image unevenness Arises)

(2) Matching with Photosensitive Drum The occurrence of scratches on the surface of the photosensitive drum and sticking of residual toner and the effect on printout images were visually evaluated.

◎: very good (not generated) 良好: good (slight flaws are observed, but there is no effect on the image) Δ: practical (possible fixation and flaws, but the effect on the image is low) X): Impossible (many sticks, causing vertical streak-like image defects)

[Evaluation of Blocking Resistance] About 10 g of the toner was put in a 100 cc polycup, left at 50 ° C. for 3 days, and the effect on the toner was visually evaluated.

◎: very good (no change) ：: good (aggregates can be seen but loosened easily) Δ: practical (easy to loose) ×: impractical (caking)

Table 3 summarizes the above evaluation results.

[0135]

[Table 1]

[0136]

[Table 2]

[0137]

[Table 3]

[0138]

As described above, according to the present invention,
By using the wax composition as described above, not only good low-temperature fixability can be achieved, but also a toner which is excellent in offset resistance and blocking resistance and does not deteriorate in developability even after long-term use can be obtained. Further, it is possible to realize a high-quality image and to obtain a toner with good matching with the image forming apparatus. Further, excessive pulverization during toner production can be prevented, and the production efficiency can be improved. The wax composition of the present invention makes it possible to attain a high degree of properties required for the toner without inconsistency.

[Brief description of the drawings]

FIG. 1 is a schematic diagram illustrating a DSC curve of a wax composition of the present invention at the first temperature rise measured by a differential scanning calorimeter (DSC).

FIG. 2 is a schematic diagram illustrating a DSC curve of a wax composition of the present invention at the time of a second temperature rise measured by a differential scanning calorimeter (DSC).

FIG. 3 is a schematic explanatory view of an image forming apparatus used in an embodiment of the present invention.

FIG. 4 is an explanatory diagram of a checker pattern for checking development characteristics of toner.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Developing device 2 Developer container 3 Latent image carrier 4 Transfer means 5 Laser light or analog light 6 Developing sleeve 7 Heating and pressurizing fixing means 8 Cleaning blade 9 Elastic blade 11 Charger 12 Bias applying means 13 Magnetic developer 14 Cleaning means 15 Magnetic field generating means 16 Erase exposure

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Matsunaga 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-8-166683 (JP, A) JP-A-7 -271095 (JP, A) JP-A-6-130723 (JP, A) JP-A-5-88412 (JP, A) JP-A-6-19204 (JP, A) JP-A-63-125950 (JP, A) JP-A-3-139663 (JP, A) JP-A-8-106173 (JP, A) JP-A-3-91764 (JP, A) JP-A-5-216273 (JP, A) JP-A-6-106273 295093 (JP, A) JP-A-6-324513 (JP, A) JP-A-60-88961 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08

Claims (7)

(57) [Claims] 1. A wax composition used for an electrostatic image developing toner, wherein the wax composition contains two or more kinds of waxes having different melting points (low-melting wax / high-melting wax) as main components, The wax composition was measured by a differential scanning calorimeter (DSC).
Regarding the endothermic peak at the time of temperature rise of the DSC curve determined, the high melting point wax component of the DSC curve obtained at the first temperature rise
Heat of fusion given by the maximum endothermic peak (P ₂ ')
(ΔHa) and the maximum endothermic peak at the second heating (P ₂ )
The heat of fusion (ΔHb) exhibited by the following equation (1) : Satisfies the relationship, with respect to an endothermic peak of the second temperature Nukutoki of the D SC curve has (a) a low melting wax component, the maximum endothermic peak at 60~90 ℃ (P _1), said maximum endothermic peak (B) the high melting point wax component has a maximum endothermic peak (P ₂ ) at 100 to 150 ° C., and (c) the onset temperature of the starting point of the endothermic peak containing (P ₁ ) is 50 ° C. or higher. Maximum endothermic peak of low melting wax component (P ₁ )
And the maximum endothermic peak (P ₂ ) of the high melting point wax component satisfies the relationship of (P ₂ peak temperature) − (P ₁ peak temperature) ≧ 20. The wax composition used. 2. The differential scanning calorimeter (D) of the wax composition.
SC), the endothermic peak at the end of the endothermic peak including the maximum endothermic peak (P ₁ ) <the endothermic peak at the end of the endothermic peak including the maximum endothermic peak (P ₁ ) <(the maximum endothermic peak (P ₂ ) The wax composition used in the toner for developing an electrostatic image according to claim 1, wherein an onset temperature of a starting point of an endothermic peak is included. 3. The endothermic peak at the time of the second temperature rise of the DSC curve of the wax composition measured by a differential scanning calorimeter, the height (h ₁ ) of the maximum endothermic peak (P ₁ ) and the maximum endotherm during the peak height of the (P ₂₎ (h ₃₎ the height minimum value between the both peaks _{(h 2), h 1:} h 2: h 3 = 1: (0~0.5): (0.1-1.
5) The wax composition for use in an electrostatic image developing toner according to claim 1 or 2 , wherein the following formula is satisfied. 4. A method for producing a wax composition used in a toner for developing an electrostatic image, comprising measuring the wax composition with a differential scanning calorimeter (DSC).
Regarding the endothermic peak at the time of temperature rise of the DSC curve determined, the high melting point wax component of the DSC curve obtained at the first temperature rise
Heat of fusion given by the maximum endothermic peak (P ₂ ')
(ΔHa) and the maximum endothermic peak at the second heating (P ₂ )
The heat of fusion exhibited by the (ΔHb) is of the following formula (1) [number 2] Satisfies the relationship, the terms second endothermic peak during heating of D SC curve has a maximum endothermic peak (P ₁₎ to 60 to 90 ° C., the endothermic peak containing said maximum endothermic peak (P ₁₎ the start point and the onset temperature of 50 ° C. or higher, further, has a maximum endothermic peak (P ₂₎ to 100 to 150 ° C., said maximum endothermic peak (P ₁₎ and said maximum endothermic peak (P ₂₎ is ( peak temperature of the P ₂₎ - (so as to satisfy the relation of peak temperature) ≧ 20 of P _1, heated melt mixing at least low melting wax component and high-melting wax component in the absence of a solvent,
A method for producing a wax composition for use in a toner for developing electrostatic images, comprising obtaining a uniform wax melt, followed by cooling and solidification at a cooling rate of 1 to 20 ° C./sec to obtain the wax composition. 5. An electrostatic image developing toner containing at least a binder resin and a wax composition, wherein the wax composition mainly comprises two or more kinds of waxes having different melting points (low-melting wax / high-melting wax). As a component, the wax composition was measured with a differential scanning calorimeter (DSC).
Regarding the endothermic peak at the time of temperature rise of the DSC curve determined, the high melting point wax component of the DSC curve obtained at the first temperature rise
Heat of fusion given by the maximum endothermic peak (P ₂ ')
(ΔHa) and the maximum endothermic peak at the second heating (P ₂ )
The heat of fusion exhibited by the (ΔHb) is of the following formula (1) [number 3] Satisfies the relationship, with respect to an endothermic peak of the second temperature Nukutoki of the D SC curve has (a) a low melting wax component, the maximum endothermic peak at 60~90 ℃ (P _1), said maximum endothermic peak (B) the high melting point wax component has a maximum endothermic peak (P ₂ ) at 100 to 150 ° C., and (c) the onset temperature of the starting point of the endothermic peak containing (P ₁ ) is 50 ° C. or higher. Maximum endothermic peak of low melting wax component (P ₁ )
And the maximum endothermic peak (P ₂ ) of the high melting point wax component satisfies the following relationship: (P ₂ peak temperature) − (P ₁ peak temperature) ≧ 20. 6. A differential scanning calorimeter (D) of the wax composition.
SC), the endothermic peak at the end of the endothermic peak including the maximum endothermic peak (P ₁ ) <the endothermic peak at the end of the endothermic peak including the maximum endothermic peak (P ₁ ) <(the maximum endothermic peak (P ₂ )) 6. The toner for developing an electrostatic image according to claim 5 , wherein the onset temperature of the starting point of the endothermic peak includes the following. 7. The endothermic peak at the time of the second temperature rise of the DSC curve of the wax composition measured by a differential scanning calorimeter, the height (h ₁ ) of the maximum endothermic peak (P ₁ ) and the maximum endotherm during the peak height of the (P ₂₎ (h ₃₎ the height minimum value between the both peaks _{(h 2), h 1:} h 2: h 3 = 1: (0~0.5): (0.1-1.
The toner according to claim 5, which satisfies the following condition: 5).