JP3108825B2 - Toner for developing electrostatic images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image suitable for heat fixing used in electrophotography, electrostatic recording and magnetic recording.

[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. It is very effective in an electrophotographic copying machine. 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 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 release properties with respect to the toner, such as silicone rubber or a fluorine-based resin. 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. However, this method is extremely effective in preventing toner offset, but has a problem that a fixing device is complicated 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 device is used in which a small amount of a release agent is added to the toner so as not to deteriorate the image, and a small amount of release oil is supplied or the offset toner is wound up with a device using a web-type member such as a web. It has been used in combination.

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, if there is no further performance improvement such as toner fixing and offset,
It is difficult to realize this without further improvement of the binder resin of the toner, the release agent and the like.

It is known that wax is used as a release agent in a toner. For example, JP-A-52-3304
JP, JP-A-52-3305, JP-A-57-5-5
No. 2574 discloses a technique.

Further, JP-A-3-50559, JP-A-2-79860, JP-A-1-109359, JP-A-62-14166, and JP-A-61-27
No. 3554, No. 61-94062, Japanese Unexamined Patent Publication No. Sho 61
-138259, JP-A-60-252361, JP-A-60-252360, JP-A-60-2
No. 17366 discloses a technique for containing waxes.

[0012] Waxes are used for improving the offset resistance of the toner at low and high temperatures and for improving the fixing property at low temperatures. However, while improving these performances, the blocking resistance is deteriorated, the developability is deteriorated when exposed to heat due to the temperature rise of a copying machine, etc., and the developability is deteriorated due to the blooming of wax when left for a long period of time. Or worse.

No conventional toner satisfies all of these aspects, causing some problems. For example, high-temperature offset and developability are excellent, but low-temperature fixability is just one step away, or low-temperature offset and low-temperature fixability are excellent, but blocking resistance is slightly inferior, and developability decreases when the temperature rises in the machine. And the offset resistance at low and high temperatures cannot be compatible.

Also, low molecular weight polypropylene (for example,
Viscole 550P, 660 manufactured by Sanyo Chemical Industry Co., Ltd.
P, etc.) are commercially available, but toners with further improved anti-offset properties and improved fixability have been desired.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic image, which solves the above-mentioned problems.

That is, an object of the present invention is to provide a toner for developing an electrostatic image, which is excellent in fixing property at low temperature and anti-offset property.

Another object of the present invention is to provide a toner for developing an electrostatic charge image which has excellent offset resistance at high temperatures.

It is a further object of the present invention to provide a toner for developing an electrostatic charge image which has excellent blocking resistance and does not deteriorate in developability even after being left for a long time.

It is another object of the present invention to provide a toner for developing an electrostatic charge image which is excellent in durability against temperature rise of a machine main body.

A main object of the present invention is to provide a toner for developing an electrostatic image, which satisfies the above objects without contradiction.

[0021]

According to the present invention, there is provided a toner for developing an electrostatic image containing at least a binder resin and a hydrocarbon wax, wherein the molecular weight distribution of the toner by GPC is from 3 × 10 ^{3 to} 5 × 10 ^3. At least one peak (P ₁ ) exists in an area of × 10 ⁴ , and at least one peak (P ₂ ) exists in an area of 10 ⁵ or more, and 10 ⁵
The following components are 50% or more, and in a DSC curve measured by a differential scanning calorimeter, the onset temperature at the endothermic peak at the time of temperature rise is 105 ° C or less, and the endothermic peak temperature is in the range of 100 to 120 ° C. Wherein the exothermic peak temperature at the time of cooling is in the range of 62 to 75 ° C., and the exothermic peak intensity ratio is 5 × 10 ⁻³ or more.

Further, the present invention relates to a toner for developing an electrostatic image containing at least a binder resin and a hydrocarbon wax, wherein the molecular weight distribution of the toner by GPC is 3 ×.
10 ³ to 5 × There are at least one peak (P ₁₎ to 10 ⁴ of the region, at least one peak (P ₂₎ is present in 10 ⁵ or more regions, 10 ⁵ The following components 50
% Or more, and the DSC curve of the hydrocarbon wax measured by a differential scanning calorimeter indicates that the onset temperature at the endothermic peak of the wax at the time of temperature rise is 50 to 9%.
0 ° C., at least one endothermic peak in a temperature range of 90 to 120 ° C., and a maximum exothermic peak at the time of temperature fall within a range of ± 9 ° C. of the peak temperature of the endothermic peak. And a toner for developing an electrostatic image.

Further, in the molecular weight distribution of the toner by GPC, at least one peak (P ₁ ) exists in a region of 3 × 10 ^{3 to} 5 × 10 ⁴ and at least one peak (P ₁ ) exists in a region of 10 ⁵ or more. ₂ ) is present, and the maximum peak height (H1) on the low molecular weight region side, the maximum peak height (H3) on the high molecular weight region side, and the minimum value height (H2) between the two peaks are H1. : H2: H3 = 3 to 25: 1: 1.5
It is preferable that the relationship of H1> H3 is satisfied.

Further, the present invention will be described in detail.

The resin component having a molecular weight of 5 × 10 ⁴ or less is a component that mainly governs the fixing property and the blocking property, and the component having a molecular weight of 10 ⁵ or more is a component that mainly governs the high-temperature offset property. By appropriately mixing these components, it is possible to balance the fixing property and the offset resistance.

According to the present invention, the molecular weight distribution of the toner by GPC is in the range of 3 × 10 ^{3 to} 5 × 10 ⁴ , preferably in the range of 3 × 10 ^{3 to} 3 × 10 ⁴ , particularly preferably 5 × 10 ^3.
It is characterized in that at least one peak (P ₁ ) exists in a region of 10 ^{3 to} 2 × 10 ⁴ , and good fixability can be obtained. 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, and preferably wherein at least one peak (P ₂₎ is present in the region of ^{3 × 10 5 ~5 × 10 6} , 3 × 10
It is particularly preferable that there is a maximum peak in a region of 10 ⁵ or more in a region of ^{5 to} 2 × 10 ⁶ , and good high-temperature offset resistance is 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 with 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 peak is a maximum peak in a region of 10 ⁵ or more.

The component in the region of 10 ⁵ or less is characterized by being 50% or more, preferably 60 to 90%, particularly preferably 65 to 85%. When the content is within this range, good fixability is exhibited, and the effect of the wax component of the present invention is sufficiently exerted to obtain good fixability and offset resistance. If it is less than 50%, not only the sufficient fixing property cannot be obtained but also the pulverizability becomes inferior. If it exceeds 90%, it tends to be weak against high-temperature offset.

Further, in the molecular weight distribution of the toner by GPC, the height (H1) of the maximum peak on the low molecular weight region side, the height (H3) of the maximum peak on the high molecular weight region side, and the height of the minimum value between the two peaks. (H2) is H1: H2: H3 = 3
２５25: 1: 1.5 to 12, preferably H1: H2: H
3 = 5 to 20: 1: 2 to 10, particularly preferably H1: H
2: H3 = 8 to 18: 1: 2 to 6 are satisfied, whereby good fixability and anti-offset property can be obtained. When H1 is less than 3 or H3 exceeds 12, or when H1 ≦ H3, good fixability is not obtained, and H1 exceeds 25 or H1
When 3 is less than 1.5, good blocking resistance,
The offset resistance cannot be obtained. (See FIG. 15) In the present invention, the molecular weight distribution of the chromatogram of the toner by GPC (gel permeation chromatography) is measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40 ° C., and 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.

A sample is prepared as follows.

The sample is placed in THF, left for several hours, shaken sufficiently, mixed well with THF (until the sample is no longer united), and allowed to stand for 12 hours or more. At this time, TH
The time of leaving in F is set to 24 hours or more. Then, a sample processing filter (pore size 0.45 to
0.5 μm, for example, Myshoridisk H-25-
5 The product passed through Tosoh Co., Ltd., and can be used as a sample of GPC. The sample concentration is
The resin component is adjusted to be 0.5 to 5 mg / ml.

Further, according to the present invention, in a DSC curve of the toner measured by a differential scanning calorimeter, the rise of an endothermic peak at the time of temperature rise is preferably 80 ° C. or more,
Excellent blocking resistance. When the temperature is lower than 80 ° C., the toner starts to undergo a plastic change in a long-term range from a relatively low temperature, and is inferior in storability or deteriorates in developability with increasing temperature. Further, the onset temperature of the endothermic peak is 105 ° C or less (preferably in the range of 90 to 102 ° C).
Which is excellent in low-temperature fixability. If the temperature exceeds 105 ° C., the temperature of the plastic change in a short time range becomes high, and the low-temperature offset resistance and the fixability become poor.

The endothermic peak temperature is 100 to 120 ° C.
(Preferably 102 to 115 ° C.), whereby good fixability and high-temperature offset resistance can be obtained. If the temperature is lower than 100 ° C., the wax component is dissolved in the binder resin before the temperature becomes high, and it is difficult to obtain sufficient offset resistance at high temperatures.
If it exceeds 120 ° C., it is difficult to obtain a sufficient fixing property.

That is, since the binder resin for toner used for heat fixing enters a viscoelastic region where fixation is possible from about 100 ° C., melting of the wax component in this temperature region causes a plasticizing effect on the resin. Thus, the fixing property can be improved, the releasing effect can be sufficiently exhibited, and the offset resistance can be improved. Therefore, it does not wrap around the fixing roller or the film and does not rely on the separation claw, so that it does not easily form a nail mark, does not stain the pressure roller, and does not wrap around the pressure roller. As long as the conditions are satisfied, peaks may be present in other regions.

When the temperature is lowered, changes in the state of the toner at normal temperature and in the state of cooling can be observed, and an exothermic peak accompanying the transition, coagulation and crystallization of the wax component is observed. In the present invention, the exothermic peak temperature is 62 to 75 ° C (preferably 65 to 75 ° C).
-72 ° C), thereby exhibiting good fixability and blocking resistance. On the other hand, 7
If the temperature exceeds 5 ° C., the temperature range in which the wax is in a molten state is narrowed, and the fixability is poor. If the temperature is lower than 62 ° C., blocking, fusing, and the like are likely to occur, and the plasticizing effect of the binder resin is maintained until a low temperature. May occur.

The exothermic peak intensity ratio is 5 × 10 ⁻³ or more (preferably 10 × 10 ⁻³ or more, particularly preferably 15 × 10 ⁻³ or more). The higher the peak intensity ratio, the higher the density of the wax component,
The crystallinity is high, the hardness is high, blocking is less likely to occur, and the triboelectricity is excellent. If it is less than 5 × 10 ⁻³ , the blocking resistance deteriorates or the developability is affected, and the developability deteriorates particularly when the temperature rises. It is easy to appear when it becomes. Further, fusion on the photoreceptor easily occurs. As long as these conditions are satisfied, peaks may be present in other regions at 75 ° C. or higher.

In the DSC measurement of the present invention, since the exchange of heat of the toner is measured and its behavior is observed, it is necessary to perform measurement with a high-precision internal heating input compensation type differential scanning calorimeter from 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. As the DSC curve used in the present invention, a DSC curve measured when the temperature is raised once, a pre-history is taken, and then the temperature is decreased and raised at a temperature rate of 10 ° C./min.
The definition of each temperature is defined as follows. Endothermic peak (the positive direction is regarded as endothermic) Peak rising temperature (LP): Temperature at which the peak curve is clearly deviated from the baseline. That is, the temperature at which the differential value of the peak curve is positive and the increase of the differential value starts to increase or the temperature at which the differential value changes from negative to positive. (A specific example is shown in FIG. 1 and FIGS. 3 to 6.) Peak temperature (PP): Peak top temperature (120 ° C.)
Largest peaks in the following areas: The peak onset temperature (OP): the tangent of the curve at the point where the differential value of the peak curve that can be attributed to the PP becomes the maximum, and the temperature at the intersection of the tangent and the baseline (a specific example is shown in FIG. 1). Exothermic peak (The negative direction is assumed to be exothermic) Exothermic peak temperature: Peak top temperature Exothermic peak intensity ratio: Curves at the points where the differential values of the curves before and after the peak top are maximum and minimum And the temperature difference between each tangent and the base line intersection is defined as ΔT, and the height from the base line to the peak top per unit weight is ΔH (value mW obtained by dividing the height of the measured peak by the weight of the measurement sample). / Mg) ΔH / Δ
T (FIGS. 2 and 7 to 10 show specific examples of ΔH and ΔT). That is, a large value indicates that the peak is sharp.

The hydrocarbon wax used in the present invention is a low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or a Ziegler catalyst under low pressure, or an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer. A hydrocarbon wax obtained by extracting and separating a specific component from a synthetic hydrocarbon obtained by hydrogenating a distillation residue of a hydrocarbon obtained from the synthesis gas consisting of carbon monoxide and hydrogen by the Atage method is used. The hydrocarbon wax is separated by a separation crystallization method using a press sweating method, a solvent method, and vacuum distillation. That is, those obtained by removing the low molecular weight components by these methods, those obtained by extracting the low molecular weight components, and those obtained by further removing the low molecular weight components therefrom.

Hydrocarbons as bases are synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often a multi-component system), such as the Zintol method and the Hydrochol method ( Hydrocarbons using a fluidized catalyst bed) or hydrocarbons with a carbon number of up to several hundreds obtained by the Aggé method (using a fixed catalyst bed), which produces a large amount of waxy hydrocarbons (finally, hydrogenated and ) Or a hydrocarbon obtained by polymerizing an alkylene such as ethylene with a Ziegler catalyst is preferred because it is a branched, small and saturated long-chain linear hydrocarbon. In particular, a hydrocarbon wax synthesized by a method that does not rely on the polymerization of alkylene is preferable because of its structure and a molecular weight distribution that can be easily separated. Further, a preferable range in the molecular weight distribution is
The number average molecular weight is 550 to 1200, preferably 600 to
1000, the weight average molecular weight is 800 to 3600, preferably 900 to 3000, and the weight average molecular weight / number average molecular weight is 3 or less, preferably 2.5 or less, particularly preferably
2.0 or less. Further, a peak exists in a region of a molecular weight of 700 to 2400 (preferably a molecular weight of 750 to 2000, particularly preferably a molecular weight of 800 to 1600). By having such a molecular weight distribution, the toner can have favorable thermal characteristics. That is, if the molecular weight is smaller than the above range, the thermal effect is excessively susceptible, blocking resistance and developability are deteriorated, and if the molecular weight is larger than the above range, heat from the outside cannot be effectively used, Excellent fixability and offset resistance cannot be obtained.

As other physical properties, the density at 25 ° C. is 0.95 (g / cm ³ ) or more and the penetration is 1.5 (10 ^−1).
mm) or less, preferably 1.0 (10 ^-1 mm) or less. If the ratio is out of these ranges, it tends to change at low temperatures and tends to be inferior in storage stability and developability.

The melt viscosity at 140 ° C. is 10
It is 0 cP or less, preferably 50 cP or less, particularly preferably 20 cP or less. When the melt viscosity exceeds 100 cP, the plasticity and the releasability become poor, and excellent fixing properties and offset resistance are affected. Further, the softening point is preferably 130 ° C. or lower, particularly preferably 120 ° C. or lower. When the softening point exceeds 130 ° C., the temperature at which the mold releasability works particularly effectively becomes high, which affects the excellent offset resistance.

Further, the acid value is less than 2.0 mgKOH / g, preferably less than 1.0 mgKOH / g. When the ratio exceeds this range, the interfacial adhesive strength with the binder resin, which is one of the components constituting the toner, is large, and the phase separation at the time of melting tends to be insufficient, so that good releasability is hardly obtained, The offset resistance at high temperatures is not good, and the triboelectricity of the toner is adversely affected, which may cause problems in developability and durability.

The content of these hydrocarbon waxes is within 20 parts by weight based on 100 parts by weight of the binder resin.
It is effective to use 0.5 to 10 parts by weight.

In the present invention, the molecular weight distribution of the hydrocarbon wax is measured by gel permeation chromatography (GPC) under the following conditions.

(GPC measurement conditions) Apparatus: GPC-150
C (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: 0.15% sample 0.4 ml injection 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. Further, it is calculated by converting to polyethylene using a conversion formula derived from the Mark-Houwink viscosity formula.

The penetration of the wax in the present invention is J
It is a value measured according to IS K-2207. Specifically, it is a numerical value representing the penetration depth when a needle having a conical tip having a diameter of about 1 mm and a vertex angle of 9 ° is penetrated with a constant load in a unit of 0.1 mm. The test conditions in the present invention are a sample temperature of 25 ° C., a load of 100 g, and a penetration time of 5 seconds.

The melt viscosity is a value measured using a Brookfield viscometer, and the conditions are a measurement temperature of 140 ° C., a shear rate of 1.32 rpm, and a sample of 10 ml.

The acid value is the number of mg of potassium hydroxide required to neutralize the acid groups contained in 1 g of a sample. (J
IS K5902), density at 25 ° C according to JIS
K6760 and softening point are values measured according to JIS K2207.

The present invention can also be attained by containing the following hydrocarbon wax as described above, and the hydrocarbon wax has an increased DSC curve measured by a differential scanning calorimeter. Endothermic peak at warm
The onset temperature of the peak is in the range of 50 to 90 ° C, at least one endothermic peak exists in the range of 90 to 120 ° C, and the maximum temperature when the temperature falls within the range of the peak temperature of the endothermic peak ± 9 ° C. It is characterized by the presence of an exothermic peak.

At the time of temperature rise, a change when heat is applied to the wax can be seen, and an endothermic peak accompanying the transition and melting of the wax is observed. Peak onset temperature is 50-9
When the temperature is within the range of 0 ° C., developability, blocking resistance, and low-temperature fixability can be satisfied. When the peak onset temperature is less than 50 ° C., the change temperature of the wax is too low, resulting in a toner having poor blocking resistance or poor developability. If it is too high, sufficient fixability cannot be obtained. 9
By having an endothermic peak in the range of 0 to 120 ° C., preferably in the range of 95 to 120 ° C., and particularly preferably in the range of 97 to 115 ° C., satisfactory fixing property and offset resistance can be satisfied. . When the peak temperature exists only below 90 ° C., the melting temperature of the wax is too low, sufficient hot offset resistance cannot be obtained, and when the peak temperature exists only in the region exceeding 120 ° C., the wax Is too high, and sufficient low-temperature offset resistance and low-temperature fixability cannot be obtained. That is, the presence of the peak temperature in this region makes it easier to balance the offset resistance and the fixability. Here, when the peak below 90 ° C. becomes the maximum peak, the same behavior as when only a peak is present in this region is exhibited. Therefore, a peak in this region may be present. It must be smaller than the peak in the region of ° C.

When the temperature is lowered, the change during cooling of the wax and the state at normal temperature can be observed, and an exothermic peak accompanying the solidification, crystallization, and transition of the wax is observed. Among the exothermic peaks at the time of temperature decrease, the largest exothermic peak is an exothermic peak accompanying solidification and crystallization of wax. The presence of an endothermic peak associated with melting at the time of temperature rise near the exothermic peak temperature indicates that the wax is more homogeneous, such as the structure and molecular weight distribution of the wax, and the difference is within 9 ° C. The temperature is preferably within 7 ° C, particularly preferably within 5 ° C. That is, by reducing this difference, the wax is sharp-melted, that is, it is hard at low temperatures, melts quickly at the time of melting, and the melt viscosity is greatly reduced, so that the developability, blocking resistance, fixability, and offset resistance are improved. You can stand up well balanced. The maximum exothermic peak is at a temperature of 85 to 115 ° C (preferably 90 to 115 ° C).
(110 ° C.).

The DSC measurement of the wax is based on the above-described toner, and the definition of each temperature is determined as follows. Endothermic peak: peak onset temperature: 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. Therefore, the definition differs from the onset temperature in the case of toner. Exothermic peak: Peak temperature: Peak-top temperature of the largest peak The content of these hydrocarbon waxes is
Used within 20 parts by weight to 0.5 part by weight
It is effective to use it in parts by weight, and it may be used in combination with other waxes.

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, and the like.
Such as dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc. Monocarboxylic acid having a heavy bond or a substituted product thereof; for example, dicarboxylic acid having a double bond such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate and the like; and substituted products thereof; for example, vinyl chloride, vinyl acetate And vinyl esters such as vinyl benzoate; ethylene-based olefins such as ethylene, propylene and butylene; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; Chirueteru, vinyl ethyl ether, vinyl ethers such as vinyl isobutyl ether; vinyl monomers are used alone or two or more.

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

As the cross-linking 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 and divinylnaphthalene; Carboxylic acid esters having two double bonds such as glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butadiol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and 3
Compounds having at least two vinyl groups are used alone or as a mixture.

The binder resin in the present invention can be produced by a usual polymerization method.

In the bulk polymerization method, a low molecular weight polymer 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 radical chain transfer 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 varies depending on the solvent used, the initiator and the polymer to be polymerized.
It is better to carry out at 0 ° C. In the solution polymerization, it is preferable to carry out the polymerization with 30 parts by weight to 400 parts by weight of the monomer per 100 parts by weight of the solvent.

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.

As a polymerization method for obtaining a high molecular weight product 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 remove the polymer. Therefore, suspension polymerization is a simple method.

In 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. In addition, any initiator can be used as long as it is insoluble or hardly soluble in water.

As the initiator, t-butylperoxy-
2-ethylhexanoate, cumin perpivalate, t
-Butylperoxy laurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-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, di-t-butyldiperoxyisophthalate, 2,2-bis (4
4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate,
Di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, diethylene glycol-bis (t-butylperoxy) Carbonate), di-t-butylperoxytrimethyl adipate, tris (t-butylperoxy) triazine, vinyltris (t-butylperoxy) silane,
And these can be used alone or in combination.

The used amount 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 toner of the present invention may contain a charge control agent.

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.

The following substances control the toner to be positively charged.

Products modified with nigrosine and fatty acid metal salts. Quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate,
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, tannin Acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.) metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin borate Diorganotin borates; these can be used alone or in combination of two or more. Of these, charge control agents such as nigrosine, quaternary ammonium salts, and triphenylmethane lake pigments are particularly preferably used.

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 silica fine powder used in the present invention is BE
The specific surface area by nitrogen adsorption measured by the T method is 30 m ² / g
Those within the above range (particularly 50 to 400 m ² / g) give good results. 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 used in the present invention is:
Silicon varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for purposes such as hydrophobicity and charge control, if necessary It is also preferable that the composition is treated with such a treating agent or in combination with various treating agents.

As other additives, lubricant powders such as, for example, Teflon powder, zinc stearate powder and polyvinylidene fluoride powder are preferable, and polyvinylidene fluoride is particularly preferable.
Alternatively, abrasives such as cerium oxide powder, silicon carbide powder, and strontium titanate powder, among which strontium titanate is preferred. Or, for example, titanium oxide powder,
Fluidity-imparting agents such as aluminum oxide powder, particularly hydrophobic ones are preferred. A small amount of a caking inhibitor, a conductivity imparting agent such as a carbon black powder, a zinc oxide powder, an antimony oxide powder, a tin oxide powder, and the like, and fine particles of white and black having opposite polarities can also be used as a developing property improver.

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

As the carrier that can be used in the present invention, known carriers can be used. For example, magnetic powders such as iron powder, ferrite powder and nickel powder, glass beads, etc. And those treated with a vinyl resin or a silicone resin.

Further, 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, the magnetic material contained in the magnetic toner includes iron oxide such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and aluminum, cobalt, copper, lead, magnesium, and tin of these metals. ,
Examples include alloys of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

These ferromagnetic substances preferably have an average particle size 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 magnetic properties when 10 K Oersted is applied are as follows: the coercive force ratio (Hc) is 20 to 300 Oersted, the saturation magnetization (σs) is 50 to 200 emu / g, and the residual magnetization (σ
r) Those having 2 to 20 emu / g are preferred.

The colorant 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 alinine black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengala, phthalocyanine blue, indanthrene blue and the like. 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. Examples include azo dyes, anthraquinone dyes, xanthene dyes, methine dyes and the like.
0.1 to 20 parts by weight, preferably 0.1 part by weight, per 0 parts by weight.
The addition amount of 3 to 10 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 substance, a charge control agent if necessary, The other additives and the like were thoroughly mixed by a mixer such as a Henschel mixer or a ball mill, and then melt-kneaded using a hot kneader such as a heating roll, kneader, or extruder to make the resins compatible with each other. The toner according to the present invention can be obtained by dispersing or dissolving a metal compound, a pigment, a dye, and a magnetic substance in the mixture, and performing cooling and solidification followed by pulverization and classification.

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

The toner of the present invention can be applied to plain paper or an overhead projector (OH
The sheet is heat-fixed to a transfer material such as a transparent sheet for P).

As the contact heating fixing means, for example, FIG.
As shown in (1), the toner 7 is heated and fixed by the fixedly supported heating element 1 and the pressing member 5 which is in pressure contact with the heating element and makes the transfer material 6 adhere to the heating element via the film 2. Fixing means.

[0089]

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

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

A hydrocarbon wax F (comparative example) synthesized by the Age method was used. From this, wax A (the present invention), wax B (the present invention) and wax C (the present invention)
Was obtained by fractional crystallization. The hydrocarbon synthesized by the Age method was oxidized to obtain wax G (comparative example).

Using a Ziegler catalyst, ethylene was polymerized at a low pressure to obtain wax H having a relatively low molecular weight (comparative example).
Wax D (the present invention) from which low molecular weight components had been removed to some extent by fractional crystallization was obtained. Wax H by similar polymerization
Higher molecular weight wax I (Comparative Example) was obtained, and low molecular weight components were extracted by fractional crystallization to obtain wax E (the present invention).
I got Tables 1, 2 and 3 show the physical properties of these waxes.
It writes in.

Next, the binder resin will be described. Synthetic Example 1 80 parts by weight of styrene 20 parts by weight of butyl acrylate 2,2 parts by weight of 2,2-bis (4,4-di-t-butyl peroxycyclohexyl) propane From the above compound, polymer A was obtained by a suspension polymerization method. I got

82 parts by weight of styrene 18 parts by weight of butyl acrylate 2.0 parts by weight of di-t-butyl peroxide From the above compound, a polymer B was obtained by a solution polymerization method using xylene as a solvent, and a polymer A and a polymer B were obtained. Was mixed at a weight ratio of 30:70 to obtain a binder resin 1. -Synthesis example 2 80 parts by weight of styrene 20 parts by weight of butyl acrylate 0.25 parts by weight of benzoyl peroxide butyl peroxycyclohexyl) propane From the above compound, a polymer C was obtained by a suspension polymerization method.

83 parts by weight of styrene 17 parts by weight of butyl acrylate 2.5 parts by weight of di-t-butyl peroxide From the above compound, a polymer D is obtained by a solution polymerization method using xylene as a solvent, and a polymer C and a polymer D are obtained. Was mixed in a weight ratio of 25:75 to obtain a binder resin 2. -Synthesis example 3 80 parts by weight of styrene 20 parts by weight of butyl acrylate 0.2 parts by weight of benzoyl peroxide A polymer E was obtained from the above compound by a suspension polymerization method.

82 parts by weight of styrene 18 parts by weight of butyl acrylate 3.0 parts by weight of di-t-butyl peroxide From the above compound, a polymer F was obtained by a solution polymerization method using xylene as a solvent, and a polymer E and a polymer F were obtained. Was mixed at a weight ratio of 40:60 to obtain a binder resin 3. -Synthesis example 4 80 parts by weight of styrene 20 parts by weight of butyl acrylate 0.3 parts by weight of benzoyl peroxide Binder resin 4 was obtained from the above compound by a solution polymerization method using xylene as a solvent. -Synthesis example 5 The binder resin 5 was obtained by mixing the solution of the polymer A and the polymer B at a weight ratio of 60:40. Synthesis Example 6 Polymer B 25 parts by weight Styrene 59.8 parts by weight butyl acrylate 15 parts by weight Divinylbenzene 0.2 parts by weight Benzoyl peroxide 0.5 parts by weight From the above compound, binder resin 6 was prepared by suspension polymerization method. Obtained.

Example 1 Binder Resin 100 parts by weight Magnetic iron oxide 80 parts by weight (average particle size 0.25 μm; saturation magnetization 80 emu / g under 10 K Oersted residual magnetization 10 emu / g, coercive force 120 Oersted) Nigrosine 2 weight Part Wax A 4 parts by weight After the above materials were preliminarily mixed, melt kneading was performed by a biaxial kneading extruder set at 130 ° C. After cooling, the kneaded material was coarsely pulverized, finely pulverized by a pulverizer using a jet stream, and further classified using an air classifier to obtain toner 1 having a weight average particle diameter of 8 μm. 0.6 part by weight of positively charged hydrophobic colloidal silica was externally added to 100 parts by weight of this toner to prepare a developer. GPC measurement result of this toner and D
The SC measurement results are shown in Tables 4 and 5, respectively.

Examples 2 to 5 Toners 2 to 5 were prepared in the same manner as in Example 1 except that the binder resins and waxes shown in Table 6 were used. G of each toner
The results of the PC measurement and the results of the DSC measurement are shown in Tables 4 and 5, respectively.

Comparative Examples 1 to 6 Comparative toners 1 to 6 were prepared in the same manner as in Example 1 except that the binder resins and waxes shown in Table 6 were used. The GPC measurement results and the DSC measurement results of each toner are shown in Tables 4 and 5, respectively.

Comparative Example 7 Comparative toner 7 was prepared in the same manner as in Example 1 except that no wax was used. The GPC measurement results and the DSC measurement results of the toner are shown in Tables 4 and 5, respectively. The endothermic peak in this case is derived from the binder resin and is also found in other toners.

Next, the following tests were conducted for the above Examples and Comparative Examples.

<Fixing and Offset Test> An unfixed image was obtained with a commercially available electrophotographic copying machine NP-1215 (manufactured by Canon Inc.), and a temperature-variable heat roller using a Teflon coat as an upper roller and a silicone rubber as a lower roller. Using a fixing machine, fixing of an unfixed toner image and an offset test were performed. Nip 3.0mm, Linear pressure 0.5Kg
/ Cm, process speed 50mm / sec 10
The temperature was adjusted every 5 ° C. within a temperature range of 0 to 230 ° C. 80 g / m ² paper was used for low temperature offset and fixability tests. In the test of high-temperature offset, evaluation was performed using 52 g / m ² paper. The fixability was as follows: the fixed image was 50 g / cm ^2.
And apply a load of silbon paper [lenz cleanin
g paper “dasper (R)” (0zu Pa
per Co. [Ltd)], and the temperature at which the density reduction rate before and after rubbing was less than 10% was defined as the fixing start point. For the offset, the temperature at which the offset disappeared visually was set as the low-temperature offset-free starting point, the temperature was raised, and the highest temperature without offset was set as the high-temperature offset-free end point. The test results are summarized in Table 6. Table 6 shows the fixing start temperature, 150
The concentration reduction rate at ° C., the low-temperature offset free start point, the high-temperature offset free end point, and the non-offset area are described.

<Blocking Test> Approximately 20 g of the developer was put in a 100 cc plastic cup, left at 50 ° C. for 3 days, and evaluated visually. The results are shown in Table 6. Excellent: Aggregates are not seen Good: Aggregates are seen but easily collapsed Possible: Aggregates are seen but collapse when shaken Impossible: Aggregates can be grasped and not easily collapsed <Developability test> Approx. 100 g Was placed in a 500 cc polycup and left at 45 ° C. for 3 days, and then the developability was evaluated using a commercially available electrophotographic copying machine FC-5II (manufactured by Canon Inc.). Table 6 shows the results of the test (image density, fog). By this test, it is possible to obtain a simulation for observing the durability against the temperature rise of the machine and the safety after long-term storage.

Further, the toners 1 to 5 of the present invention were fixed by a commercially available electrophotographic copying machine FC-2 (manufactured by Canon Inc.) at an environmental temperature of 7.5 ° C. in a first copy immediately after power-on without low-temperature offset and fixing. Properties (concentration reduction rate 5
% Or less) was also good.

Further, at 23.5 ° C., even after copying 50 sheets of continuous postcards and copying with 52 g / m ² paper, no offset due to the temperature rise at the end of the fixing machine was observed. When a copy test was performed in an environment of 32.5 ° C., a clear image was always obtained, the toner could be used up to the end in a good state, no fusion occurred, and there was no blocking at the cleaner portion.

Example 6 Binder Resin 6 100 parts by weight Magnetic iron oxide (same as in Example 1) 85 parts by weight Nigrosine 2 parts by weight Wax A 4 parts by weight After premixing the above materials, the same procedure as in Example 1 was carried out. Thus, a toner 6 having a weight average particle size of 8 μm was obtained. This toner 100
0.5 parts by weight of hydrophobic colloidal silica was externally added to parts by weight to obtain a developer. The peaks P ₁ and P ₂ in the molecular weight distribution of this developer by GPC were 15,200, respectively.
It was 2,550,000.

This developer was used in a commercially available electrophotographic copying machine NP-
The test was performed using 3825 (manufactured by Canon Inc.). Fifteen
After turning on the power in a condition where the copying machine is sufficiently cooled in an environment of ° C, one minute of A3 transfer paper (80 g paper)
When 50 consecutive copies were made, no offset occurred and the fixability of the 150th copy (density reduction rate 12%)
Was also good. Further, when a copying test was continuously performed on 20,000 sheets, a fog-free image having an image density of 1.32 to 1.36 was obtained, and no fusing or the like occurred.

[0108]

[Table 1]

[0109]

[Table 2]

[0110]

[Table 3]

[0111]

[Table 4]

[0112]

[Table 5]

[0113]

[Table 6]

[0114]

According to the present invention, favorable thermal characteristics can be imparted to a toner by incorporating a specific binder resin and a hydrocarbon wax into the toner, so that the following excellent effects are exhibited. Things.

The present invention can provide a toner for developing an electrostatic image, which is excellent in fixing property at low temperature and anti-offset property.

The present invention can provide a toner for developing an electrostatic charge image having excellent offset resistance at high temperatures.

The present invention can provide a toner for developing an electrostatic charge image which is excellent in blocking resistance and does not deteriorate in developability even when left for a long period of time.

The present invention can provide a toner for developing an electrostatic image, which is excellent in durability against temperature rise of a machine body such as a copying machine or a printer.

The present invention can provide a toner for developing an electrostatic image, which can achieve the above effects without contradiction.

[Brief description of the drawings]

FIG. 1 is a view showing a DSC curve when a temperature of a toner 1 is raised.

FIG. 2 is a diagram showing a DSC curve when the temperature of toner 1 is lowered.

FIG. 3 is a diagram showing an example of an endothermic peak pattern.

FIG. 4 is a diagram showing an example of an endothermic peak pattern.

FIG. 5 is a diagram showing an example of an endothermic peak pattern.

FIG. 6 is a diagram showing an example of an endothermic peak pattern.

FIG. 7 is an explanatory diagram of a peak intensity ratio (ΔH / ΔT) of an exothermic peak.

FIG. 8 is an explanatory diagram of a peak intensity ratio (ΔH / ΔT) of an exothermic peak.

FIG. 9 is an explanatory diagram of a peak intensity ratio (ΔH / ΔT) of an exothermic peak.

FIG. 10 is an explanatory diagram of a peak intensity ratio (ΔH / ΔT) of an exothermic peak.

FIG. 11 is a view showing a DSC curve when the temperature of wax A is raised.

FIG. 12 is a view showing a DSC curve when the temperature of wax A is lowered.

FIG. 13 is a view showing a DSC curve when the temperature of wax F is raised.

FIG. 14 is a view showing a DSC curve when the temperature of wax F is lowered.

FIG. 15 shows H in the molecular weight distribution of the toner by GPC.
It is explanatory drawing of 1, H2 and H3.

FIG. 16 is a schematic diagram illustrating an example of a fixing unit.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroaki Kawakami 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Masaji Fujiwara 3-30-2 Shimomaruko, Ota-ku, Tokyo (56) References JP-A-56-16144 (JP, A) JP-A-61-87162 (JP, A) JP-A-62-115170 (JP, A) JP-A-53-96839 (JP) JP-A-58-223155 (JP, A) JP-A-63-216063 (JP, A) JP-A-61-62045 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB (Name) G03G 9/08

Claims (4)

(57) [Claims] 1. A toner for developing an electrostatic image containing at least a binder resin and a hydrocarbon wax, wherein the molecular weight distribution of the toner by GPC is 3 × 10 ^{3 to} 5 × 10 ^4.
And at least one peak (P ₁ ) exists in the region of 10 ⁵ or more.
₂ ) is present, and the component of 10 ⁵ or less is 50% or more;
In the DSC curve measured by the differential scanning calorimeter, the onset temperature at the endothermic peak at the time of temperature rise is 10
5 ° C. or less, the endothermic peak temperature is in the range of 100 to 120 ° C., the exothermic peak temperature upon cooling is in the range of 62 to 75 ° C., and the exothermic peak intensity ratio is 5 × 10 ⁻³ or more. Characteristic toner for developing electrostatic images. 2. The molecular weight distribution measured by GPC is 3 × 10 ³
At least one peak in the region of ~5 × 10 ⁴ (P
₁ ), at least one peak (P ₂ ) exists in a region of 10 ⁵ or more, and the height (H1) of the maximum peak on the low molecular weight region side and the height (H3) of the maximum peak on the high molecular weight region side ) And the height of the minimum between the two peaks (H2) is H
1: H2: H3 = 3 to 25: 1: 1.5 to 12,
2. The electrostatic image developing toner according to claim 1, wherein a relationship of H1> H3 is satisfied. 3. In a toner for developing an electrostatic image containing at least a binder resin and a hydrocarbon wax, the molecular weight distribution of the toner by GPC is 3 × 10 ^{3 to} 5 × 1.
0 at least one peak (P ₁₎ is present in the ^fourth region, at least one peak at 10 ⁵ or more regions (P
₂ ) is present, and the component of 10 ⁵ or less is 50% or more;
In the DSC curve of the hydrocarbon wax measured by a differential scanning calorimeter, the onset temperature at the endothermic peak at the time of temperature rise is in the range of 50 to 90 ° C, and the temperature of the wax is in the range of 90 to 120 ° C. There is at least one endothermic peak, and ± 9 ° C. of the peak temperature of the endothermic peak
Characterized by having a maximum heat generation peak at the time of temperature fall within the range of (1). 4. The molecular weight distribution measured by GPC is 3 × 10 ³
At least one peak in the region of ~5 × 10 ⁴ (P
₁ ), at least one peak (P ₂ ) exists in a region of 10 ⁵ or more, and the height (H1) of the maximum peak on the low molecular weight region side and the height (H3) of the maximum peak on the high molecular weight region side ) And the height of the minimum between the two peaks (H2) is H
1: H2: H3 = 3 to 25: 1: 1.5 to 12,
4. The electrostatic image developing toner according to claim 3, wherein a relationship of H1> H3 is satisfied.