JP2984564B2 - Electrostatic image developing toner and heat fixing method - 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, and to heat a toner image formed by using the toner. The present invention relates to a heat fixing method for fixing a recording material by a fixing unit.

[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 Application Publication No. JP-B-43-24748 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 image is fixed by fixing means such as heating, pressing or solvent vapor to obtain a copy, and remains on the photoconductor without being transferred. The toner is cleaned in various ways,
The above steps are repeated.

[0003] 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 becomes higher, and if the performance of the toner cannot be improved,
Better machines are no longer available.

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

A heating method using a heating roller or a film fixes the toner 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 with respect to the toner. Is what you do. 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 electrophotographic copying machines. 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. One of the essential conditions of the heat fixing method is to prevent toner from adhering to the heat fixing roller and the film surface.
It is one.

Conventionally, for the purpose of preventing toner from adhering to the surface of the fixing roller, for example, the roller surface is formed of a material having excellent releasability with respect to the toner, such as silicone rubber or fluorine-based resin, and furthermore, the surface thereof is prevented from being offset. In order to prevent the roller surface from being fatigued, the roller surface is coated with a thin film of a liquid having good releasability such as silicone oil. However, although this method is extremely effective in preventing toner offset, it has a problem in 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 the silicone oil 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 has been proposed. ing. If a large amount of such an additive is added in order to obtain a sufficient effect, filming of the photoconductor and contamination of the surface of the toner carrier such as a carrier and a sleeve occur, and the image is deteriorated and practically used. It becomes a problem. Therefore, a device is used in which a small amount of a 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 winding type device using a member such as a web. They are used together.

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

[0010] The incorporation of wax as a release agent in the toner is disclosed in, for example, JP-A-52-3304, JP-A-52-3305 and JP-A-57-52574.

Further, JP-A-3-50559, JP-A-2-79860, JP-A-1-109359, JP-A-62-14166, and JP-A-61-2
73554, JP-A-61-94062, JP-A-61-138259, and JP-A-60-2523
No. 61, JP-A-60-252360 and JP-A-60-217366 disclose techniques 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 developing property is deteriorated when the toner is exposed to heat due to the temperature rise in the copying machine, and the developing property is deteriorated by blooming of the wax when left for a long period of time. Or worse.

None of the conventional toners 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 inside the machine rises. There has been an adverse effect, or offset resistance at low and high temperatures has not been compatible.

A toner containing low molecular weight polypropylene (for example, Viscol 550P, 660P, etc., manufactured by Sanyo Chemical Industries, Ltd.) is commercially available, but a toner further improved in low-temperature offset property and fixing property is expected. ing.

In order to improve the fixability of the toner, the binder resin in the toner has also been improved. If only the fixability is considered, it is required to lower the molecular weight and the glass transition point of the binder resin. You. However, this in turn causes a reduction in high-temperature offset resistance and blocking resistance.

In order to solve such disadvantages, for example, Japanese Patent Publication No. 51-23354 proposes a toner using a crosslinked polymer (vinyl polymer) as a binder resin.
No. 5,689,955 discloses a binder resin having a wide molecular weight distribution such that the ratio between the weight average molecular weight and the number average molecular weight of α, β unsaturated ethylene monomer as a constitutional unit is 3.5 to 40. Containing toner has been proposed.
No. 6,144, proposes a toner containing a binder resin having a peak in each of a low molecular weight region and a high molecular weight region in a GPC chromatogram of a vinyl polymer. Certainly, the toner according to these proposals achieves both high-temperature offset resistance and, at the same time, fixing performance at a certain level, but further improvement is desired.

As to these vinyl-based addition polymerization type binder resins, materials which are suitable for polycondensation type polyester low-temperature fixing have been conventionally proposed.

For example, Japanese Patent Application Laid-Open No. Sho 59-7960 proposes an improved toner using a specific polyester as a binder resin.

Certainly, the low-temperature fixability is superior to that of the vinyl resin, but there is a problem that the wax as a releasing component is poorly dispersed and the offset resistance is inferior.

Further, Japanese Patent Application Laid-Open No. 5-197192 proposes a toner containing a hydrocarbon wax having specific thermal characteristics. Since the hydrocarbon wax having the specific thermal characteristics can impart favorable thermal characteristics to the toner, it is excellent in fixing properties at low temperatures, anti-offset properties and anti-blocking properties. In order to further exert the effects of the hydrocarbon wax having the above, a more excellent dispersibility of the hydrocarbon wax in the binder resin is desired, and there is a point to be further improved.

Japanese Patent Application Laid-Open No. Hei 5-249735 discloses a toner containing a binder resin having a functional group (styrene type) and a hydrocarbon type wax. It has been proposed to improve the properties, offset resistance and blocking resistance.

However, the performance (especially the fixing property) of these disclosed techniques alone is limited. In order to sufficiently bring out the performance of the polyester matching low-temperature fixing, it is desired to further improve the performance while maintaining other toner characteristics such as blocking resistance and developability.

[0023]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner which solves the problems of the prior art as described above, and a method for heating and fixing the toner.

An object of the present invention is to provide a toner excellent in fixing property at low temperature and anti-offset property, and a method for heating and fixing the toner.

An object of the present invention is to provide a toner having excellent offset resistance at high temperatures and a method for heat-fixing the toner.

An object of the present invention is to provide a toner which is excellent in blocking resistance and does not deteriorate in developability even when left for a long period of time, and a method for heating and fixing the toner.

An object of the present invention is to provide a toner excellent in durability against a temperature rise of a machine main body and a method for heating and fixing the toner.

An object of the present invention is to provide a toner excellent in the rise of charge in a high-humidity environment and a method for heating and fixing the toner.

[0029]

The present invention achieves the above object by the following constitutions.

According to the present invention, there is provided a toner for developing an electrostatic image having at least a binder resin and a wax, wherein the binder resin contains a polyester resin having a soft segment as a main component. In the DSC curve by the scanning calorimeter, regarding the endothermic peak at the time of temperature rise and the exothermic peak at the time of temperature decrease, the onset temperature of endotherm is in the range of 50 to 110 ° C. Has an endothermic peak P ₁ at the time,
A toner for developing electrostatic images which is characterized by having a maximum exothermic peak at the time of temperature drop within a range of ± 9 ° C. of the endothermic peak P _1.

According to the present invention, in a heat fixing method for fixing a toner image on a recording material by a heat fixing means, the toner image is formed by a toner having at least a binder resin and wax, and the binder resin is Containing a polyester resin having a soft segment as a main component, and, in a DSC curve of the wax by a differential scanning calorimeter, regarding an endothermic peak at the time of temperature rise and an exothermic peak at the time of temperature decrease, an onset temperature of endotherm is in the range of 50 to 110 ° C., at least one has an endothermic peak P ₁ during heating, the maximum heat generation at the time of temperature drop within a range of ± 9 ° C. of endothermic peaks P ₁ in the region of the temperature 70 to 130 ° C. The present invention relates to a heat fixing method characterized by having a peak.

The present inventors have conducted intensive studies on the improvement of the fixing property, offset resistance, blocking resistance and developing property of the toner. As a result, using a polyester resin having a soft segment as a main component of the binder resin, By using a sharp-melting wax having specific thermal properties as a wax that functions as a toner release agent,
It is considered that the soft segment of the polyester resin acts to improve the dispersibility of the wax having a specific thermal property in the polyester resin, and the polyester resin having the soft segment is a main component of the binder resin. As a result, the wax component having a specific thermal property is uniformly dispersed in the binder resin of the toner, whereby the toner can maintain the anti-offset property and the anti-blocking property from low to high temperatures, and further improve the low-temperature property. It has been found that it has fixability and is excellent in developability.

The toner of the present invention comprises at least a binder resin and a wax.

The wax used in the present invention has (i) an endothermic peak in the range of 50 to 110 ° C. in the endothermic peak at the time of temperature rise and the exothermic peak at the time of temperature decrease in the DSC curve of the wax measured by the differential scanning calorimeter. (Ii) has at least one endothermic peak (P ₁ ) at the time of temperature rise in the range of 70 to 130 ° C., and (ii)
i) It has a maximum exothermic peak at the time of temperature fall within a range of ± 9 ° C. of the endothermic peak (P ₁ ).

At the time of raising the temperature, a change when the wax is heated can be seen, and an endothermic peak accompanying the phase transition and melting of the wax is observed. Endothermic onset temperature is 50-1
10 ° C., preferably 50 to 90 ° C., more preferably 60 ° C.
When the temperature is within the range of from 90 ° C. to 90 ° C., not only blocking resistance and low-temperature fixability but also developability can be satisfied.

When the endothermic onset temperature is less than 50 ° C., the change temperature of the wax is too low, so that the blocking resistance and the developability at the time of temperature rise are inferior. Since the skeleton has a soft segment for imparting plasticity to the toner, the blocking resistance of the toner is particularly deteriorated when the onset temperature of heat absorption is less than 50 ° C. If the onset temperature of the heat absorption exceeds 110 ° C., the temperature at which the wax changes is too high, so that sufficient fixability cannot be obtained.

When the endothermic peak is within the range of 70 to 130 ° C.,
Preferably 70-120 ° C, more preferably 95-12.
By being at 0 ° C., particularly preferably within the range of 97 ° C. to 115 ° C., good fixability and offset resistance can be satisfied.

If the peak temperature exists only at less than 70 ° C., the melting temperature of the wax is too low, and sufficient hot offset resistance cannot be obtained. If the peak temperature exists only at a temperature exceeding 130 ° C., the melting temperature of the wax is too high, and sufficient low-temperature offset resistance and low-temperature fixability cannot be obtained.

Here, when the peak below 70 ° C. becomes the maximum peak, the behavior is the same as when there is a peak only in this region. Therefore, a peak may exist in this region.
In that case, it is necessary to be smaller than the peak in the region of 70 to 130 ° 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 phase transition of the wax is observed. The largest exothermic peak at the time of cooling is the exothermic peak accompanying the coagulation and crystallization of the 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 structure is more homogeneous and the molecular weight distribution is sharper, and the difference is 9%. The temperature is preferably within ° C, preferably within 7 ° C, more preferably within 5 ° C. By reducing this difference, the wax can be sharp-melted, hard at low temperatures, melts quickly at the time of melting, and the melt viscosity decreases greatly, resulting in developability, blocking resistance, fixability and offset resistance. It can be achieved in a well-balanced manner.

The maximum exothermic peak is preferably in the temperature range of 85 to 115 ° C., preferably 90 to 110 ° C.

Since the DSC measurement of the wax measures the exchange of heat of the wax and observes its behavior, it is necessary to perform measurement with a highly accurate internal heating input compensation type differential scanning calorimeter from such a measurement principle. For example, PerkinElmer D
SC-7 is available.

The measurement is performed according to ASTM D3418-82. The DSC curve used in the present invention has a temperature rate of 10 ° C./mi after the temperature is raised once to remove the previous history.
n. And a DSC curve measured when the temperature is lowered or raised in the temperature range of 0 to 200 ° C. The definition of each temperature is defined as follows.

Endothermic onset temperature: The lowest temperature at which the differential value of the curve at the time of temperature rise is maximized.

Endothermic peak temperature: The peak top temperature of the endothermic peak during temperature rise.

Exothermic peak temperature: The peak top temperature of the maximum exothermic peak during cooling.

The wax used in the present invention is obtained by fractionating as necessary based on the following wax.

Examples of the base wax include paraffin wax and its derivatives, montan wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, and polyolefin wax and its derivatives. Includes block copolymers with oxides and vinyl monomers and graft-modified products.

Other base waxes include higher fatty alcohols, higher fatty acids and their esterified products, higher fatty acid amides, ketone waxes, hydrogenated castor oil and derivatives thereof, as well as vegetable waxes such as carnauba wax and derivatives thereof. Animal wax, mineral wax or petrolactam can also be used.

Particularly preferred are synthetic hydrocarbon waxes synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst, such as the Zintol method,
Hydrocoll method (using a fluidized catalyst bed) or the Aage method (using a fixed catalyst bed), which produces a large amount of waxy hydrocarbons
And polyolefins obtained by polymerization with an alkylene Ziegler catalyst such as ethylene, and by-products at this time.

Based on these waxes, the waxes obtained by fractionating waxes according to their molecular weights by using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a molten liquid crystal deposition method are used in the present invention. It is preferably used.
Among these methods, the supercritical gas extraction method (this method can easily separate and recover the solvent because the solvent is in a gaseous state and obtains a molecular weight fraction according to the purpose), vacuum distillation and distillate obtained therefrom Is particularly preferable to be subjected to a melt liquid crystal precipitation and a crystal filtration.

That is, those having an arbitrary molecular weight distribution such as 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 are obtained. In addition, you may perform oxidation and graft modification after fractionation.

In the present invention, the preferred molecular weight of the wax depends on its structure and cannot be limited unconditionally.
Number average molecular weight of 3 in molecular weight distribution in PC measurement
It is preferably about 00 to 1500. For example, in the case of hydrocarbons such as polyolefins, the preferred range is a number average molecular weight of 300 to 1500, preferably 400 to 12
00, more preferably 600 to 1000,
500 to 6000, preferably 600 in weight average molecular weight
~ 3500, more preferably 800-2000,
Mw / Mn is preferably 3.0 or less, preferably 2.5 or less, more preferably 2.0 or less.

For measurement of molecular weight and molecular weight distribution, a viscosity method is used.
The boiling point rising method, the freezing point falling method, the vapor pressure falling method, the terminal group quantification method, the high temperature gas chromatography method and the GPC method can be used, and when measurement is possible by GPC, the measurement is performed under the following conditions.

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

In calculating the molecular weight of the sample, a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used. Further, it is calculated by performing a conversion according to the wax structure using a conversion formula derived from the Mark-Houwink viscosity formula.

The physical properties obtained from the preferred molecular weight distribution for each structure can be viewed as a substitute for the DSC characteristics. If there are unnecessarily low molecular weight components depending on the structure,
The onset temperature of the endothermic peak is less than 50 ° C. On the other hand, if there is a higher molecular weight component than necessary, the peak top temperature of the maximum endothermic peak will exceed 130 ° C. Then, the effect of the wax is reduced or adverse effects are caused.

Other physical properties of the wax are as follows: 25 ° C.
Density of 0.95 g / cm ³ or more and penetration of 1.5
(10 ^-1 mm) or less, preferably 1.0 (10 ^-1 mm)
It is as follows. If the ratio is out of these ranges, it tends to change at a low temperature and tends to be inferior in storability and developability.

The melt viscosity at 140 ° C. is 100 cp or less, preferably 50 cp or less, more preferably 20 cp or less.
It is as follows. When the melt viscosity exceeds 100 cp, the plasticity and the releasability become poor, and the fixing property and the offset resistance are affected.

Further, the softening point is preferably 130 ° C. or lower, particularly preferably 120 ° C. or lower. If the softening point exceeds 130 ° C., the temperature at which the releasability works effectively increases, and the offset resistance is affected.

The content of these waxes depends on the binder resin 1
Used within 20 parts by weight with respect to 00 parts by weight,
It is particularly effective to use 10 parts by weight.

The penetration of the wax in the present invention is J
This is a value measured according to IS K2207. Specifically, it is a numerical value representing a penetration depth when a needle having a diameter of 1 mm and a conical tip having a vertex angle of 9 ° is penetrated with a constant load in a unit of 0.1 mm. The test condition in the present invention is a sample temperature 2
5 ° C., load 100 g and penetration time 5 seconds.

The melt viscosity is a value measured using a Brookfield type viscometer.
° C, a shear rate of 1.32 rpm and a sample of 10 ml.
The density is a value measured by a ring and ball method according to JIS K6760 at a measurement temperature of 25 ° C., and the softening point is measured according to JIS K2207.

The wax having the above-mentioned specific thermal properties used in the present invention is hardly dispersed in the binder resin because of its melting property of a sharp melt. In the case of a toner that requires durability, better dispersion of the wax having the specific thermal characteristics in the binder resin is required.

However, since the binder resin used in the present invention has a polyester resin having a soft segment as a main component, the reason is unknown, but it has a heat generation characteristic corresponding to such endothermic characteristics. The wax was well dispersed in the polyester having the soft segment in the skeleton, and therefore, it was possible to achieve a higher level of developability, blocking resistance, fixing property, and offset resistance.

In the present invention, the main component in the binder resin means a resin having the largest content among the components contained in the binder resin.

In the present invention, the polyester resin having a soft segment is specifically introduced by introducing the soft segment (that is, an alkyl group or an alkenyl group having 5 to 30 carbon atoms) into the skeleton of the polyester. Such a polyester resin,
It can be obtained by synthesizing an aliphatic dicarboxylic acid substituted with a soft segment or an aliphatic diol substituted with a soft segment as a monomer component.

In the polyester having a soft segment used in the present invention, when the dicarboxylic acid has a substituent for the soft segment, the aliphatic dicarboxylic acid substituted with the soft segment is used in an amount of 2 to 30% of the total monomer components. It is preferable that the diols have a soft segment substituent. When the diols have a soft segment substituent, the aliphatic diols substituted with the soft segment may be contained in all monomers. It is preferable to contain 2 to 30 mol% in the components,
More preferably, it is contained in an amount of 5 to 20 mol%. When both dicarboxylic acids and diols have a soft segment substituent, the soft segment is substituted with an aliphatic dicarboxylic acid substituted with the soft segment. It is preferable that the total amount of the aliphatic diols is 2 to 30 mol%, more preferably 5 to 20 mol%. 2 mol% of all monomers substituted with soft segment
If the content is less than 30 mol%, the toner will have poor blocking resistance and poor developability at elevated temperatures.

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

As the divalent acid component, for example, phthalic acid,
Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid or phthalic anhydride or anhydrides and lower alkyl esters; aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid or azelaic acid or anhydrides and lower alkyl esters; Aliphatic unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid or itaconic acid or anhydrides and lower alkyl esters; and soft segments (alkyl groups having 5 to 30 carbon atoms or Aliphatic dicarboxylic acids or their anhydrides and lower alkyl esters substituted with an alkenyl group).

Examples of the aliphatic dicarboxylic acids substituted with a soft segment include n-dodecenylsuccinic acid, n-dodecylsuccinic acid, isododecenylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, and n-octenylsuccinic acid. -Octyl succinic acid, among which n-dodecenyl succinic acid and n-dodecyl succinic acid are preferred.

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

[0073]

[Outside 1] (Wherein, R represents an ethylene or propylene group, x, y
Is an integer of 0 or more, and the average value of x + y is 0 to 10. Or a derivative thereof; or the following formula (B):

[0074]

[Outside 2] And diols represented by

Further, aliphatic diols substituted by a soft segment (an alkyl or alkenyl group having 5 to 30 carbon atoms) which is an essential component of the polyester of the present invention, for example, n-dodecenyl ethylene glycol and n-dodecenyl ethylene glycol Dodecenyl triethylene glycol can also be mentioned.

The trivalent or higher polyvalent carboxylic acid component in the present invention includes, for example, trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5
-Benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-
Hexanetricarboxylic acid, 1,3-dicarboxyl-2
Polycarboxylic acids such as -methyl-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid or empoletrimer acid, or anhydrides and lower alkyl esters thereof; C) Formula,

[0077]

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

The trihydric or higher polyhydric alcohol component includes
For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol,
1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane or 1,3 , 5-trihydroxybenzene.

The polyvalent monomer component such as the trivalent or higher polyvalent carboxylic acid component and the polyhydric alcohol component for forming the non-linear polyester resin may be used in an amount of 5 to 60 mol% of the total monomer components. Preferably, it is more preferably 7 to 30 mol%.

If the amount of the trivalent or higher polyvalent monomer component is less than 5 mol%, the high-temperature offset resistance becomes poor, and if it exceeds 60 mol%, the low-temperature fixability is impaired. .

However, when auxiliary means for applying a releasing agent such as silicone oil is applied to the fixing roller, the amount may be less than 5 mol%.

In the present invention, the binder resin is composed of a polyester resin. The polyester resin is composed of a linear polyester resin synthesized from a divalent carboxylic acid component and a dihydric alcohol component and a trivalent or higher polyvalent carboxylic acid. It is more preferable to use in combination with a non-linear polyester resin synthesized by further using an acid component or a polyhydric alcohol component, from the viewpoint of high compatibility between the fixing property and the offset resistance.

The non-linear polyester resin functions particularly for offset resistance, and the linear polyester resin functions for fixability. The non-linear polyester resin and the linear polyester resin , Preferably 5:
95-60: 40, more preferably 10: 90-50:
It is good to mix at a ratio of 50, particularly preferably 10:90 to 40:60.

When the ratio of the non-linear polyester resin is less than 5, the high-temperature offset resistance is poor, and when it is more than 60, the low-temperature fixability is poor.

When the linear polyester resin and the non-linear polyester resin are used in combination, the offset resistance tends to decrease due to the influence of the linear polyester resin. It is preferable to improve the offset resistance while maintaining a good fixing property by performing a reaction, and to improve a decrease in the offset resistance when a linear polyester resin and a non-linear polyester resin are used in combination.

As a substance capable of undergoing a crosslinking reaction during the melt-kneading, an inorganic or organic metal compound such as a metal salt, a metal complex and an organometallic compound can be used.

The crosslinking reaction at the time of melt-kneading is mainly carried out by a non-linear polyester resin having many molecular chain terminals, and a functional group such as a carboxyl group or a hydroxyl group at the terminal is coordinated via a metal in the metal compound. In the case of a linear polyester resin with a small number of terminals, the molecular chain is broken during melt-kneading to reveal the terminal, and the functional group at the terminal is similarly cross-linked to some extent by a metal compound. Is applied.

Therefore, in the present invention, when a non-linear polyester resin and a linear polyester resin are used in combination as the binder resin, and the polyester resin is metal-crosslinked at the time of melt-kneading using a metal compound, the binder resin The acid value is preferably 10 mgKOH / g or less, more preferably 9 KOH / g or less, and still more preferably 6 KOH / g or less.

The acid value of this binder resin is 10 mgKOH / g
If it is larger, the metal cross-linking using the metal compound proceeds excessively, and the fixing property is reduced.

In the present invention, the binder resin of the toner is preferably composed mainly of a polyester resin having a soft segment (that is, the polyester resin having the largest content in the binder resin). Is preferably 50% by weight or more, more preferably 70% by weight or more, in order to favorably disperse the wax having the above-mentioned specific thermal properties in the binder resin.

In the present invention, as a binder resin of the toner, a secondary component which can be used in combination with a polyester resin having a soft segment includes a styrene polymer, a styrene-acryl copolymer, and a styrene-butadiene copolymer. Styrene resins such as styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer; acrylic resin, methacrylic resin, silicone resin, polyester, polyurethane, polyamide resin,
Furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, chromanindene resin and petroleum-based resin may be mentioned, and particularly preferably, considering the dispersibility of wax having specific thermal properties to the binder resin, A polyester resin is also good as a subcomponent to be combined with a polyester resin having a soft segment as a component.

The reason is that the wax having a specific thermal property is well dispersed in the polyester resin having the soft segment, and the polyester resin having the soft segment has compatibility with the polyester resin if the resin to be combined is a polyester resin. This is because the dispersibility of the wax having the specific thermal properties in the entire binder resin is further improved because of being favorable.

In the above description, the use of a polyester resin having a soft segment as a main component as a binder resin in combination with another binder resin as a subcomponent has been described. When used as a binder resin, the wax having specific thermal characteristics naturally has high dispersibility in the entire binder resin.

Further, in the present invention, the acid value of the polyester resin having a soft segment is preferably 10 mgKOH / g or less in consideration of the influence of humidity.
More preferably, it is 9 mgKOH / g or less, further preferably 6 mgKOH / g or less.

Since the polyester resin having a soft segment is easily affected by heat and humidity, the toner tends to deteriorate particularly in a high-temperature and high-humidity environment, and when the acid value of the polyester resin is more than 10 mgKOH / g. However, since the toner is more susceptible to humidity, the chargeability of the toner is reduced, so that the image density is reduced and the fog is easily increased.

Further, the total acid value of the polyester resin used in the present invention is preferably 10 mg KOH / g or less, more preferably 9 mg KOH / g, in consideration of the environment dependency of the toner.
KOH / g or less, more preferably 6 mgKOH / g or less.

The acid value of the entire polyester resin is 10 mgK
If it is larger than OH / g, the toner is susceptible to the influence of humidity, particularly in a high-humidity environment, and the charge leakage increases, resulting in a decrease in the chargeability of the toner.

On the other hand, when a binder resin having a low acid value is used, as described above, it is less likely to be affected by humidity and environmental characteristics are improved. However, the rising charge of the toner tends to be slow because of the low charging ability of the resin itself.However, when a polyester resin is used as the binder resin, the terminal carboxyl group expressed as an acid value is used. Even when the amount of the polyester resin is reduced, the rising of the charge is originally good because the polyester itself has an ester bond (especially with a negative charge), and a high image density can be obtained from the beginning. Has an effect.

The acid value of the polyester resin can be lowered by, for example, reducing the unreacted carboxyl groups in the polyester resin by accelerating the ester reaction, which will be specifically described later. As described in detail in Examples, it can be carried out by controlling the pressure in the reaction vessel during the synthesis of the polyester resin.

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

As a substance for controlling the toner to be negatively charged, for example, an organic metal complex and a chelate compound are effective, and a monoazo metal complex, an acetylacetone metal complex, an aromatic hydroxycarboxylic acid and an aromatic dicarboxylic acid-based metal complex are effective. There is. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenols, and urea compounds.

The toner can be controlled to be positively charged by denaturation with nigrosine and a fatty acid metal salt, and quaternary ammonium such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate. Salts and onium salts such as phosnium salts, which are analogs thereof, and further lake pigments thereof; triphenylmethane dyes and these lake pigments (phosphorotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, Tannic acid, lauric acid, gallic acid, ferricyanide and ferrocyanide). Metal salts of higher fatty acids are also used, and specific examples include diorganotin oxides such as dibutyltin oxide, dioctyltin oxide and dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate and dicyclohexyltin borate. . These can be used alone or in combination of two or more. Among these, charge control agents such as nigrosine and quaternary ammonium salts 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 fine silica powder used in the present invention has a specific surface area by nitrogen adsorption of 30 measured by the BET method.
m ² / g or more, more preferably those in the range of 50 to 400 m ² / g give good results. The fine silica powder is used in an amount of 0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner.

The silica fine powder used in the present invention may contain a silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, a silane coupling agent, and a functional group for the purpose of hydrophobicity or charge control as required. It is also preferable that the silane coupling agent is treated with one or a plurality of treating agents such as a silane coupling agent and another organosilicon compound.

Other additives include lubricating powders such as Teflon powder, zinc stearate powder and polyvinylidene fluoride powder (polyvinylidene fluoride is preferred); cerium oxide powder, silicon carbide powder and strontium titanate. Abrasives such as powders (preferably strontium titanate); Fluidity-imparting agents such as titanium oxide powder and aluminum oxide powder (particularly preferably hydrophobic); Anti-caking agent; carbon black powder; zinc oxide powder And a conductivity-imparting agent such as antimony oxide powder and tin oxide powder; and a developing property improver for white fine particles and black fine particles of opposite polarity. These may be used in a small amount.

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 a toner concentration, preferably 0.5 to 10% by weight.
% By weight, more preferably 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 or nickel powder, glass beads, and the surfaces thereof are made of fluorine resin, Those treated with a vinyl-based resin or a silicone-based resin may be used.

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

These ferromagnetic materials 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 about 20 to 200 parts by weight, preferably 40 to 150 parts by weight, per 100 parts by weight of the resin component.
Parts by weight are good.

The magnetic properties at the application of 10 kOe are as follows: the coercive force (Hc) is 20 to 300 Oe, the saturation magnetization (σs) is 50 to 200 emu / g, and the residual magnetization (σr)
Those having 2 to 20 emu / g are preferred.

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

To prepare the toner for developing an electrostatic image according to the present invention, a binder resin, a wax, a metal salt or a metal complex, a pigment or dye as a colorant, a magnetic substance, a charge control agent if necessary Are thoroughly mixed with 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. , Pigments, dyes, disperse or dissolve the magnetic material,
After cooling and solidifying, the mixture is pulverized and classified to obtain the toner for developing an electrostatic image of the present invention.

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 of the present invention.

The heating and fixing method of the present invention will be described with reference to FIGS.

The toner of the present invention can be prepared by using a plain paper or an overhead projector (OHP) by a contact heating and fixing means.
Is fixed on a recording material (transfer material) such as a transparent sheet for heating.

As the contact heating fixing means, a heating means fixed by a heating / pressing roll fixing device or a fixedly supported heating body is pressed against the heating body and the transfer material is brought into close contact with the heating body via a film. A fixing unit that heats and fixes the toner depending on the pressing member to be used. FIG. 5 shows an example of the fixing means.

In the fixing device shown in FIG. 5, the heating element has a smaller heat capacity than that of a conventional heat roll and has a linear heating section. The maximum temperature of the heating section is 100 to 300 ° C.
It is preferred that

The film located between the heating element and the pressing member is preferably a heat-resistant sheet having a thickness of 1 to 100 μm.
Polymer sheet such as polyester, PET (polyethylene terephthalate), PFA (tetrafluoroethylene-perfluoroalkylvinyl ether copolymer), PTFE (polytetrafluoroethylene), polyimide or polyamide, metal sheet such as aluminum, and metal sheet and polymer sheet Is used.

A more preferable film structure is that these heat-resistant sheets have a release layer and / or a low-resistance layer.

A specific example of the fixing device will be described with reference to FIG.

In the figure, reference numeral 1 denotes a low-heat-capacity linear heating element (heating means) fixedly supported by the apparatus, and has a thickness of 1.times.
An alumina substrate 10 having a width of 0 mm, a width of 10 mm, and a length of 240 mm is coated with a resistance material 9 to a width of 1.0 mm. Energization is cycle 2 of DC100V
A pulse having a pulse shape of 0 msec according to a desired temperature and energy release amount controlled by the temperature detecting element 11 is given by changing its pulse width. The approximate pulse width is 0.5 msec to 5 msec. The fixing film 2 moves in the direction indicated by the arrow in the drawing while coming into contact with the heating element 1 whose energy and temperature are controlled in this manner. Heat fixing means
The heating element 1 and the fixing film 2 are constituted.

An example of the fixing film has a thickness of 20 μm.
m heat-resistant film (e.g., polyimide, polyetherimide, PES or PFA
It is an endless film in which a release layer obtained by adding a conductive agent to a fluororesin such as TFE and PAF) is coated at 10 μm. Generally, the total thickness is less than 100 μm, more preferably less than 40 μm. The film is driven without wrinkles in the direction of the arrow by the driving and tension of the driving roller 3 and the driven roller 4.

In the drawing, reference numeral 5 denotes a pressure roller having a rubber elastic layer having good releasability such as silicone rubber.
The heating element 1 is pressurized via the film 2 with the pressure of kg, and is rotated while being pressed against the film. The unfixed toner (toner image) 7 on the recording material 6 is guided to a fixing unit by an entrance guide 8 and obtains a fixed image by heating by the above-described heating and fixing unit.

Although the fixing film has been described as an endless film, it may be an endless film using a sheet feeding shaft and a winding shaft.

FIG. 6 shows another fixing device which can be used in the heat fixing method of the present invention.

In the figure, reference numeral 21 denotes a heat fixing means having a fixing roller 22 and a pressure roller 23. The fixing roller 22 and the pressure roller 23 are pressed against each other with a predetermined pressure, and the recording material 2 having an unfixed toner image 26 is formed.
5 passes between the heating roller 22 and the pressure roller 23, the recording material 25 is given heat and pressure, and the unfixed toner image 26 is fixed on the recording material 25 and fixed. The formed toner image 27 is formed. The heating roller 22 has a heating means 24 such as a halogen heater provided inside.

The fixing method of the present invention can be applied to a fixing device of an image forming apparatus that forms an image using toner, such as a copying machine, a printer, and a facsimile.

[0128]

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

Production Example 1 ( Production of Nonlinear Polyester A) Polyoxyethylene (3) -2,2-bis (4-hydroxyphenyl) propane 48 mol% terephthalic acid 18 mol% trimellitic anhydride 18 mol% n -Dodecenyl succinic acid 16 mol% A total of 1500 g of the raw material was put into a four-necked flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube and a falling condenser. Next, the flask was placed in a mantle heater, and nitrogen gas was introduced to keep the inside of the reactor under an inert gas atmosphere and heated. Thereafter, 0.05 g of dibutyltin oxide was added, and a polycondensation reaction was performed at 210 ° C. for 12 hours to obtain a non-linear polyester A. The acid value of the non-linear polyester resin A was 15 mgKOH / g. The acid value was measured according to JIS K5902.

Production Example 2 ( Production of linear polyester resin B) Polyoxypropylene (2,5) -2,2-bis (4-
(Hydroxyphenyl) propane 50 mol% triethylene glycol 12 mol% fumaric acid 17 mol% n-dodecenyl succinic acid 21 mol% The above raw materials were subjected to a polycondensation reaction in the same manner as in Production Example 1 to obtain a linear polyester B. The acid value of this polyester resin B was 12 mgKOH / g.

Production Example 3 ( Production of Nonlinear Polyester C) Polyoxyethylene (3) -2,2-bis (4-hydroxyphenyl) propane 52 mol% Terephthalic acid 30 mol% Trimellitic anhydride 18 mol% or more Was subjected to a polycondensation reaction in the same manner as in Production Example 1 to obtain a non-linear polyester C. The acid value of this non-linear polyester resin was 13 mgKOH / g.

Production Example 4 ( Production of Nonlinear Polyester D) Polyoxyethylene (3) -2,2-bis (4-hydroxyphenyl) propane 45 mol% Terephthalic acid 5 mol% Trimellitic anhydride 18 mol% n -Dodecenyl succinic acid 32 mol% The starting material was subjected to polycondensation reaction in the same manner as in Production Example 1 to obtain a non-linear polyester D. The acid value of this non-linear polyester resin was 15 mgKOH / g.

Production Example 5 ( Production of Linear Polyester E) Polyoxypropylene (2,5) -2,2-bis (4-
(Hydroxyphenyl) propane 50 mol% triethylene glycol 12 mol% fumaric acid 38 mol% The above raw materials were subjected to a polycondensation reaction in the same manner as in Production Example 1 to obtain a linear polyester E. The acid value of this linear polyester resin was 12 mgKOH / g.

Production Example 6 ( Production of Nonlinear Polyester A-1) The same raw materials as in Production Example 1 were charged into a stainless steel reactor having a distillation tower, a decompression device and a stirring blade, and the stirring blade was rotated at 210 ° C. When the distillation of water in the system was stopped after 4 hours, the pressure in the system was reduced to 5 mmHg. As the diol component distilled, the rotational load of the stirring blade gradually increased, and after 1.5 hours, The load began to increase rapidly. Here, when the pressure in the system was changed to 50 mmHg, the increase in the stirring load became slow. When this operation was repeated several times until the pressure in the system reached 150 mmHg, almost no distillate component was generated, and the stirring load was within three times that at the start of the reaction. At this time, the pressure in the system was returned to normal pressure, and stirring was continued. After the pressure was reduced to normal pressure, the load of stirring was hardly increased, and after 1 hour, the polymer was taken out to obtain a non-linear polyester A-1. The acid value of this non-linear polyester A-1 was 8 mgKOH / g.

Production Example 7 ( Production of Nonlinear Polyester A-2) The same raw material as in Production Example 1 was charged into a stainless steel reactor having a distillation tower, a decompression device and a stirring blade, and kept at 210 ° C., and the stirring blade was rotated. When the distillation of water in the system was stopped after 4 hours, the pressure in the system was reduced to 5 mmHg. As the diol component distilled, the rotational load of the stirring blade gradually increased, and after 1.5 hours, The load began to increase rapidly. Here, when the pressure in the system was changed to 50 mmHg, the increase in the stirring load became slow. When this operation was repeated several times until the pressure in the system reached 300 mmHg, almost no distillate component was generated, and the stirring load was within three times that at the start of the reaction. At this time, the pressure in the system was returned to normal pressure, and stirring was continued. After the pressure was reduced to normal pressure, the load of stirring was hardly increased, and after 1 hour, the polymer was taken out to obtain a non-linear polyester A-2. The acid value of this non-linear polyester A-2 was 1.0 mgKOH / g.

Production Example 8 ( Production of linear polyester B-1) A polymerization reaction was carried out in the same manner as in Production Example 6 except that the raw materials used in Production Example 6 were changed to the same raw materials as in Production Example 2. Polyester B-1 was obtained. This linear polyester B-1
Has an acid value of 7 mgKOH / g.

Production Example 9 ( Production of linear polyester B-2) A polymerization reaction was carried out in the same manner as in Production Example 7 except that the raw materials used in Production Example 7 were changed to the same raw materials as in Production Example 2. Polyester B-2 was obtained. This linear polyester B-2
Was 2.0 mgKOH / g.

Production Example 10 ( Production of non-linear polyester C-1) A polymerization reaction was carried out in the same manner as in Production Example 7 except that the raw materials used in Production Example 7 were changed to the same raw materials as in Production Example 3. A linear polyester C-1 was obtained. This non-linear polyester C
The acid value of -1 was 1.5 mgKOH / g.

Production Example 11 ( Production of linear polyester E-1) A polymerization reaction was carried out in the same manner as in Production Example 7 except that the raw materials used in Production Example 7 were changed to the same raw materials as in Production Example 5. Polyester E-1 was obtained. This linear polyester E-1
Was 3.0 mgKOH / g.

Wax AG From a hydrocarbon wax F synthesized from a synthesis gas consisting of carbon monoxide and hydrogen by the Age method, wax A,
Wax B and wax C were obtained by crystal fractionation.

Using a Ziegler catalyst, ethylene was subjected to low pressure polymerization to obtain wax E having a relatively low molecular weight, and wax D was obtained by extracting and removing low molecular weight components by fractional crystallization.

A low-molecular-weight polypropylene, biscol 550p (wax G), which is a commercially available pyrolytic wax, was obtained.

Tables 1 and 2 show the physical properties of these waxes AG.
And Table 3. Further, the DSC curve of wax A is shown in FIG.
2 and FIG. 2 show DSC curves of wax F in FIG. 3 and FIG.

[0144]

[Table 1]

[0145]

[Table 2]

[0146]

[Table 3]

Preparation of Toner 1 Non-linear polyester A 100 parts by weight Magnetite 70 parts by weight Urea-based negative charge control agent 2 parts by weight Wax A 4 parts by weight After premixing the above materials, biaxial extrusion set at 130 ° C. Melt kneading was performed by a kneader. The kneaded material was cooled, coarsely pulverized, finely pulverized with a pulverizer using a jet stream, and further obtained with an air classifier to obtain toner particles (toner) having a weight average diameter of 11.5 μm. Toner 1 was prepared by externally adding 0.4 parts by weight of colloidal silica fine powder, and this was used as a one-component developer.

Production of Toner 2 Toner 2 was prepared in the same manner as in the production of Toner 1 except that Wax A was replaced with Wax B, and this was used as a one-component developer.

Production of Toner 3 A toner 3 was prepared in the same manner as in the production of the toner 1 except that the wax A was replaced with the wax C, and this was used as a one-component developer.

Production of Toner 4 A toner 4 was prepared in the same manner as in the production of the toner 1 except that the wax A was replaced with the wax D, and this was used as a one-component developer.

Production of Toner 5 In place of the non-linear polyester A, a linear polyester B was used.
Is the same as in the production of toner 1, except that 75 parts by weight is used, 25 parts by weight of the non-linear polyester C is used, and 2 parts by weight of the monoazochrome complex-based negative charge control agent is used instead of the urea-based negative charge control agent. To prepare a toner 5, which was used as a one-component developer.

Production of Toner 6 In place of the non-linear polyester A, a linear polyester E was used.
Is the same as in the production of toner 1, except that 50 parts by weight of the non-linear polyester A and 50 parts by weight of the non-linear polyester A, and 2 parts by weight of the monoazochrome complex-based negative charge control agent instead of the urea-based negative charge control agent. Thus, a toner 6 was prepared and used as a one-component developer.

Production of Toner 7 In place of the non-linear polyester A, a linear polyester B was used.
75 parts by weight, 15 parts by weight of non-linear polyester A and 10 parts by weight of non-linear polyester C, and 2 parts by weight of monoazochrome complex-based negative charge control agent instead of urea-based negative charge control agent. Except for this, a toner 7 was prepared in the same manner as in the production of the toner 1, and this was used as a one-component developer.

Production of Toner 8 In place of the non-linear polyester A, a linear polyester B was used.
Is the same as in the production of toner 1, except that 75 parts by weight of the non-linear polyester A and 25 parts by weight of the non-linear polyester A, and 2 parts by weight of the monoazochrome complex-based negative charge control agent instead of the urea-based negative charge control agent. Thus, a toner 8 was prepared and used as a one-component developer.

Production of Toner 9 A toner 9 was prepared in the same manner as in the production of the toner 1 except that the wax A was replaced with the wax E, and this was used as a one-component developer.

Production of Toner 10 Toner 10 was prepared in the same manner as in the production of Toner 1 except that wax A was replaced with wax F, and this was used as a one-component developer.

Production of Toner 11 Toner 11 was prepared in the same manner as in the production of toner 1 except that wax G was used instead of wax A, and this was used as a one-component developer.

Preparation of Toner 12 Toner 12 was prepared in the same manner as in the preparation of Toner 1 except that non-linear polyester D was used instead of non-linear polyester A and wax E was used instead of wax A. Was used as a one-component developer.

Production of Toner 13 Non-linear polyester C was used instead of non-linear polyester A
A toner 13 was prepared in the same manner as in the production of the toner 1 except that this was used as a one-component developer.

Production of Toner 14 Non-linear polyester A in place of non-linear polyester A
Of toner 1 in the same manner as in the production of toner 1 except that 30 parts by weight of
4 was prepared and used as a one-component developer.

Production of Toner 15 Toner 15 was prepared in the same manner as in Production Example 1 of Toner 1 except that 75 parts by weight of linear polyester E and 25% by weight of non-linear polyester C were used instead of non-linear polyester A. Was used as a one-component developer.

Table 4 shows the structures of the toners 1 to 15.

[0163]

[Table 4]

(Examples 1 to 8 and Comparative Examples 1 to 7) Using toners 1 to 15, the following fixing and offset test-1, fixing and offset test-2, blocking test and developability test were performed.

Fixing and offset test-1 Commercially available electrophotographic copying machine NP-6650 (manufactured by Canon Inc .:
An unfixed image is obtained by using a fixing unit as shown in FIG. 6), and an unfixed toner image is fixed and an offset test is performed using a temperature-variable heat roller fixing machine obtained by modifying a heat roller fixing machine of NP-6650. Was done. The test was performed by adjusting the temperature every 5 ° C. in a temperature range of 100 to 230 ° C. at a process speed of 100 mm / sec.

For the low-temperature offset and fixability tests,
80 g / m ² paper was used. For hot offset testing,
Evaluation was performed using 52 g / m ² paper. The fixability was measured by applying a load of 50 g / cm ² to the fixed image and using a silk-bon paper [lenz].
cleaning paper “dasper
(R) "(Ozu paper Co. Ltd) rubbed, and the temperature at which the density reduction ratio before and after rubbing was less than 10% was defined as the fixing start point. The offset was defined as the temperature at which no offset was visually observed and the low-temperature offset-free starting point. The test results are summarized in Table 5. Table 5 shows the fixing start temperature, the density decrease rate at 150 ° C, the low temperature offset free start point, and the high temperature offset. Describe the free end point and the non-offset area.

Fixing and offset test-2 Commercially available electrophotographic copying machine NP-6650 (manufactured by Canon Inc.)
As shown in FIG. 5, an unfixed image formed on a recording material is pressed against a heating member 1 and a transfer member 6 is brought into close contact with the heating member 1 via a film 2 as shown in FIG. Fixing and offset tests were performed using an external fixing machine. As a material of the fixing film 2, an endless film in which a release layer of a fluororesin obtained by adding a conductive agent to a polyimide film was coated at 10 μm was used. The test was performed using silicone rubber as the pressure roller 5 with a nip of 3.5 mm, a total pressure between the heating body 1 and the pressure roller 5 of 8 kg, a process speed of 50 mm / sec, and a variable temperature.
The film was driven by driving and tension by a driving roller 3 and a driven roller 4 to apply energy to the low-heat-capacity linear heating element 1 in a pulsed manner to control the temperature.

For the low-temperature offset and fixability tests,
80 g / m ² paper was used. For hot offset testing,
Evaluation was performed using 52 g / m ² paper. The fixability was measured by applying a load of 50 g / cm ² to the fixed image and using a silk-bon paper [lenz].
cleaning paper “dasper
(R) "(Ozu paper Co. Ltd) rubbed, and the temperature at which the density reduction ratio before and after rubbing was less than 10% was defined as the fixing start point. The offset was defined as the temperature at which no offset was visually observed and the low-temperature offset-free starting point. The test results are summarized in Table 6. Table 6 shows the fixing start temperature, the density reduction rate at 150 ° C, the low temperature offset free start point, and the high temperature offset. Describe the free end point and the non-offset area.

Blocking Test Approximately 20 g of the developer was placed in a 100 cc plastic
After leaving it at 3 ° C. for 3 days, it was visually evaluated. Table 7 shows the results.
It writes in.

Developability test Approximately 100 g of the developer was placed in a 500 cc polyethylene cup, left at 45 ° C. for 3 days, and after copying 20 sheets with a commercially available electrophotographic copying machine NP-270Z (manufactured by Canon Inc.). The developability was evaluated with the image of No. Table 7 shows the results of the test (image density, fog). This test can be used as a simulation to see the durability against the temperature rise of the machine and the safety due to long-term storage.

[0171]

[Table 5]

[0172]

[Table 6]

[0173]

[Table 7]

Preparation of Toner 16 Non-linear Polyester A 100 parts by weight Carbon black 5 parts by weight Monoazochrome complex-based negative charge control agent 2 parts by weight Wax A 4 parts by weight After premixing the above materials, the temperature was set to 130 ° C. Melt kneading was performed by a shaft extrusion kneader. The kneaded material was cooled, coarsely pulverized, finely pulverized with a pulverizer using a jet stream, and further obtained with an air classifier to obtain toner particles (toner) having a weight average diameter of 8 μm. Toner 16 was prepared by externally adding 1.0 part by weight of colloidal silica fine powder. To 100 parts by weight of a ferrite carrier coated with a styrene-acrylic resin and a fluororesin, 10 parts by weight of a toner 16 was mixed as a starting agent,
Further, a developer using an externally added toner as a replenishing agent was obtained.

Preparation of Toner 17 A toner 17 was prepared in the same manner as in the preparation of the toner 16 except that the non-linear polyester A was changed to the non-linear polyester A-1. I got

Preparation of Toner 18 Toner 18 was prepared in the same manner as in the preparation of Toner 16, except that the non-linear polyester A was replaced with the non-linear polyester A-2, and mixed with a ferrite carrier to form a developer. I got

Preparation of Toner 19 Toner 19 was prepared in the same manner as in the preparation of Toner 16 except that 100 parts by weight of non-linear polyester A was replaced by 75 parts by weight of linear polyester B and 25 parts by weight of non-linear polyester A. 19 was prepared and mixed with a ferrite carrier to obtain a developer.

Production of Toner 20 100 parts by weight of non-linear polyester A, 75 parts by weight of linear polyester B-1 and 2 parts by weight of non-linear polyester A-1
A toner 20 was prepared in the same manner as in the production of the toner 16 except that the amount was changed to 5 parts by weight, and mixed with a ferrite carrier to obtain a developer.

Production of Toner 21 100 parts by weight of non-linear polyester A, 75 parts by weight of linear polyester B-2 and 2 parts of non-linear polyester A-2
A toner 21 was prepared in the same manner as in the production of the toner 16 except that the amount was changed to 5 parts by weight, and mixed with a ferrite carrier to obtain a developer.

Preparation of Toner 22 Toner 22 was prepared in the same manner as in the preparation of toner 16 except that 100 parts by weight of non-linear polyester A was replaced by 75 parts by weight of linear polyester E and 25 parts by weight of non-linear polyester C. No. 22 was prepared and mixed with a ferrite carrier to obtain a developer.

Preparation of Toner 23 100 parts by weight of non-linear polyester A, 75 parts by weight of linear polyester E-1 and 2 parts by weight of non-linear polyester C-1
A toner 23 was prepared in the same manner as in the production of the toner 16 except that the amount was changed to 5 parts by weight, and mixed with a ferrite carrier to obtain a developer.

Table 8 shows the structures of the toners 16 to 23.

[0183]

[Table 8]

(Examples 9 to 14 and Comparative Examples 8 and 9)
Using toners 16 to 23, the following fixing and offset test-3, blocking test, developability test-1 and developability test-2 were performed.

Fixing and offset test-3 Commercially available electrophotographic copying machine NP-6650 (manufactured by Canon Inc.)
As shown in FIG. 5, an unfixed image formed by using a two-component developer having the above-mentioned toners 16 to 23 as a color developer is pressed against a heating member 1 and transferred to a transfer material via a film 2. Fixing and offset tests were performed using an external fixing machine comprising a pressure member 5 for bringing the heating member 6 into close contact with the heating element 1. As a material of the fixing film 2, an endless film in which a release layer of a fluororesin obtained by adding a conductive agent to a polyimide film was coated at 10 μm was used. Pressure roller 5
Use silicone rubber as the nip 3.5mm,
The test was performed with a total pressure of 8 kg between the heating body 1 and the pressure roller 5, a process speed of 50 mm / sec, and a variable temperature. The film was driven by driving and tension by a driving roller 3 and a driven roller 4 to apply energy to the low-heat-capacity linear heating element 1 in a pulsed manner to control the temperature.

For the low-temperature offset and fixability tests,
80 g / m ² paper was used. For hot offset testing,
Evaluation was performed using 52 g / m ² paper. The fixability was measured by applying a load of 50 g / cm ² to the fixed image and using a silk-bon paper [lenz].
cleaning paper “dasper
(R) "(Ozu paper Co. Ltd) rubbed, and the temperature at which the density reduction ratio before and after rubbing was less than 10% was defined as the fixing start point. The offset was defined as the temperature at which no offset was visually observed and the low-temperature offset-free starting point. The maximum temperature at which no offset occurs was defined as the free end point of the high-temperature offset.The test results are summarized in Table 9. Table 9 shows the fixing start temperature, the density reduction rate at 150 ° C., the low-temperature offset free start point, and the high-temperature offset. Describe the free end point and the non-offset area.

Blocking Test Approximately 20 g of the developer was placed in a 100 cc plastic
After leaving it at 3 ° C. for 3 days, it was visually evaluated. Table 1 shows the results.
Write 0.

Developability Test-1 Approximately 100 g of the developer was placed in a 500 cc polyethylene cup, left at 45 ° C. for 3 days, and then 20 sheets were printed with a commercially available electrophotographic copying machine NP-270Z (manufactured by Canon Inc.). The developability of the image after copying was evaluated. Table 10 shows the results of the test (image density, fog). This test can be used as a simulation to see the durability against the temperature rise of the machine and the stability after long-term storage.

Developability test-2 About 100 g of a developer was placed in a 500 cc polyethylene cup, left at 32.5 ° C./85% Rh for 3 days, and then a commercially available electrophotographic copying machine NP-270Z (Canon Inc.) Developability was evaluated on the images after the first and twentieth copies. Table 10 shows the results of the test (image density, fog). This test can be used to simulate the rise of toner charge.

[0190]

[Table 9]

[0191]

[Table 10]

[0192]

The toner for developing electrostatic images of the present invention has at least a binder resin and a wax, and the binder resin has a polyester resin having a soft segment as a main component. Has a specific thermal property, so that the wax having the specific thermal property is well dispersed in the binder resin. Since it has sufficient effects, it has better low-temperature fixability and excellent developability while maintaining offset resistance and blocking resistance from low to high temperatures.

When a toner image formed using this toner is fixed on a recording material by using a heat fixing means, no offset occurs in a wide temperature range from low temperature to high humidity, and the toner image is fixed well in a low temperature range. It is possible to

[Brief description of the drawings]

FIG. 1 is a view showing a DSC curve when a temperature of wax A used in an example is raised.

FIG. 2 is a view showing a DSC curve when the temperature of wax A used in Examples is lowered.

FIG. 3 is a view showing a DSC curve when a temperature of wax F used in a comparative example is raised.

FIG. 4 is a view showing a DSC curve when the temperature of wax F used in a comparative example is lowered.

FIG. 5 is a schematic explanatory view showing a specific example of a fixing device for performing the heat fixing method of the present invention.

FIG. 6 is a schematic explanatory view showing a specific example of another fixing device for performing the heat fixing method of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 heating means 2 fixing film 3 drive roller 4 driven roller 5 pressure roller 6 recording material 7 toner image 8 entrance guide 9 resistance material 10 alumina substrate 11 temperature measuring element 21 heat fixing means 22 fixing roller 23 pressure roller 24 heating means 25 recording Material 26 Unfixed toner image 27 Fixed toner image

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Hirohide Tanigawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Tsutomu Onuma 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon JP-A-6-250438 (JP, A) JP-A-6-324513 (JP, A) JP-A-6-118699 (JP, A) JP-A-6-118685 (JP, A A) JP-A-5-346684 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03G 9/08

Claims (38)

(57) [Claims] 1. An electrostatic image developing toner having at least a binder resin and a wax, wherein the binder resin contains a polyester resin having a soft segment as a main component, and a differential scanning calorie of the wax. In the DSC curve by the meter, regarding the endothermic peak at the time of temperature rise and the exothermic peak at the time of temperature decrease, the onset temperature of endotherm is in the range of 50 to 110 ° C., and the temperature is in the range of 70 to 1
At least one endothermic peak P at the time of temperature rise in the region of 30 ° C.
Having _1, maximum heating toner for developing electrostatic images which is characterized in that it has a peak during the temperature decrease in a range of ± 9 ° C. of the endothermic peak P _1. 2. The binder resin according to claim 1, wherein the polyester resin having the soft segment is 5% based on the weight of the binder resin.
2. The electrostatic image developing toner according to claim 1, wherein the toner is contained in an amount of 0% by weight or more. 3. The binder resin is a polyester resin having the soft segment, based on the weight of the binder resin.
2. The electrostatic image developing toner according to claim 1, wherein the toner is contained in an amount of 0% by weight or more. 4. The soft segment has 5 to 30 carbon atoms.
4. The toner according to claim 1, wherein the toner is an alkyl group or an alkenyl group having 5 to 30 carbon atoms. 5. The electrostatic image developing toner according to claim 1, wherein the soft segment is introduced into the skeleton of the polyester resin by being branched. 6. The polyester resin having the soft segment is obtained by synthesizing using at least one monomer of an aliphatic dicarboxylic acid substituted with a soft segment and an aliphatic diol substituted with a soft segment. 6. The electrostatic image developing toner according to claim 1, wherein the toner is a toner. 7. The toner according to claim 1, wherein the binder resin comprises a mixture of a non-linear polyester resin and a linear polyester resin. 8. The mixing ratio of the non-linear polyester resin and the linear polyester resin in the binder resin is from 5:95 to 6
The electrostatic image developing toner according to claim 7, wherein the ratio is 0:40. 9. The mixing ratio of the non-linear polyester resin and the linear polyester resin in the binder resin is from 10:90 to
The toner according to claim 7, wherein the ratio is 50:50. 10. The mixing ratio of the non-linear polyester resin and the linear polyester resin in the binder resin is 10:90.
The toner for developing an electrostatic image according to claim 7, wherein the ratio is from 40 to 60. 11. The toner comprises (i) a binder resin having a mixture of a non-linear polyester resin and a linear polyester resin, and (ii) at least one of an inorganic metal oxide and an organic metal oxide. The toner for developing an electrostatic image according to claim 7, wherein: 12. The electrostatic image development according to claim 11, wherein the toner has a metal cross-linking structure between the binder resin and at least one of the inorganic metal oxide and the organic metal oxide. For toner. 13. The binder resin has an acid value of 10 mg KOH /
The toner for developing an electrostatic image according to claim 11, wherein the toner has a value of g or less. 14. The binder resin has an acid value of 9 mgKOH / g.
The toner for developing an electrostatic image according to claim 11, wherein the toner has the following. 15. The binder resin has an acid value of 6 mgKOH / g.
The toner for developing an electrostatic image according to claim 11, wherein the toner has the following. 16. The binder resin has a styrene resin, an acrylic resin, a methacryl resin, a silicone resin, a polyester, a polyurethane, a polyamide resin, a furan resin, an epoxy resin, a xylene resin, a polyvinyl butyral, a terpene resin and a chromanindene as subcomponents. 2. The electrostatic image developing toner according to claim 1, comprising at least one resin selected from the group consisting of resins and petroleum resins. 17. The toner for developing an electrostatic image according to claim 1, wherein the polyester resin having the soft segment has an acid value of 10 mgKOH / g or less. 18. The toner according to claim 1, wherein the polyester resin having the soft segment has an acid value of 9 mgKOH / g or less. 19. The toner for developing an electrostatic image according to claim 1, wherein the polyester resin having the soft segment has an acid value of 6 mgKOH / g or less. 20. A heat fixing method for fixing a toner image on a recording material by a heat fixing means, wherein the toner image is formed by a toner having at least a binder resin and a wax, and the binder resin is a soft resin. It contains a polyester resin having a segment as a main component, and in a DSC curve of the wax by a differential scanning calorimeter, with respect to an endothermic peak at the time of temperature rise and an exothermic peak at the time of temperature decrease, the onset temperature of endotherm is 50 to 1
In the range of 10 ° C., it has an endothermic peak P ₁ of at least one heating to a region of temperature 70 to 130 ° C., the maximum exothermic peak at the time of temperature drop within a range of ± 9 ° C. of endothermic peaks P ₁ A heat fixing method characterized by having. 21. The binder resin according to claim 2, wherein the polyester resin having the soft segment is contained in an amount of 50% by weight or more based on the weight of the binder resin.
0. The heat fixing method according to item 0. 22. The binder resin according to claim 2, wherein the polyester resin having the soft segment is contained in an amount of 70% by weight or more based on the weight of the binder resin.
0. The heat fixing method according to item 0. 23. The soft segment has 5 to 3 carbon atoms.
23. The heat fixing method according to claim 20, wherein the alkyl group is 0 or an alkenyl group having 5 to 30 carbon atoms. 24. The heat fixing method according to claim 20, wherein the soft segment is introduced by being branched into a skeleton of the polyester resin. 25. The polyester resin having the soft segment is obtained by synthesizing using at least one monomer of an aliphatic dicarboxylic acid substituted with a soft segment and an aliphatic diol substituted with a soft segment. 25. The heat fixing method according to claim 29, wherein the heat fixing method is performed. 26. The heat fixing method according to claim 20, wherein the binder resin comprises a mixture of a non-linear polyester resin and a linear polyester resin. 27. The mixing ratio of the non-linear polyester resin and the linear polyester resin in the binder resin is from 5:95 to
27. The heat fixing method according to claim 26, wherein the ratio is 60:40. 28. The mixing ratio of the non-linear polyester resin and the linear polyester resin in the binder resin is 10:90.
The heating fixing method according to claim 26, wherein the ratio is 50 to 50. 29. The mixing ratio of the non-linear polyester resin to the linear polyester resin in the binder resin is from 10:90 to
27. The heat fixing method according to claim 26, wherein the ratio is 40:60. 30. The toner comprises (i) a binder resin having a mixture of a non-linear polyester resin and a linear polyester resin, and (ii) at least one of an inorganic metal oxide and an organic metal oxide. The heat fixing method according to claim 26, wherein the heat fixing is performed. 31. The heat fixing method according to claim 30, wherein the toner has a metal crosslinked structure of the binder resin and at least one of the inorganic metal oxide and the organic metal oxide. 32. The binder resin has an acid value of 10 mg KOH /
31. The heat fixing method according to claim 30, wherein the value is equal to or less than g. 33. The binder resin has an acid value of 9 mgKOH / g.
31. The heat fixing method according to claim 30, comprising: 34. The binder resin has an acid value of 6 mgKOH / g.
31. The heat fixing method according to claim 30, comprising: 35. The binder resin as a sub-component is a styrene-based resin, an acrylic resin, a methacrylic resin, a silicone resin, a polyester, a polyurethane, a polyamide resin, a furan resin, an epoxy resin, a xylene resin, a polyvinyl butyral, a terpene resin, and a chromanindene. 21. At least one resin selected from the group consisting of resin and petroleum resin.
The heat fixing method described in the above. 36. The heat fixing method according to claim 20, wherein the polyester resin having the soft segment has an acid value of 10 mgKOH / g or less. 37. The heat fixing method according to claim 20, wherein the polyester resin having the soft segment has an acid value of 9 mgKOH / g or less. 38. The heat fixing method according to claim 20, wherein the polyester resin having the soft segment has an acid value of 6 mgKOH / g or less.