JP2987791B2 - Non-magnetic one-component 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 and a magnetic latent image in electrophotography, electrostatic printing, magnetic recording and the like. In particular, the present invention relates to a non-magnetic one-component toner used in a heat fixing method such as heat roller fixing and a heat fixing method.

[0002]

2. Description of the Related Art U.S. Pat.
A number of methods are known as described in JP-A-69-169, JP-B-42-23910, JP-B-43-24748, and the like. In general, various methods using a photoconductive substance are used. Means for forming an electric latent image on the photoreceptor, developing the latent image with toner, transferring a toner image to a transfer material such as paper as necessary, and then applying heat, pressure, and heat. The toner is fixed by pressure or solvent vapor to obtain a copy, and the remaining toner not transferred onto the photoreceptor is cleaned by various methods, and the above steps are repeated.

In recent years, such copying apparatuses have become smaller and smaller.
Lighter weight, lower power consumption, and higher reliability have been strictly pursued, and as a result, the performance required of the toner has also become higher.

As a method of developing an electrostatic charge image, a two-component developing method using a mixture of toner and carrier and a one-component developing method using only a magnetic toner are generally used. The development method uses a carrier and a so-called AT that adjusts the mixing ratio of the toner and the carrier.
Considering the necessity of the R machine, it contradicts demands for miniaturization and weight reduction. On the other hand, the one-system split development method has a problem that it is difficult to cope with color toner because magnetic toner is used.

In response to such a demand, Japanese Patent Laid-Open Publication No. 58-1
No. 16559, JP-A-60-120368,
The non-magnetic one-component developing method disclosed in Japanese Patent Application Laid-Open No. 63-271371 has attracted attention as a developing method for solving the above problems. In the non-magnetic one-component developing method,
The toner is coated on the toner carrier using a toner application roller, a blade, or the like. The toner is charged by friction with the blade or the surface of the toner carrier, but when the coating layer is thick, there is a toner that cannot be sufficiently charged. Since this causes fogging and scattering, the toner must be coated in a thin layer. Therefore, the blade must be pressed against the toner carrier with a sufficient pressure, and at this time, the blade must be pressed against the developer carrier with a sufficient pressure. In a developing method or a one-component developing method using a magnetic toner, the force is larger than that of the toner. For this reason, deterioration of the toner is apt to occur, and image deterioration such as fogging and density reduction occurs.

That is, the toner used in the non-magnetic one-component developing method is required to have high mechanical strength and thermal strength. However, simply increasing these strengths leads to an increase in thermal energy required for fixing, which is contrary to the demand for low power consumption.

With respect to fixing, a heat fixing method using a heat roller or a film is performed while a toner image surface of a sheet to be fixed is brought into contact with the surface of a heat roller or a film having a surface formed of a material having releasability from toner. The fixing is carried out by passing through. 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 the fixing roller or the film surface because the heat roller or the film surface and the toner image come into contact with each other in a molten state, and transfer,
This re-transfers to the next sheet to be fixed, causing a so-called offset phenomenon, which may stain the sheet to be fixed. 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 a 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 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. .

This is in the opposite direction to miniaturization and weight reduction. In addition, 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 the photoreceptor or contamination of the surface of the toner carrier such as a sleeve will cause deterioration of the 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 a wax is contained in a toner as a release agent. For example, JP-A-52-330
No. 4, JP-A-52-3305, JP-A-57-3305.
A technique such as 52574 is disclosed.

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.

[0013] 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 low-temperature offset properties and improved fixability have been desired. As described above, in the non-magnetic one-component developing method, high performance is required for all of the developing property, the fixing property, and the anti-offset property.

[0016]

SUMMARY OF THE INVENTION An object of the present invention is to provide a non-magnetic one-component toner which has solved the above-mentioned problems, and a method for fixing the toner by heating.

That is, an object of the present invention is to provide a non-magnetic one-component toner excellent in fixing property at low temperature and anti-offset property, and a method of heat fixing the toner.

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

It is a further object of the present invention to provide a non-magnetic one-component toner which has excellent blocking resistance and does not deteriorate in developability even after being left for a long period of time, and a method for heat-fixing the toner.

Another object of the present invention is to provide a non-magnetic one-component toner excellent in durability against temperature rise of a machine main body, and a method of heating and fixing the toner.

A main object of the present invention is to provide a non-magnetic one-component toner which can satisfy the above objects without inconsistency, and a method for heat-fixing the toner.

[0022]

According to the present invention, a supply roller for supplying a toner to a toner carrier is pressed against the toner carrier at a non-zero contact pressure, and a non-zero speed. Used in a non-magnetic one-component developing type developing device in which a toner applying blade provided on the downstream side of the supply roller is pressed against the toner carrier with a non-zero contact pressure. In a non-magnetic one-component toner containing at least a binder resin and a hydrocarbon wax, the hydrocarbon wax has the following characteristic in a DSC curve measured by a differential 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 the endothermic peak is in the range of 50 to 90 ° C., and there is at least one endothermic peak P _{1 in} the region of the temperature of 90 to 120 ° C. of peak temperature ± peak P ₁ 9
A non-magnetic one-component toner, which satisfies a maximum exothermic peak at the time of temperature fall within a range of ° C.

Further, according to the present invention, in the DSC curve of the non-magnetic one-component toner measured by a differential scanning calorimeter,
The onset temperature at the first endothermic peak appearing at 80 ° C. or higher at the time of temperature rise is 105 ° C. or less, the endothermic peak temperature is in the range of 100 to 120 ° C., and the exothermic peak temperature at the time of temperature decrease is 90 to 90 ° C. The present invention relates to a non-magnetic one-component toner having a temperature of 115 ° C.

Further, in the present invention, the onset temperature of the endothermic peak in the DSC curve measured by the differential scanning calorimeter with respect to the endothermic peak at the time of temperature rise and the exothermic peak at the time of temperature fall is in the range of 50 to 90 ° C., Temperature 90-120 ° C
At least one has an endothermic peak P ₁ in the area, there is a maximum exothermic peak at the time of cooling in the range of endothermic peak temperature ± 9 ° C. peak P _1, the hydrocarbon wax and the binder resin satisfies the property The present invention relates to a heat fixing method characterized by fixing a toner image formed with a non-magnetic one-component toner to a transfer material by a contact heat fixing unit.

Further, according to the present invention, the DSC curve of the toner measured by a differential scanning
The onset temperature at the first endothermic peak appearing above is 105 ° C. or less, and the endothermic peak temperature is 100 to 1
A heat-fixing toner image formed of a non-magnetic one-component toner satisfying a temperature range of 20 ° C. and a heat generation peak temperature in the range of 90 to 115 ° C. with respect to a heat generation peak at the time of cooling is fixed to a transfer material by heating with contact. The present invention relates to a heat fixing method characterized by fixing by means.

Further, the present invention will be described in detail.

The behavior between heat and toner can be determined by analyzing data obtained by measuring the toner with a differential scanning calorimeter. That is, it is possible to know the exchange of heat with the toner and the change in the state of the toner from the data. For example, it is possible to know whether the offset phenomenon can be prevented, and to know the effect of heat during storage or actual use, for example, what is the anti-blocking property, and how much the temperature increase affects the developability. it can.

When the temperature is increased, changes in the state when heat is applied to the toner can be seen, and the transition, melting,
An endothermic peak due to dissolution is observed. The present invention is at 80 ° C.
The onset temperature of the first endothermic peak that appears above is 1
It is characterized in that the temperature is not higher than 05 ° C (preferably in the range of 90 to 102 ° C), whereby the low-temperature fixability is excellent. On the other hand, when 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 fixing property become poor. Further, the toner of the present invention preferably has a rising endothermic peak of 80 ° C. or higher, and has excellent blocking resistance.

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. On the other hand, when the temperature is lower than 100 ° C., the wax component dissolves in the binder resin before the temperature becomes high, and it is difficult to obtain sufficient offset resistance at high temperatures. On the other hand, when the temperature 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 90 to 115 ° C (preferably 9 to 115 ° C).
(8 to 110 ° C.), thereby exhibiting good fixability and blocking resistance. on the other hand,
If the temperature exceeds 115 ° 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 90 ° C., blocking, fusion and the like are likely to occur,
Further, the plasticizing effect of the binder resin may be maintained until a low temperature, and a nail mark may be formed on an image portion in a paper discharge portion, or a transfer material may be adhered on a paper discharge tray.

In the DSC measurement according to the present invention, since the exchange of heat of the toner is measured and its behavior is observed, it is necessary to measure 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. (Specific examples are shown in FIGS. 1 and 3 to 6.) Peak temperature (PP): Peak top temperature (1)
The largest peak in the region below 20 ° C. ). Peak onset temperature (OP): The tangent of the peak at the point where the differential value of the peak curve that can be attributed to the PP becomes the maximum is drawn, and the temperature at the intersection of the tangent and the base line (a specific example in FIG. 1) The exothermic peak (negative direction is assumed to be exothermic) Exothermic peak temperature: peak top temperature The hydrocarbon wax used in the present invention is obtained by polymerizing alkylene by radical polymerization under high pressure or by Ziegler catalyst under low pressure. Hydrogenated alkylene polymer obtained by pyrolysis of a high molecular weight alkylene polymer, an alkylene polymer obtained by thermal decomposition of a high molecular weight alkylene polymer, carbon monoxide, and a hydrocarbon distillation residue obtained by the Age method from a synthesis gas consisting of hydrogen. A hydrocarbon wax obtained by extracting and separating a specific component from a synthetic hydrocarbon or the like 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, with these methods,
Examples include those from which low molecular weight components have been removed, those from which low molecular weight components have been extracted, and those from which low molecular weight components have been further removed.

The hydrocarbon as a base is synthesized by a reaction between carbon monoxide and hydrogen using a metal oxide-based catalyst (often a multi-component system of two or more types), for example, a zincol method, a 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
Number average molecular weight (Mn) is 550 to 1200, preferably 600 to 1000, and weight average molecular weight (Mw) is 800 to
3600, preferably 900 to 3000, Mw / Mn is 3 or less, preferably 2.5 or less, particularly preferably 2.
0 or less. Further, a molecular weight of 700 to 2400 (preferably a molecular weight of 750 to 2000, particularly preferably a molecular weight of 8
00 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 determined by gel permeation chromatography (G
PC) 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 the sample. (J
IS K5902), density at 25 ° C according to JIS
K6760 and softening point are values measured according to JIS K2207.

As described above, the present invention can also be achieved by the following non-magnetic one-component toner. In a non-magnetic one-component toner containing at least a binder resin and a hydrocarbon wax, the hydrocarbon wax has the following characteristics, a DSC curve measured by a differential scanning calorimeter, an endothermic peak at the time of temperature rise, and a peak. of in the range onset temperature is 50 to 90 ° C., at least one endothermic peak P ₁ is present and lowered within the range of the peak temperature ± 9 ° C. of endothermic peaks P ₁ in the range of 90 to 120 ° C. A non-magnetic one-component toner satisfying the following condition.

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. If 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 at elevated temperatures. Is too high, and sufficient fixability cannot be obtained. Within the range of 90 to 120 ° C, preferably 95 to 1
By having an endothermic peak in the range of 20 ° C, particularly preferably in the range of 97 to 115 ° C, satisfactory fixability and offset resistance can be satisfied. If 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 120 ° C.
If the peak temperature exists only in a region exceeding the temperature, the melting temperature of 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 seen, 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 defined 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. Peak temperature: Peak top temperature Exothermic peak: Peak temperature: Maximum peak peak temperature The content of these hydrocarbon waxes is determined by the binder resin 100.
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 non-magnetic one-component 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 substituted products thereof; 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 a mixed resin.

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

The 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.

Modified products such as 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. Among these, charge control agents such as nigrosine and quaternary ammonium salts are particularly preferably used.

In the toner of the present invention, the charge 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 comprises:
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, among which polyvinylidene fluoride is 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.

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 aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengalara, phthalocyanine blue, and indanthrene blue. These are used in an amount necessary and sufficient to maintain the optical density of the fixed image, and 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, per 100 parts by weight of the resin.
Good addition amount by weight. A dye is further used for the same purpose. 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 non-magnetic one-component toner 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 charge control agent as required, and other additives are added. The agent and the like are mixed thoroughly by a mixer such as a Henschel mixer or a ball mill, and then heated and kneaded using a hot kneader such as a kneader or an extruder to melt and knead the resins with each other while mixing the metal compound, The toner according to the present invention can be obtained by dispersing or dissolving pigments and dyes, cooling and solidifying, and then performing pulverization and classification.

Further, if necessary, desired additives are sufficiently mixed by a mixer such as a Henschel mixer to obtain a non-magnetic one-component toner according to the present invention.

Next, an example of the developing device used in the present invention will be described, but the present invention is not limited to this.
In FIG. 12, reference numeral 12 denotes a latent image holding member, and a latent image is formed by electrophotographic processing means or electrostatic recording means (not shown). Reference numeral 13 denotes a developer carrier, which is made of a non-magnetic sleeve made of aluminum or stainless steel. The developer carrier may be a crude tube of aluminum or stainless steel as it is, but preferably the surface is uniformly roughened by spraying glass beads or the like, the surface is mirror-finished, or the surface is coated with a resin or the like. Is good. The developer 17 is stored in a hopper 14 and is supplied onto a developer carrier by a supply roller 15. The supply roller is made of a foamed material such as polyurethane foam, and rotates in a forward or reverse direction at a relative speed other than 0 with respect to the developer carrier, and together with the supply of the developer, the development after development on the developer carrier is performed. The developer (undeveloped developer) is also stripped.
The developer supplied onto the developer carrier is uniformly and thinly applied by the developer application blade 16. The contact pressure between the developer coating blade and the developer carrier is 3 to 250 g / cm, preferably 1 to 250 g / cm, as the linear pressure in the sleeve generatrix direction.
0 to 120 g / cm is effective. Contact pressure is 3g / c
If it is smaller than m, it is difficult to uniformly apply the toner, and the charge amount distribution of the toner becomes broad, which causes fogging and scattering. On the other hand, when the contact pressure exceeds 250 g / cm, a large pressure is applied to the developer, and the external additive of the developer is deteriorated. Further, a large torque is required to drive the developer carrier, which is not preferable. The developer coating blade is preferably made of a triboelectric material suitable for charging the developer to a desired polarity. For example, if the developer is positively charged, silicon rubber, polyurethane, fluorine rubber, polychlorobutadiene rubber, etc. is used. If the developer is negatively charged, styrene butadiene rubber, nylon, etc. is used as a blade. The charging efficiency is higher. Also, by blending silica, resin fine particles, etc.,
It is also possible to adjust the triboelectric charging property of the blade to the developer. In addition, by imparting appropriate conductivity to the blade by blending a conductive powder such as carbon or titanium oxide, it is possible to prevent the developer from being excessively charged.

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

As the contact heating fixing means, a heating and pressurizing roll fixing device or a fixedly supported heating element is brought into pressure contact with the heating element, and the transfer material is brought into close contact with the heating element via a film. A fixing unit that heats and fixes the toner with the pressing member can be used. FIG. 11 shows an example of the fixing unit.
Shown in

The heating element in the fixing device shown in FIG.
It has a smaller heat capacity than conventional heat rolls and has a linear heating part, and the maximum temperature of the heating part is 100 to 30
Preferably it is 0 ° C.

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. Examples of the heat-resistant sheet include polyester, PET (polyethylene) having high heat resistance. Terephthalate), PFA (tetrafluoroethylene-perfluoroalkylvinyl ether copolymer), PTFE (polytetrafluoroethylene), polyimide, polymer sheet such as polyamide, metal sheet such as aluminum, and metal sheet and polymer sheet. A laminate sheet is used.

A more preferable structure of the film 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.

Reference numeral 10 denotes a low-heat-capacity linear heating element fixedly supported by the apparatus, and has a thickness of 1.0 mm and a width of 10 mm, for example.
mm, an alumina substrate 9 having a longitudinal length of 240 mm
Is applied to a width of 1.0 mm, and is energized from both ends in the longitudinal direction. The energization is performed by applying a pulse corresponding to a desired temperature and energy release amount controlled by the temperature detecting element 11 by changing the pulse width in a pulse-like waveform of DC 100 V and a cycle of 20 msec. Approximate pulse width is 0.5msec ~
5 msec. The fixing film 2 moves in the direction of the arrow in the figure by contacting the heating element 10 whose energy and temperature are controlled in this manner.

An example of the fixing film has a thickness of 20 μm.
m is a heat-resistant film (for example, polyimide, polyetherimide, PES or PFA, at least on the image contact surface side, a fluororesin such as PTFE or PAF) coated with a release layer having a thickness of 10 μm and coated with a release layer. Generally, the total thickness is less than 100μ, more preferably 4
Less than 0μ is good. 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.

Reference numeral 5 denotes a pressure roller having a rubber elastic layer having good releasability such as silicone rubber.
The heating element is pressurized through the film with g, and is rotated by pressing against the film. The unfixed toner 7 on the transfer material 6 is guided to a fixing unit by an entrance guide 8 and obtains a fixed image by the above-described heating.

In the above description, the endless belt has been described.
A sheet feeding shaft and a winding shaft are used, and the fixing film may be an edged film.

The image forming apparatus is applicable to a fixing device of an apparatus for forming an image using a toner such as a copying machine, a printer, and a fax.

[0077]

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 a 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 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 These physical properties are shown in Tables 1, 2 and 3.

Example 1 100 parts by weight of styrene-butyl acrylate copolymer (copolymerization weight ratio 89:11; number average molecular weight of about 5000) 0.5 parts by weight of quaternary ammonium salt 5.0 monoazo red pigment 5.0 2.5 parts by weight wax a 2.5 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 product 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 12 μm. 100 parts by weight of this toner, 1.0 part by weight of positively chargeable colloidal silica fine powder and 0.5 part of polyvinylidene fluoride powder were mixed (externally added) to obtain a developer.

Table 4 shows the DSC measurement results of the toner 1. FIG. 1 shows a DSC curve when the temperature of the toner 1 is raised, and FIG. 2 shows a DSC curve when the temperature is lowered.

Examples 2 to 5 Toners 2 to 5 were prepared in the same manner as in Example 1 except that waxes b to e were used. DS of each toner
Table 4 shows the C measurement results.

Example 6 Example 1 was repeated except that 1.0 part by weight of positively chargeable colloidal silica powder, 0.5 part by weight of polyvinylidene fluoride powder and 0.5 part by weight of strontium titanate powder were used as external additives. In the same manner as in Example 1, a toner 1a was obtained.

Comparative Examples 1 to 4 Toners 6 to 9 were prepared in the same manner as in Example 1 except that waxes fi were used. Table 4 shows the DSC measurement results of these toners.

Comparative Example 5 A toner 10 was prepared in the same manner as in Example 1 except that no wax was used. Table 4 shows the DSC measurement result of this toner.

Comparative Example 6 A toner 12 was prepared in the same manner as in Example 1 except that a low molecular weight polypropylene wax (Viscol 550P) manufactured by Sanyo Chemical Industries, Ltd. was used. Toner 12
Is shown in Table 5.

(Fixing and Offset Test) An unfixed image was obtained by 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 4.0mm, linear pressure 0.4kg
/ Cm, process speed 45mm / 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. Fixability is as follows: fixed image is 50 g / cm
^2. Apply a load of ² on silbon paper [lenz cleanin
g paper "dasper (R)" (Ozu 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 5. Table 5 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: No aggregate was observed. Good: Aggregates are seen but easily collapse. OK: Aggregates are seen, but collapse when shaken. Impossible: Aggregates can be caught and do not collapse easily.

(Developability test) About 75 g of developer was
After placing in a cc polycup and allowed to stand at 45 ° C. and 90% environment for 7 days, the developing device of a commercially available electrophotographic copying machine FC-2 (manufactured by Canon Inc.) was developed by a copying machine modified as shown in FIG. The sex was evaluated. Table 6 shows the results of the test (image density, fog, drum fusion, filming). By this test, it is possible to make a simulation to check the durability of the machine against the temperature rise and the safety by leaving it for a long time.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

[0094]

[Table 4]

[0095]

[Table 5]

[0096]

[Table 6] Examples 6 to 10 and Comparative Examples 7 to 11 Unfixed images of the toners 1 to 10 were pressed against a heating member 1 as shown in FIG. Adhere to 1. Fixing and offset tests were performed using an external fixing machine including the pressing member 5. As a material of the fixing film 2, an endless film in which a release layer of a fluororesin obtained by adding a conductive material to a polyimide film was coated by 10 μm was used.

The pressure roller 5 is made of silicone rubber, has a nip of 3.5 mm, a total pressure of 8 kg between the heating element 1 and the pressure roller 5, and a process speed of 50 mm / s.
The test was performed as ec. The film was driven by driving and tension by a driving roller 3 and a driven roller 4, and energy was applied to the heating element 1 having a low heat capacity linear shape in a pulsed manner to control the temperature. The evaluation was performed in the same manner as in Example 1, and the results are shown in Table 7.

As can be seen from Tables 5 to 7, the toners containing the waxes a, b, or c were even better overall than the toners containing the alkylene polymer-based waxes d or e.

[0099]

[Table 7] Example 12 100 parts by weight of polyester resin (Mn = 5280, Mw = 181300) 2 parts by weight of quaternary ammonium salt 3 parts by weight of wax A 4 parts by weight of copper phthalocyanine Similarly, a nonmagnetic one-component toner 11 having a weight average particle diameter of 12 μm was obtained.
1.0 part by weight of hydrophobic colloidal silica fine powder was externally added to 100 parts by weight of the toner. Table 8 shows the DSC data.

This developer was tested using a copying machine obtained by modifying a commercially available FC-2 (manufactured by Canon Inc.) developing apparatus as shown in FIG. At an environmental temperature of 7.5 ° C., there was no low-temperature offset even in the first copy immediately after the power was turned on, and the fixability was good.

At 23.5 ° C., even after copying 50 sheets of continuous postcards and copying with 52 g / m ² paper, no offset was observed due to the temperature rise at the end of the fixing machine. In addition, temperature 32.5
When a copy test was conducted in an environment of 90 ° C. and 90% humidity, a clear blue image was always obtained, the toner could be used up in a good state to the end, no fusing occurred, and there was no blocking in the cleaning section. Was. Add 45 more cartridges
A clear image free from fog was obtained even when the image was left standing for one week in an environment at 90 ° C. and 90% and evaluated.

[0102]

[Table 8]

[0103]

According to the present invention, by including a specific hydrocarbon-based wax in a toner, favorable thermal characteristics can be imparted to the toner, and the following excellent effects are exhibited.

The present invention can provide a toner excellent in fixing property at low temperature and anti-offset property, and a heat fixing method.

The present invention can provide a toner excellent in offset resistance at high temperatures and a heat fixing method.

The present invention can provide a toner which is excellent in blocking resistance and does not deteriorate in developability even when left for a long time.

The present invention can provide a toner 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 that achieves 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 endothermic peak portion of a DSC curve at the time of temperature rise.

FIG. 4 is a diagram showing an endothermic peak portion of a DSC curve at the time of temperature rise.

FIG. 5 is a diagram showing an endothermic peak portion of a DSC curve at the time of temperature rise.

FIG. 6 is a diagram showing an endothermic peak portion of a DSC curve at the time of temperature rise.

FIG. 7 shows the DS of the wax a according to the present invention when the temperature is raised.
It is a figure showing a C curve.

FIG. 8 shows the DS of the wax a according to the present invention when the temperature is lowered.
It is a figure showing a C curve.

FIG. 9 shows the DSC of wax f (comparative example) during temperature rise
It is a figure showing a curve.

FIG. 10 shows the DS of wax f (comparative example) when the temperature is lowered.
It is a figure showing a C curve.

FIG. 11 is a schematic explanatory view showing a specific example of a fixing device for performing the heat fixing method of the present invention.

FIG. 12 is a diagram illustrating an example of a developing device used in a non-magnetic one-component developing method.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 heating element 2 fixing film 3 drive roller 4 driven roller 5 pressure roller 6 transfer material 7 toner 8 entrance guide 9 resistive material 10 alumina substrate 11 detection element 12 photoconductor (latent image holder) 13 developer carrier 14 hopper 15 Developer supply roller 16 Developer application roller 17 Toner (developer)

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masashi Jimbo 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Tsutomu Onuma 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (58) Investigated field (Int.Cl. ⁶ , DB name) G03G 9/08

Claims (4)

(57) [Claims] 1. A supply roller for supplying toner to a toner carrier is pressed against said toner carrier at a non-zero contact pressure and rotates at a non-zero speed. Contains at least a binder resin and a hydrocarbon wax used in a non-magnetic one-component developing type developing device in which a toner coating blade provided on the downstream side is pressed against the toner carrier with a non-zero contact pressure. In the non-magnetic one-component toner, the hydrocarbon wax has the following characteristics. In a DSC curve measured by a differential 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 the endothermic peak is in the range of 50 to 90 ° C., and there is at least one endothermic peak P _{1 in} the region of the temperature of 90 to 120 ° C. of peak temperature ± peak P ₁ 9
A non-magnetic one-component toner which satisfies a maximum exothermic peak when the temperature falls within a range of ° C. 2. The DSC curve of the non-magnetic one-component toner measured by a differential scanning calorimeter shows that the
The onset temperature at the first endothermic peak appearing at or above 100 ° C. is 105 ° C. or less, and the endothermic peak temperature is 100 to 1
A non-magnetic one-component toner having a temperature in the range of 20 ° C. and a heat generation peak temperature in the range of 90 to 115 ° C. with respect to a heat generation peak at the time of cooling. 3. DS measured by a differential scanning calorimeter
In the C curve, regarding the endothermic peak at the time of temperature rise and the exothermic peak at the time of temperature decrease, the onset temperature of the endothermic peak is 50 to 9%.
0 in the range of ° C., there is at least one endothermic peak P ₁ in the region of the temperature 90 to 120 ° C., there is a maximum exothermic peak at the time of cooling in the range of endothermic peak temperature ± 9 ° C. peak P _1, characteristic Fixing a toner image formed of a non-magnetic one-component toner containing a hydrocarbon wax and a binder resin to a transfer material by a contact heating fixing means. 4. DSC measured by a differential scanning calorimeter
In the curve, the onset temperature at the first endothermic peak appearing at 80 ° C. or more at the time of temperature rise is 105 ° C. or less,
The endothermic peak temperature is in the range of 100 to 120 ° C., and the exothermic peak temperature is 90 to 115
A heat fixing method comprising fixing a toner image formed of a non-magnetic one-component toner satisfying a temperature range of ℃ to a transfer material by a contact heat fixing unit.