JP3945801B2 - Oilless toner - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a toner for electrophotography, and more particularly, to an oilless toner having a good fixability and having a low offset which is made of a cyclic olefin resin as a main material. Further, the present invention is a toner that can be widely applied to a copying machine, a printer, a fax machine, a color copying machine, a color laser printer, an electrophotographic high-speed printing machine, etc. using a heating roller type fixing machine, and a dry magnetic one-component system, When fixing a dry non-magnetic one-component system, a dry two-component system, a dry polymerization system, a liquid dry system and a liquid toner system developer, it is possible to form a clear and excellent image with excellent fixability, toner spent prevention effect, In particular, the present invention relates to a toner in which a temperature range in which a so-called offset phenomenon does not occur (hereinafter, referred to as a non-offset temperature range) is sufficiently ensured and has excellent high-speed fixing properties.
[0002]
[Prior art]
Under rapid technological innovation, there is an increasing demand for a copy image that is excellent in fixability and can prevent an offset phenomenon in an electrophotographic copying machine and a printer.
[0003]
In Japanese Patent Application Laid-Open No. 9-101631, a fixing structure is improved by selecting a high-viscosity olefin-based polymer having a cyclic structure as a binder resin for toner, and a melting point for preventing an offset phenomenon. It has been proposed to add wax at 60-170 ° C.
[0004]
In addition, in International Publication No. WO 98/29783, an olefin polymer having the above-mentioned cyclic structure and having a high viscosity is selected as a toner binder in order to prevent an offset phenomenon, and an amide wax, carnauba wax, It has been proposed to use a wax selected from fatty acids and esters thereof, higher fatty acid metal soaps, partially saponified higher fatty acid esters, higher aliphatic alcohols, polyolefin waxes, paraffin waxes, but the non-offset range is 30-40. It is in the range of ° C and is not practical.
[0006]
[Problems to be solved by the invention]
The object of the present invention is to solve the above-mentioned problems, and in an oilless toner for image formation, by mixing polyethylene glycol with a cyclic olefin resin, an extreme decrease in viscosity and occurrence of stickiness can be prevented, and a complete oilless toner can be obtained. An object of the present invention is to provide a toner having high offset resistance and suitable for color copying and the like.
[0007]
[Means for Solving the Problems]
The above object of the present invention is achieved by the following means. According to the present invention, the toner of claim 1 is an oilless toner containing a mixture of a cyclic olefin resin and polyethylene glycol , wherein the polyethylene glycol is incompatible and dispersed in the cyclic olefin resin. Features.
[0009]
Secondly, toner according to claim 1, the mixing ratio of the cyclic olefin resin and a polyethylene glycol 100: 1 to 100: for mainly characterized in that 3 is 0.
[0012]
Thirdly , the toner according to claim 1 or 2 further uses at least one selected from an ester selected from carnauba, candelilla, montan, rice, esparto, caster, or an acid wax. This is the main feature.
[0013]
Fourthly , the toner according to claim 1, 2 or 3 is mainly characterized in that at least one selected from paraffin, olefin, microcrystalline, or these oxidized waxes is used in combination of 1 to 20%. .
[0014]
Fifth , the toner according to claim 1, 2, 3 or 4 is mainly characterized in that the penetration of the wax used at 25 ° C. is 40 or less.
[0015]
Sixth , the toner according to claim 3 , 4 or 5 , wherein the wax has a melt viscosity of 1 to 10000000 centipoise at 150 ° C. ( c poise ) is a main feature.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below.
As the cyclic olefin which is a constituent component of the toner of the present invention, a cyclic olefin manufactured by Ticona Gesellshaft Mitt Beschlenktel Huffung was used as a sample. However, the cyclic olefin manufactured by the manufacturer is not limited.
Any cyclic olefin that falls within the category of so-called conventional petroleum resins can be used in the present invention.
[0017]
Actually, details of the cyclic olefin resin used in the experiment are described in JP-A-2000-0066438.
[0018]
The olefin polymer having a cyclic structure as the binder resin is a lower alkene having 2 to 12, preferably 2 to 6 carbon atoms, for example, an α-olefin such as ethylene, propylene and butylene (acyclic olefin in a broad sense). ) And cyclic and / or polycyclic compounds having 3 to 17, preferably 5 to 12 carbon atoms and having at least one double bond such as norbornene, tetracyclododecene, dicyclopentadiene, cyclohexene (cyclic ( Cyclo) olefin), particularly preferably a copolymer with norbornene or tetracyclododecene, which is colorless and transparent and has a high light transmittance.
[0019]
Olefin-based polymers having this cyclic structure include, for example, metallocene-based catalysts, Ziegler-based catalysts, and metathese polymerizations, that is, polymerization using a catalyst for double bond opening and ring-opening polymerization reactions. It is a polymer obtained by a legal method. Examples of the synthesis of the olefin polymer having this structure include JP-A-5-339327, JP-A-5-9223, JP-A-6-271628, European Patent Application Publication (A) No. 203799, No. 407870, No. 283164, No. 156464, JP-A-7-253315, and the like.
[0020]
According to these, one or more monomers of the above cyclic olefin are optionally combined with one of the above acyclic olefin-monomers and an aluminoxane at −78 to 150 ° C., preferably 20 to 80 ° C. and a pressure of 0.01 to 64 bar. It is obtained by polymerizing in the presence of a catalyst comprising at least one kind of a co-catalyst such as zirconium or hafnium. Other useful polymers are described in European Patent Application (A) 317262, and hydrogenated polymers and copolymers of styrene and dicyclopentadiene can also be used.
[0021]
Since the metallocene catalyst is activated in a state where the metallocene catalyst is dissolved in the inert hydrocarbon of the aliphatic or aromatic hydrocarbon, for example, the metallocene catalyst is dissolved in toluene, and the preliminary activity and reaction are performed in a solvent. The important properties of an olefin polymer having a cyclic structure are softening point, melting point, viscosity, dielectric properties, non-offset temperature range and transparency. These can be advantageously adjusted by the choice of monomer / comonomer, ie intermonomer ratio in the copolymer, molecular weight, molecular weight distribution, hybrid polymer, blends and additives.
[0022]
In addition, the reaction charge molar ratio of the acyclic olefin and the cyclic olefin can be varied in a wide range depending on the olefin polymer having a target cyclic structure, preferably 50: 1 to 1:50, particularly preferably. Is adjusted from 20: 1 to 1:20.
[0023]
For example, when the copolymer component is charged with a total of two compounds, ethylene as an acyclic olefin and norbornene as a cyclic olefin, the glass transition point (Tg) of an olefin polymer having a cyclic structure as a reaction product. Is greatly affected by these charging ratios, and when the norbornene content is increased, Tg tends to increase. For example, when the content of norbornene is about 60% by weight, Tg is about 60 to 70 ° C. Physical properties such as number average molecular weight are adjusted as known from the literature.
[0024]
The resin actually used as the sample of the present invention is an olefin polymer having a ring structure that is colorless and transparent and has high light transmittance, and the following low viscosity (low molecular weight) polymer or polymer fraction (a): It is characterized by comprising a high viscosity (high molecular weight) polymer or polymer fraction (b). That is, the olefin polymer having a cyclic structure may be a mixture of the polymer (a) and the polymer (b), or a polymer having a number average molecular weight of less than 7500 with one molecular weight distribution in the peak. Having a fraction and a polymer fraction having a number average molecular weight of 7500 or more, or having two or more peaks in the molecular weight distribution, and a polymer fraction having at least one of them has a number average molecular weight of less than 7500 The polymer fraction having other peaks may have a number average molecular weight of 7500 or more.
[0025]
The olefin polymer having a cyclic structure is composed of a low viscosity (low molecular weight) polymer or polymer fraction (a) and a high viscosity (high molecular weight) polymer or polymer fraction (b). This is because the non-offset temperature range extends to both the high temperature side and the low temperature side, so that the toner fixability at high speed copying is improved and the fixability at low temperature and low pressure is simultaneously improved.
[0026]
The polymer or polymer fraction (a) (hereinafter referred to as component a) has a number average molecular weight measured by GPC (gel permeation chromatography) in terms of polyethylene, and the number average molecular weight is less than 7,500, preferably less than 1,000 to 7,500 More preferably 2,000 to less than 7,500; weight average molecular weight less than 15,000, preferably 1,000 to less than 15,000, more preferably less than 4,000 to 15,000; intrinsic viscosity (iv; 1.0 g of the polymer was uniformly dissolved in 100 mL of decalin The intrinsic viscosity at 135 ° C) is less than 0.25 dl / g; the glass transition point (Tg) is preferably less than 70 ° C.
[0027]
The polymer or polymer fraction (b) (hereinafter referred to as component b) has a number average molecular weight of 7,500 or more, preferably 7,500 to 50,000; a weight average molecular weight of 15,000 or more, preferably 15,000 to 500,000; an intrinsic viscosity (iv) It is 0.25 dl / g or more.
[0028]
Furthermore, the content of the component b is less than 50% by weight, preferably 5 to 35% by weight of the entire binder resin. Component b imparts a structural viscosity to the toner, thereby improving the anti-offset effect and adhesion to a substrate to be copied such as paper or film. However, when the content is 50% by weight or more, the uniform kneading property is extremely high. The toner performance decreases and the toner performance is hindered. That is, it becomes difficult to obtain a high-quality, that is, a clear image having high fixing strength and excellent heat response, or it is technically difficult to obtain a particle size necessary for the toner due to a decrease in mechanical grindability.
[0029]
Here, the polymer or polymer fraction is a polymer component before mixing when the olefin polymer having a cyclic structure is composed of a mixture of different components such as various number average molecular weights, In other cases, it refers to a polymer segment obtained by fractionating the final synthesized product by an appropriate means such as GPC. Here, when these polymer fractions are monodispersed or close to monodispersed, the number average molecular weight (Mn) of 7500 corresponds to the weight average molecular weight (Mw) of about 15000.
[0030]
The low-viscosity component a constituting the olefin polymer having a cyclic structure contributes to widen the non-offset temperature range to the low temperature side, and conversely the high-viscosity component b contributes to widen to the high temperature side. In order to more effectively expand the non-offset temperature range to the high temperature side, the presence of a high-viscosity component b having a number average molecular weight of 20000 or more is preferable. When the total amount of the binder resin is 100 parts by weight, the contents of the components a and b constituting the olefin polymer are each 0.5 parts by weight or more, and particularly preferably 5 to 100 parts by weight. In both cases, if it is less than 0.5 parts by weight, a practical wide non-offset temperature range tends to be difficult to obtain.
[0031]
The high viscosity (high molecular weight) / low viscosity (low molecular weight) of the olefin polymer having a cyclic structure has the number average molecular weight (Mn), the weight average molecular weight (Mw), and the intrinsic viscosity (iv) as described above. Since the Mw / Mn indicating the degree of dispersion of the molecular weight distribution is as small as 1 to 2.5, it is possible to produce a toner having a fast heat response and a high fixing strength because it is close to monodispersion or monodispersion. In addition to being able to be fixed, it contributes to the storage stability of the toner, the spent toner properties, the uniformity of the charge amount distribution, and the electrical stability indicating the constant charging / discharging efficiency. Here, in particular, when the low-viscosity polymer or polymer fraction is monodispersed or close to monodispersed, it is preferable because it exhibits excellent heat response as a so-called toner such as instantaneous melting and solidification behavior.
[0032]
Further, since the olefin polymer having a cyclic structure is colorless and transparent and has high light transmittance, for example, after adding “Permanentorubin F6B” (manufactured by Clariant) as an azo pigment and kneading sufficiently. Since it was confirmed that the sheet formed by the press machine is also excellent in transparency, it can be sufficiently applied to color toners. In addition, the olefin polymer has a very low heat of fusion as measured by the DSC method (differential scanning calorimetry), and it can be expected that the energy consumption for fixing the toner is greatly reduced.
[0033]
By modifying the olefin polymer having a cyclic structure, the following toner can be improved. That is, by introducing a carboxyl group into an olefin polymer having a cyclic structure, the compatibility with other resins can be improved, and the dispersibility of the pigment in the toner can be improved. By introducing such a carboxyl group, it is possible to improve the adhesion of the toner to the substrate to be copied such as paper or film and to increase the fixing property.
[0034]
As a method for introducing a carboxyl group, a two-stage reaction method is preferred, in which an olefin polymer having a cyclic structure is first prepared and then a carboxyl group is introduced. There are at least two methods for introducing this carboxyl group. One is to oxidize an alkyl group such as a methyl group at the end of the polymer by a melted air oxidation method to form a carboxyl group. However, in this method, in the case of an olefin polymer having a cyclic structure synthesized with a metallocene catalyst, it is difficult to introduce many carboxyl groups because there is almost no branching.
[0035]
Specifically, the maleic anhydride, acrylic acid or acrylic acid is used so that the graft ratio is preferably 1 to 5% by weight, particularly preferably 3 to 5% by weight with respect to the olefin polymer having a cyclic structure. A carboxyl group is introduced by graft polymerization of methacrylic acid using a peroxide such as t-butanol peroxide as an initiator. If the amount is less than 1% by weight, the effect of improving the compatibility described above is not sufficient. On the other hand, if the amount exceeds 5% by weight, intermolecular crosslinking occurs in the olefin polymer, the molecular weight increases, and kneadability and grindability are impractical. In addition, since it exhibits extreme yellowing and devitrification, it tends to be unsuitable for color toners that require colorless transparency. A similar improvement can be realized by introducing a hydroxyl group or an amino group by a known method.
[0036]
Further, in order to improve the fixing property of the toner, a crosslinked structure can be introduced into the olefin polymer having a cyclic structure. One method for introducing this crosslinked structure is to add a diene monomer such as cyclopentadiene, cyclohexadiene, norbornadiene, tetracyclododecadiene, butadiene, etc. together with acyclic olefin and cyclic olefin during polymerization of the olefin polymer. By original copolymerization.
By this method, the olefin polymer has a terminal that shows activity without a crosslinking agent, and has a crosslinked structure by a known chemical reaction such as oxidation or epoxidation, or by adding a crosslinking agent, and is functionalized. Is done. As another method, a metal such as zinc, copper, or calcium is added to the olefin polymer having a cyclic structure into which the carboxyl group is introduced, and then mixed and melted with a screw or the like, and the metal is finely divided into the polymer. It is also possible to give a cross-linked structure by dispersing in an ionomer.
[0037]
The ionomer technology itself discloses ethylene terpolymers containing carboxyl groups that can be partially or fully neutralized to form divalent metal salts, eg, for the purpose of toughness (US Pat. No. 4,693,494). No. 6-500348 discloses, for the same purpose, a polyester resin molded article containing an ionomer of an unsaturated carboxylic acid containing about 20 to 80% of the carboxylic acid group of zinc, cobalt, nickel. Also reported are those neutralized with aluminum or copper (II).
[0038]
Other components that constitute the binder resin include the following. Other resin components other than the olefin polymer having the above cyclic structure can be blended as the binder resin. For example, an olefin resin other than an olefin polymer having the above cyclic structure such as a polyester resin such as poly (bisphenol-A) -terephthalate, an epoxy resin, an ethylene / propylene copolymer; a vinyl acetate resin, an ethylene / vinyl acetate copolymer There is a vinyl acetate resin such as a polymer; one kind selected from acrylic resins such as a styrene-acrylic resin, or a mixture or hybrid polymer of two or more of the above polymers.
[0039]
In this case, the use ratio of the olefin polymer having a cyclic structure in the binder resin and the other resin is preferably 1 to 100 parts by weight of the former and 100% by weight of the latter when the entire binder resin is 100 parts by weight. 99 to 0 parts by weight, more preferably 20 to 90 parts by weight of the former and 80 to 10 parts by weight of the latter, particularly preferably 50 to 90 parts by weight of the former and 50 to 10 parts by weight of the latter. If the proportion of the olefin polymer having a cyclic structure is less than 1 part by weight, it tends to be difficult to obtain a high-quality image.
[0040]
If a resin made based on this concept is used and a wax is appropriately selected, a good toner without offset should be obtained. Therefore, when actually forming a toner based on the cyclic olefin resin thus obtained, a wax having a melting point of 60 ° C. to 80 ° C. is mixed with an oilless toner in order to provide offset resistance to the fixing roller. did. However, as a matter of fact, even when relatively polar waxes such as carnauba, fatty acid amides, polyethylene oxide, etc. are mixed with cyclic olefins, the cyclic olefin resin dissolves very well in these waxes, causing an extremely low viscosity and effective. A large rubber zone width could not be obtained. In addition, when a low polarity wax such as paraffin wax or polymerized olefin wax is used, the viscosity is further lowered and an effective rubber width cannot be obtained. Furthermore, the same was true when these high polarity waxes and low polarity waxes were used in combination. To make matters worse, when these waxes are added, the viscosity of the toner is too low and the rubber zone width cannot be taken, and the toner becomes sticky and tends to adhere to the fixing roller. This tendency occurs not only when the wax is mixed, but also when so-called CCA is mixed, and this is the biggest obstacle to using this cyclic olefin resin.
[0041]
Even if such toner is used, a roller or silicon roller coated with silicone oil can barely escape offset, but a system using these silicone oils or a system using silicon rollers is expensive. This is a disadvantage to the user.
[0042]
Result of studying these problems intensively and found to be able to prevent these extreme viscosity reduction and tacky by mixing poly ethylene glycol instead of the wax added to the cyclic olefin. It is only a hypothesis to explain this phenomenon, but in general, polyethylene glycol structurally contains oxygen between ethylene units, and ethylene has an ether bond with this oxygen. Since the electronegativity of the oxygen to be formed is high, intramolecular polarization occurs and the polarity is high. Therefore, a resin having a structure that does not have a particularly high electronegativity atom in the molecule, such as a cyclic olefin, has a very low polarity, and the polarity is too different from that of polyethylene glycol. . Due to this difference in polarity, polyethylene glycol is not completely compatible with the cyclic olefin, and tries to take a dispersed form. When fixed, polyethylene glycol oozes out and oilless properties are exhibited. However, the compatibility of the polyethylene glycol and the cyclic olefin resin is better than the relationship between the conventional wax and styrene, or the acrylic ester resin and the polyester resin. Generally, the wax does not disperse if there is no pigment. In spite of this, polyethylene glycol can be easily dispersed in the resin even in the absence of a pigment or the like in the cyclic olefin resin.
[0043]
In this way, polyethylene glycol dispersed in the cyclic olefin resin while maintaining a certain degree of compatibility state is optimal as an oilless agent, and this appears as a difference from the case where the cyclic olefin and the wax are mixed, It is considered that there is no extreme decrease in viscosity or occurrence of stickiness. Therefore, when the cyclic olefin resin and polyethylene glycol are mixed, an extremely low viscosity and stickiness are suppressed, and a complete oil-less property is obtained.
[0044]
Further, the hydroxyl groups at both ends or at one end of polyethylene glycol can be modified to alkyl ether, alkyl ester, alkylphenyl ether, alkylphenyl ester or the like, and this modification can adjust the compatibility and dispersibility with the cyclic olefin resin. In addition, it is also possible to use wax together with polyethylene glycol. In particular, esters such as carnauba, candelilla, montan, rice, esparto, and caster, or acid wax can be used in combination.
When a large amount of wax is used, the fluidity of the toner tends to be deteriorated, but the effect of improving the sliding of the toner particle ring is expressed by using paraffin, olefin, microcrystalline, or these oxidized waxes in combination. This can be prevented by prescribing about 20%.
[0045]
Further, in order to exhibit the oil-less property of the toner of the present invention, the viscosity of the wax needs to be 1 to 10000000 cpoise, and if it is out of this range, the releasability tends to become incomplete.
[0046]
Examples of the subresin that can be used in the present invention include the following.
Examples of binder resins used for each toner include homopolymers of styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene and the like; styrene-p-chlorostyrene copolymers, styrene-propylene copolymers Polymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate Copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, Styrene-vinyl methyl ketone copolymer Styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc .; Methyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin , Aromatic petroleum resins, chlorinated paraffins, etc., which can be used alone or in combination, but are not particularly limited thereto, and carbon black and color pigments are kneaded and dispersed in these resins as necessary Of course, the charge control agent Combined use is also possible.
Further, after powdering, additives such as silica, titanium, strontium and the like may be added in order to adjust the fluidity of the toner.
[0047]
[Example]
Next, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples.
Example 1
Cyclic olefin resin 95 parts Polyethylene glycol 5 parts Carbon black 10 parts CCA 1 part The toner of the above formulation was kneaded in two rolls for 1 hour, then pulverized and classified, and a fixing test using a Teflon roller was performed.
As a result, fixing was possible up to 220 ° C. without causing hot offset.
[0048]
Example 2
Cyclic olefin resin 85 parts Polyethylene glycol 3 parts Carnauba 12 parts Carbon black 12 parts CCA 2 parts The toner of the above formulation was kneaded with two rolls for 1 hour, then pulverized and classified, and a fixing test using a Teflon roller was performed.
As a result, fixing was possible up to 220 ° C. without causing hot offset.
[0049]
Example 3
Cyclic olefin resin 85 parts Polyethylene glycol 5 parts Polymerized olefin wax 5 parts Carnauba 5 parts Carbon black 13 parts CCA 2 parts The toner of the above formulation is kneaded with two rolls for 1 hour, then crushed and classified, and a fixing test with a Teflon roller is performed. went.
As a result, fixing was possible up to 220 ° C. without causing hot offset.
In addition, the fluidity of the toner was improved compared to other toners, and a smooth image with less dust was obtained.
[0050]
Example 4
Cyclic olefin resin 83 parts Polyethylene glycol 7 parts Polystyrene 10 parts Carbon black 10 parts CCA 1 part The toner of the above formulation was kneaded with two rolls for 1 hour, then pulverized and classified, and a fixing test using a Teflon roller was performed.
As a result, fixing was possible up to 220 ° C. without causing hot offset.
[0051]
Example 5
Cyclic olefin resin 83 parts Polyethylene glycol 7 parts Polyester 10 parts Carbon black 10 parts CCA 2 parts The toner of the above formulation was kneaded with two rolls for 1 hour, then pulverized and classified, and a fixing test using a Teflon roller was performed.
As a result, fixing was possible up to 220 ° C. without causing hot offset.
[0052]
Example 6
Cyclic olefin resin 83 parts Polyethylene glycol 7 parts Polyacrylic ester resin 10 parts Carbon black 10 parts CCA 1 part The toner of the above formulation is kneaded with two rolls for 1 hour, then pulverized and classified, and a fixing test with a Teflon roller is performed. went.
As a result, fixing was possible up to 220 ° C. without causing hot offset.
[0053]
Comparative Example 1
Cyclic olefin resin 90 parts Carnauba 5 parts Polymerized olefin wax 5 parts Carbon black 10 parts CCA 1 part When the toner of the above formulation is kneaded with two rolls for 1 hour, the melt viscosity is extremely lowered, and it is very sticky. In terms of the preparation of the toner, problems such as stickiness to the spatula and the roller and winding around the cooling and rolling roller were very serious.
The toner thus kneaded and kneaded was pulverized and classified, and a fixing test using a Teflon roller was performed.
As a result, not only the hot offset was generated at 140 ° C. to 220 ° C., but also it was easily wound around the fixing roller.
[0054]
【The invention's effect】
An oilless toner comprising a mixture of the cyclic olefin resin and polyethylene glycol according to claim 1 , wherein the polyethylene glycol is incompatible and dispersed in the cyclic olefin resin. Since the polarities of cyclic olefin resin and polyethylene glycol are greatly different, they are optimal as oil-less materials, can prevent extreme viscosity drop and stickiness, and can improve offset resistance, color image characteristics, etc. .
[0056]
The toner according to claim 1 , wherein the mixing ratio of the cyclic olefin resin of claim 2 and polyethylene glycol is 100: 1 to 100: 30, and the extreme viscosity is within the mixing ratio within this range. It is possible to prevent the occurrence of lowering and stickiness and to obtain good oil-less characteristics.
[0059]
In particular carnauba of claim 3, candelilla, montan, rice, esparto, according to the toner according to claim 1 or 2, characterized in that further combination an ester or acid wax, such as castor, without offset wax Good performance is obtained.
[0060]
Especially paraffins according to claim 4, olefins, microcrystalline or according to any of the toners of claims 1-3, wherein the combination of these oxidized waxes 1-20%, extreme viscosity reduction or adhesive, Therefore, toner having no offset can be obtained.
[0061]
According to claim 1-4 or a toner for electrophotography according to penetration at 25 ° C. of wax used according to claim 5, characterized in that it is 40 or less, good enough hardness of the wax is high Performance is obtained.
[0062]
According to one of the toners of claims 1 to 5, wherein the melt viscosity of the wax according to claim 6, characterized in that a 1-10000000 Cpoise at 0.99 ° C., oilless property is exhibited good results .

Claims (6)

An oilless toner comprising a mixture of a cyclic olefin resin and polyethylene glycol , wherein the polyethylene glycol is incompatible and dispersed in the cyclic olefin resin . A cyclic olefin resin, the mixing ratio of polyethylene glycol 100: 1 to 100: The toner according to claim 1, characterized in that 3 is 0. In particular carnauba toner according to candelilla, montan, rice, esparto, to claim 1 or 2, characterized in that further in combination at least one selected from the ester or acid wax is selected from Custer. Paraffins, olefins, microcrystalline or the toner according to any one of claims 1 to 3, characterized in that for at least one of 1-20% 併 chosen from the oxidized wax. DOO toner according to any one of claims 1 to 4 penetration at 25 ° C. of wax used is characterized in that it is 40 or less. In the melt viscosity of the wax is 0.99 ° C., the toner according to any one of claims 3 to 5, characterized in that a 1 to 10,000,000 centipoise (cps).