JP2003035971A - Oilless toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which adjusts its softening point, melting point, viscosity and dielectric property by utilizing properties of an olefin polymer having a cyclic structure, extends an anti-offsetting temperature range to both high temperature and low temperature sides, improves fixability in high-speed copying as well as fixability at low temperature and low pressure, has good transparency and is suitable even for color copying by selecting the ratio between monomers in a copolymer of an olefin polymer, molecular weight, molecular weight distribution, a hybrid polymer, a blend and additives. SOLUTION: The oilless toner is manufactured by mixing a cycloolefin resin, a wax and a resin having a segment containing a double bond in its structure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic toner, and more particularly to an oilless toner which is mainly composed of a cyclic olefin resin and which has a good fixing property and which hardly causes an offset. Further, the present invention is a toner that can be widely applied to copiers, printers, fax machines, color copiers, color laser printers, electrophotographic high-speed printers and the like that use a heating roller type fixing device, 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 image with excellent fixability, toner spent prevention effect and transparency. In particular, a temperature range where the so-called offset phenomenon does not occur (hereinafter referred to as non-offset temperature range) is sufficiently secured,
Moreover, the present invention relates to a toner excellent in high-speed fixing property.

[0002]

2. Description of the Related Art Due to rapid technological innovation, there has been an increasing demand for a copy image which is excellent in fixability and which can prevent an offset phenomenon from occurring in electrophotographic copying machines and printers.

For example, International Publication WO98 / 2978.
No. 3, in order to prevent the offset phenomenon, an olefin polymer having the above-mentioned cyclic structure and a high viscosity is selected as a binder for toner, and further, amide wax, carnauba wax, higher fatty acid and its ester, higher It has been proposed to use a wax selected from fatty acid metal soap, partially saponified higher fatty acid ester, higher aliphatic alcohol, polyolefin wax, and paraffin wax, but the non-offset range is 30 to 40 ° C. Not at all.

Further, Japanese Unexamined Patent Publication No. 2000-066438 proposes a combination of polar wax and nonpolar wax, but unsatisfactory results have been obtained with respect to fixing of Teflon (registered trademark) roller.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems by selecting the ratio of the monomers to each other in the copolymer of the olefinic polymer, the molecular weight, the molecular weight distribution, the hybrid polymer, the blend and the additives. By adjusting the softening point, melting point, viscosity, and dielectric properties by utilizing the properties of olefinic polymers with a cyclic structure, the non-offset temperature range is expanded to both high and low temperature sides, and the fixability during high-speed copying is improved. It is an object of the present invention to provide a toner having improved transparency, improved fixability at low temperature and low pressure, and having good transparency and suitable for color copying.

[0006]

The above object of the present invention can be achieved by the following means. According to claim 1, in a system in which a cyclic olefin resin and a wax are mixed and used, a toner obtained by mixing the system with a resin having a segment containing a double bond in the structure is the main feature. .

Secondly, the toner according to claim 1 is characterized mainly in that a resin having a cyclic olefin and a double bond as a segment, that is, a so-called polydiene resin is used in combination with a wax.

Thirdly, the toner according to claim 1 or 2 is characterized mainly in that the mixing ratio of the cyclic olefin resin and the resin having a double bond in the structure is 100: 3 to 5: 100. To do.

Fourthly, the toner according to claim 1, 2 or 3 is characterized mainly in that the resin having a double bond is cyclized polyisoprene or cyclized polybutadiene.

Fifth, in the toner according to claim 1, 2, 3 or 4, the composition ratio of wax to resin is 30:10.
The main feature is that it is 0 to 100: 3.

Sixth, the toner according to claim 1, 2, 3, 4 or 5 is characterized mainly in that the wax used has a penetration of 40 or less at 25 ° C.

Seventh, the toner according to the first, second, third, fourth, fifth or sixth aspect is, in particular, an ester such as carnauba, candelilla, montan, rice, espart, caster or an acid wax. The main feature is that there is.

Eighth, the toner according to claim 1, 2, 3, 4, 5, 6 or 7 contains 1 to 20% of wax, particularly paraffin, olefin, microcrystalline, or an oxidized wax thereof. Is the main feature.

Ninth, claims 1, 2, 3, 4, 5, 6,
The toner of 7 or 8 has a wax melt viscosity of 15
The main feature is that it is 1 to 10,000,000 c poise at 0 ° C.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. The present inventors have found the present invention after verifying the prior art and clarifying the problems. Hereinafter, the verification results of the prior art will be described, and then the present invention will be described.

(Preliminary Experiment / Verification of Prior Art) As a cyclic olefin which is a constituent component of the toner of the present invention, a cyclic olefin manufactured by Ticona Gezelshaft Mitt Beschlenktel Haftung was used as a sample. However, it is not limited to the cyclic olefin produced by the manufacturer. All cyclic olefins falling within the category of so-called conventional petroleum resins can be used in the present invention.

Actually, the cyclic olefin resin used in the experiment is described in detail in JP-A-2000-066438.

The olefin polymer having a cyclic structure as a binder resin has 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
Lower alkenes such as α-olefins such as ethylene, propylene and butylene (acyclic olefins in a broad sense)
And a cyclic and / or polycyclic compound having at least one double bond and having 3 to 17, preferably 5 to 12 carbon atoms, such as norbornene, tetracyclododecene, dicyclopentadiene, and cyclohexene (cyclic (cyclo (cyclo ) Olefin), particularly preferably a copolymer with norbornene or tetracyclododecene, which is colorless and transparent and has a high light transmittance.

The olefin polymer having a cyclic structure is used as a catalyst for, for example, a metallocene catalyst, a Ziegler catalyst and a metathesis polymerization, that is, a double bond opening and a ring opening polymerization reaction. It is a polymer obtained by the used polymerization method. Examples of synthesizing an olefin polymer having this structure are JP-A-5-339327 and JP-A-5-92.
No. 23, JP-A-6-271628, European Patent Application Publication (A) 203799, No. 4
No. 07870, No. 283164, No. 156464, and Japanese Unexamined Patent Publication No. 7-253315.

According to these, one of the above cyclic olefins is
More than one type of monomer, optionally one of the above acyclic olefin-monomers, and -78 to 150 ° C, preferably 20 to 80 ° C and a pressure of 0.01 to 64 bar and a cocatalyst such as aluminoxane and for example zirconium or hafnium. Obtained by polymerizing in the presence of a catalyst consisting of at least one metallocene. Other useful polymers are disclosed in European Patent Application Publication (A) No. 3172.
No. 62, and hydrogenated polymers and copolymers of styrene and dicyclopentadiene can also be used.

Since the metallocene catalyst is activated in a state where the metallocene catalyst is dissolved in an inert hydrocarbon such as an aliphatic or aromatic hydrocarbon, for example, the metallocene catalyst is dissolved in toluene and pre-activation and reaction are performed in a solvent. Be seen. Important properties of the olefin polymer having a cyclic structure are softening point, melting point, viscosity, dielectric property, non-offset temperature range and transparency. These can be advantageously adjusted by the selection of the monomer / comonomer, ie the ratio of the monomers in the copolymer, the molecular weight, the molecular weight distribution, the hybrid polymer, the blend and the additives.

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 the desired cyclic structure, and is preferably 50: 1 to 1:50. And particularly preferably adjusted to 20: 1 to 1:20.

For example, when a copolymer component is charged with two kinds of compounds, ie, ethylene as an acyclic olefin and norbornene as a cyclic olefin and reacted, a glass transition point of an olefin polymer having a cyclic structure of a reaction product. (Tg) is greatly influenced by these charging ratios, and when the content of norbornene is increased, Tg also tends to increase. For example, the norbornene content is about 60% by weight.
If it is set, Tg will be about 60-70 degreeC. Physical properties such as number average molecular weight are adjusted as known from the literature.

The resin actually used as a sample of the present invention is an olefin-based polymer having a colorless and transparent cyclic structure with high light transmittance, and has the following low viscosity (low molecular weight) polymer or polymer fraction ( a) and high viscosity (high molecular weight)
Or a polymer fraction (b). That is, the olefin-based polymer having a cyclic structure may be a mixture of the polymer (a) and the polymer (b), or a polymer having a peak having one molecular weight distribution and a number average molecular weight of less than 7500. 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 the peaks having a number average molecular weight of less than 7500 And the polymer fraction with other peaks is 75
It may have a number average molecular weight of 00 or more.

The olefinic polymer having a cyclic structure is obtained from a low viscosity (low molecular weight) polymer or polymer fraction (a) and a high viscosity (high molecular weight) polymer or polymer fraction (b). As a result, the non-offset temperature range spreads to both high and low temperature sides,
This is because the toner fixability during high-speed copying is improved and the fixability at low temperature and low pressure is simultaneously improved.

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 has a number average molecular weight of less than 7,500, preferably 1,000. ~ 7,
Less than 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 4,000 to less than 15,000; intrinsic viscosity (i.
v .; Intrinsic viscosity at 135 ° C. when 1.0 g of the polymer is uniformly dissolved in 100 mL of decalin) is less than 0.25 dl / g; Glass transition point (Tg) is preferably less than 70 ° C.

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; and an intrinsic viscosity ( iv)
It is 0.25 dl / g or more.

Further, the content of the component b is less than 50% by weight, preferably 5 to 35% by weight, based on the whole binder resin. The component b imparts structural viscosity to the toner, thereby improving the offset prevention effect and the adhesiveness to the substrate to be copied such as paper and film, but when the content is 50% by weight or more, the uniform kneading property becomes extremely high. And deteriorates toner performance. In other words, it becomes difficult to obtain a high-quality image, that is, a clear image having high fixing strength and excellent heat response, and mechanical grindability is deteriorated, so that it becomes technically difficult to obtain a particle size required for the toner.

The term "polymer or polymer fraction" as used herein means that each polymer before mixing means an olefin polymer having a cyclic structure composed of a mixture of different components such as various number average molecular weights. Component, otherwise, refers to a polymer segment obtained by fractionating the final synthetic product by a suitable means such as GPC. When these polymer fractions are monodisperse or close to monodisperse, the number average molecular weight (Mn) of 7500 means the weight average molecular weight (M
w) corresponds approximately to 15000.

The low viscosity component a constituting the olefin polymer having a cyclic structure contributes to widen the non-offset temperature region to the low temperature side, and conversely, the high viscosity component b contributes to the high temperature side. To do. In order to more effectively widen the non-offset temperature range to the high temperature side, the presence of the highly viscous component b having a number average molecular weight of 20,000 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 part by weight or more,
Particularly, 5 to 100 parts by weight is preferable. If both are less than 0.5 parts by weight, it tends to be difficult to obtain a practical wide non-offset temperature range.

The high viscosity (high molecular weight) / low viscosity (low molecular weight) of the olefin polymer having a cyclic structure is the number average molecular weight (Mn), the weight average molecular weight (Mw),
Since it has an intrinsic viscosity (iv), Mw / Mn, which indicates the degree of dispersion of the molecular weight distribution, is as small as 1 to 2.5. Therefore, it is possible to produce a toner having a fast heat response and a high fixing strength because it is monodisperse or nearly monodisperse. The toner can be fixed at a low temperature and a low pressure, and it contributes to the storage stability of the toner, the spent toner property, the uniformity of the charge amount distribution, and the electrical stability which shows a constant charging / discharging efficiency. Here, in particular, when the low-viscosity polymer or polymer fraction is monodisperse or close to monodisperse, it is preferable because the toner exhibits excellent heat response such as instantaneous melting and solidification behavior.

Further, since the olefin polymer having a cyclic structure is colorless and transparent and has a high light transmittance, for example, the azo pigment "Permanent Rubin F6B" (manufactured by Clariant Co., Ltd.) is added to sufficiently After kneading, it was confirmed that a sheet formed by a press machine has excellent transparency, and thus it can be sufficiently applied to a color toner. Further, the olefin polymer has a very small heat of fusion when measured by the DSC method (differential scanning calorimetry), and it can be expected that the energy consumption for fixing the toner is significantly reduced.

By modifying the olefinic 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, it is possible to improve the compatibility with other resins and the dispersibility of the pigment in the toner. By introducing such a carboxyl group, it is possible to improve the adhesiveness of the toner with respect to the base material to be copied such as paper or film, and increase the fixing property.

The method of introducing the carboxyl group is preferably a two-step reaction method in which an olefin polymer having a cyclic structure is first prepared and then the carboxyl group is introduced. There are at least two methods of introducing this carboxyl group. One is to oxidize an alkyl group such as a methyl group at the end of the polymer into a carboxyl group by a melt air oxidation method. However, in this method, in the case of an olefin-based polymer having a cyclic structure synthesized by a metallocene catalyst, there is almost no branching, and therefore it is difficult to introduce many carboxyl groups.

Specifically, the graft ratio is preferably 1 by weight ratio with respect to the olefin polymer having a cyclic structure.
To 5% by weight, particularly preferably 3 to 5% by weight, maleic anhydride, acrylic acid or methacrylic acid is added to t-.
A carboxyl group is introduced by graft polymerization using a peroxide such as butanol peroxide as an initiator. 1% by weight
If it is less than the effect of improving the compatibility described above is not sufficient,
On the other hand, if it exceeds 5% by weight, intermolecular crosslinking occurs in the olefin polymer, the molecular weight increases, and the kneading property and pulverizability become impractical. In addition, an extreme yellow discoloration occurs and devitrification occurs, so colorless transparency is required. It tends to be unsuitable for color toners. Similar improvements can be realized by introducing a hydroxyl group and an amino group by a known method.

Further, in order to improve the fixing property of the toner, a cross-linking structure can be introduced into the olefin polymer having a cyclic structure. One of the methods for introducing this crosslinked structure is
During the polymerization of the olefin-based polymer, a terpolymer is obtained by adding a diene monomer such as cyclopentadiene, cyclohexadiene, norbornadiene, tetracyclododecadiene, or butadiene together with the acyclic olefin and the cyclic olefin. By this method, the olefin-based polymer has an active terminal even without a crosslinking agent,
By a known chemical reaction such as oxidation or epoxidation, or by adding a cross-linking agent, it has a cross-linked structure and is functionalized. As another method, a metal such as zinc, copper, or calcium is added to the above-mentioned olefin polymer having a cyclic structure having a carboxyl group introduced, and then mixed and melted with a screw or the like, and the metal is used as fine particles in the polymer. It is also possible to give a crosslinked structure by dispersing it into an ionomer.

The ionomer technology itself discloses a terpolymer of ethylene containing a carboxyl group which can be partially or fully neutralized to form the divalent metal salt for the purpose of, for example, toughness (US Pat. Patent No. 4693941
No. 6-300348,
For the same purpose, a polyester resin molded product containing an ionomer of an unsaturated carboxylic acid is added to about 20 to 8 of its carboxylic acid group.
It is also reported that 0% is neutralized with zinc, cobalt, nickel, aluminum or copper (II).

Other components constituting the binder resin are as follows. As the binder resin, a resin component other than the above-mentioned olefin polymer having a cyclic structure can be blended. For example, poly (bisphenol-A)-
Polyester resin such as terephthalate, epoxy resin,
Olefin resins other than olefin polymers having the above cyclic structure such as ethylene / propylene copolymers; vinyl acetate resins such as vinyl acetate resins and ethylene / vinyl acetate copolymers; acrylic resins such as styrene-acrylic resins There is one or a mixture of two or more of each of the above polymers or a hybrid polymer.

In this case, the ratio of the olefinic polymer having a cyclic structure to the other resin in the binder resin is preferably 1 when the binder resin is 100 parts by weight as a whole.
To 100 parts by weight, the latter is 99 to 0 parts by weight, more preferably the former is 20 to 90 parts by weight and the latter is 80 to 10 parts by weight, particularly preferably the former is 50 to 90 parts by weight and the latter is 5 parts by weight.
It is 0 to 10 parts by weight. 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.

If a resin made on the basis of such a concept is used and a wax is appropriately selected, a good toner without offset should be obtained. Therefore, when actually using the cyclic olefin resin thus obtained as a toner, a wax having a melting point of 60 ° C. to 80 ° C. is mixed to obtain an oilless toner in order to obtain offset resistance to the fixing roller. did. But as a matter of fact Carnauba,
Even if a relatively polar wax such as a fatty acid amide or polyethylene oxide is mixed with a cyclic olefin, the cyclic olefin resin dissolves very well in these waxes, resulting in an extreme decrease in viscosity and taking an effective rubber range. I couldn't. When a wax having a low polarity such as paraffin wax or polymerized olefin wax is used, the viscosity is further lowered and the effective rubber range cannot be obtained. Further, the same was true when these high polarity wax and low polarity wax were mixed and used. To make matters worse, when these waxes are added, not only does the viscosity of the toner decrease too much to keep the rubber region width, but also the toner becomes sticky and easily adheres to the fixing roller. This tendency occurs not only when the wax is mixed, but also when the so-called CCA is mixed, which is the biggest obstacle in using this cyclic olefin resin.

Even with such a toner, a roller coated with silicone oil or a silicone roller can barely escape the offset, but a system using these silicone oils and a system utilizing a silicone roller are barely available. The cost is high and it is a disadvantage to the user.

(Oilless toner according to the present invention) As a result of diligent studies on these problems, by mixing a resin having a segment containing a double bond in the structure with a cyclic olefin, it is possible to reduce these extreme viscosities. It has been discovered that stickiness can be prevented.

The hypothesis of this phenomenon is as follows. The resin having a double bond in the structure used in the experiment is a cyclized polyisoprene, which is completely soluble in the wax. However, in general, polyisoprene can disperse the wax but does not dissolve in the wax. From this, it is considered that the cyclized polyisoprene is completely dissolved in the wax due to the good affinity between the cyclic portion and the wax due to the partial cyclization of the polyisoprene structure. However, from the macroscopic point of view of the molecule, it can be said that the cyclized polyisoprene is dissolved in the wax.
Considering the cyclic part or the isoprene part of the cyclized polyisoprene separately, the cyclic part has a complete affinity, but the isoprene part has a double bond, and therefore is not compatible with a single bond wax. This appears as a difference from the cyclic olefin, and it is considered that there is no extreme decrease in viscosity or occurrence of tackiness. Therefore, when a resin having a segment containing a double bond in these structures and a cyclic olefin resin are mixed, an extreme decrease in viscosity and stickiness can be suppressed.

As a result of actually mixing various ratios to form a toner, the mixing ratio of the cyclic olefin resin and the resin having a double bond in the structure is 100: 3 to 5: 100, preferably 100: 5 to 10. : 100, more preferably 100:
10 to 20: 100, preferably 100: 20 to 30:
It has been found that an oilless toner having the above-mentioned performance can be produced when the value is 100. If the composition of the wax with respect to the resin component is 30: 100 to 100: 3, desired performance can be obtained, and preferably 50: 100 to 10.
0: 4, more preferably 100: 100 to 100: 6,
It was found that 100: 50 to 100: 10 is preferable.

In general, it has been found that the wax used should have a higher hardness. Further, it has been found that the penetration at 25 ° C. is preferably 40 or less, preferably 20 or less, more preferably 15 or less. Further, it has been found that the fluidity of a toner containing a large amount of wax tends to be poor, but the slippage between toner particles tends to be improved by using paraffin, polymerized olefin, and microcrystalline wax together. It has been found that a formulation of about 1 to 20% improves the slip between toner particles and does not adversely affect the properties of the wax / toner. In order to exhibit the oilless property of the toner of the present invention, the wax has a viscosity of 1 to 10,000,000 c.
It must be poise, and if it deviates from this range, the releasability tends to be incomplete.

As the resin having the double bond, for example, cyclized polyisoprene or cyclized polybutadiene can be adopted, but the resin is not limited to these. An example of the method for producing such a resin (method for producing a cyclized product) is as follows. According to the Fisher method, 5% of concentrated sulfuric acid was kneaded into the rubber and heated at 130 ° C. for 15 hours to obtain a cyclized rubber. Further, there is a method of cyclizing using an organic sulfonic acid as a cyclizing agent, tin chloride, iron chloride, non-metal halides and halogenated first and second stannous acids,
Various resinous plastics can be made. The prepared cyclized rubber (resinous plastic substance) undergoes an isomerization phenomenon as shown in the following chemical formula 1 due to the action of an oxidizing chemical, and the specific gravity increases and the degree of unsaturation decreases, so that the raw material has no property. It is a different substance. In the present invention, a different substance is obtained, and the cyclized rubber in the present invention can be made into a resin having a segment containing a double bond in the structure by such a method.

[0047]

[Chemical 1]

Further, polydiene resins such as homopolymers and copolymers of diene monomers may be adopted. As the polydiene resin, trans-1,4-
Poly-1,3-butadiene, cis-2-tert-butyl-1,4-poly-1,3-butadiene, trans-1
-Methoxy-1,4-poly-1,3-butadiene, transchloroprene, trans-1,4-polyisoprene, isotactic-trans-1,4-poly-1,
3-pentadiene, isotactic-trans-1,
4-poly-1,3-heptadiene, isotactic-
Trans-6-methyl-1,4-poly-1,3-heptadiene, isotactic-trans-1,4-poly-
1,3-hexadiene, isotactic-trans-
5-methyl-1,4-poly-1,3-hexadiene, trans-erythro-di-isotactic-2,5-poly-2,4-hexadiene, isotactic-trans-1,4-poly- Examples thereof include 1,3-octadiene and copolymers of monomer components of these polymers, but are not limited to these examples. Further, one or more of these compounds may be mixed and used.

The toner of the present invention may contain a sub-resin. Examples of the binder resin (sub-resin) include polystyrene, poly (p-chlorostyrene), homopolymers of styrene such as polyvinyltoluene, and substitution products thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, 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-
Styrene series such as vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Copolymer; polymethylmethacrylate, polybutylmethacrylate, polyvinyl chloride, polyvinyl acetate, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or fat Examples thereof include aromatic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and the like, which may be used alone or in combination, but are not particularly limited to these. Use by kneading and dispersing color pigments It may also be naturally used in combination of charge control agents.

Further, after pulverization, additives such as silica, titanium and strontium may be added to adjust the fluidity of the toner.

(Example) Next, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following examples. In the following description, "part by weight" will be referred to as "part" only.

Example 1 Cyclic olefin resin 60 parts Cyclized polyisoprene 25 parts Carnauba 15 parts Carbon black 10 parts CCA 1 part After kneading the toner of the above formulation with a two-roll for one hour,
It was crushed and classified, and a fixing test using a Teflon roller was performed.
As a result, fixing could be performed up to 220 ° C. without causing hot offset.

Example 2 Cyclic olefin resin 55 parts Cyclized polybutadiene 27 parts Montanoic acid ester 18 parts Carbon black 12 parts CCA 2 parts The toner of the above formulation was kneaded with a two-roll for 1 hour,
It was crushed and classified, and a fixing test using a Teflon roller was performed.
As a result, fixing could be performed up to 220 ° C. without causing hot offset.

Example 3 Cyclic olefin resin 65 parts Trans 1,4 polyisoprene 25 parts polymerized olefin wax 4 parts carnauba 6 parts carbon black 13 parts CCA 2 parts After kneading the toner of the above formulation with two rolls for 1 hour,
It was crushed and classified, and a fixing test using a Teflon roller was performed.
As a result, fixing could be performed 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.

Example 4 Cyclic olefin resin 55 parts Cyclized polyisoprene 20 parts Polystyrene 10 parts Carnauba 15 parts Carbon black 10 parts CCA 1 part After kneading the toner of the above formulation with a two-roll for 1 hour,
It was crushed and classified, and a fixing test using a Teflon roller was performed.
As a result, fixing could be performed up to 220 ° C. without causing hot offset.

Example 5 Cyclic olefin resin 55 parts Cyclized polyisoprene 20 parts Polyester 10 parts Carnauba 15 parts Carbon black 10 parts CCA 2 parts After kneading the toner of the above formulation with a two-roll for 1 hour,
It was crushed and classified, and a fixing test using a Teflon roller was performed.
As a result, fixing could be performed up to 220 ° C. without causing hot offset.

Example 6 Cyclic olefin resin 55 parts Cyclized polybutadiene 20 parts Polyacrylic ester resin 10 parts Carnauba 15 parts Carbon black 10 parts CCA 1 part After kneading the toner of the above formulation for 1 hour with two rolls,
It was crushed and classified, and a fixing test using a Teflon roller was performed.
As a result, fixing could be performed up to 220 ° C. without causing hot offset.

Comparative Example 1 Cyclic olefin resin 90 parts Carnauba 10 parts Carbon black 10 parts CCA 1 part The toner of the above formulation was kneaded with two rolls for 1 hour,
The melt viscosity was extremely lowered, and the tackiness was very high. In terms of handling of toner production, problems such as stickiness on a spatula or a roller and winding on a cold rolling roller were very serious. The toner thus kneaded in a difficult manner was crushed and classified, and a fixing test using a Teflon roller was conducted. As a result, not only hot offset occurred at 140 ° C. to 220 ° C., but also the fixing roller was easily wound around.

[0059]

According to the present invention, in a system in which a cyclic olefin resin and a wax are mixed and used, a resin having a segment having a double bond in the structure is mixed with the system. According to
By mixing a resin having a segment containing a double bond in the structure, it is possible to prevent an extreme decrease in viscosity and the occurrence of tackiness, and an olefin polymer having a cyclic structure is a low viscosity (low molecular weight) polymer. Alternatively, since it is composed of a polymer fraction and a high-viscosity (high molecular weight) polymer or polymer fraction, the non-offset temperature range is spread to both the high temperature and the low temperature side, resulting in improvement of toner fixing property during high-speed copying. , Improve the fixability at low temperature and low pressure at the same time.

According to the toner of claim 1, wherein the resin having a cyclic olefin and the double bond as a segment, that is, a so-called polydiene resin is used in combination with the wax. Can be prevented and the range of wax selection can be expanded.

The mixing ratio of the cyclic olefin resin of claim 3 to the resin having a double bond in the structure is 100: 3 to 5:10.
According to the toner of any one of claims 1 and 2, which is 0, it is possible to prevent an extreme decrease in viscosity and the occurrence of tackiness.

According to the toner of any one of claims 1 to 3, wherein the resin having a double bond in claim 4 is cyclized polyisoprene or cyclized polybutadiene. It is possible to prevent the occurrence of tackiness.

According to the toner of any one of claims 1 to 5, wherein the composition ratio of the wax to the resin of claim 5 is 30: 100 to 100: 3, the viscosity is extremely lowered and the tackiness is increased. Can be prevented, and a toner without offset can be obtained.

The wax used in claim 6 has a penetration of 40 or less at 25 ° C.
According to any of the toners described in 1 to 5, the higher the hardness of the wax, the better the performance.

In the seventh aspect, the types of wax are carnauba, candelilla, montan, rice, espart,
According to the toner of any one of claims 1 to 5, which is an ester such as caster or an acid wax, it is possible to prevent an extreme decrease in viscosity and the occurrence of tackiness, and to obtain a toner without offset. .

The electrophotographic toner according to any one of claims 1 to 7, characterized in that the wax of claim 8 is added with 1 to 20% of paraffin, olefin, microcrystalline, or an oxidized wax thereof. If so, the slip between the toners is improved.

The wax of claim 9 has a melt viscosity of 150 ° C.
In the toner according to any one of claims 1 to 8, which is 1 to 10,000,000 cpoise, the oilless property is exhibited and a good result is obtained.

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Claims (9)

[Claims] 1. An oilless toner produced by mixing a cyclic olefin resin, a wax, and a resin having a segment containing a double bond in its structure. 2. An oilless toner in which a resin having a cyclic olefin and a double bond as a segment is used in combination with a wax. 3. The oilless toner according to claim 1, wherein the mixing ratio of the cyclic olefin resin to the resin having a double bond in the structure is 100: 3 to 5: 100. 4. The oilless toner according to claim 1, wherein the resin having a double bond is cyclized polyisoprene or cyclized polybutadiene. 5. The composition ratio of resin and wax is 30:10.
It is 0-100: 3, It is characterized by the above-mentioned.
Oilless toner. 6. The oilless toner according to claim 1, wherein a penetration of the wax at 25 ° C. is 40 or less. 7. The oilless toner according to claim 1, wherein the wax is at least one of ester and acid wax such as carnauba, candelilla, montan, rice, espart, caster and the like. 8. The wax contains paraffin, olefin, microcrystalline and / or oxidized wax thereof as an additive, and the proportion of the additive in the wax is 1 to 20%. Item 7. An oilless toner according to items 1 to 7. 9. The oilless toner according to claim 1, wherein the wax has a melt viscosity of 1 to 10,000,000 c poise at 150 ° C.