JP4849850B2 - toner - Google Patents

Description

  The present invention relates to an electrophotographic toner used in a copying machine, a facsimile, a printer, and the like.

Conventionally, thermal fixing is often used for fixing toner.
As a principle of fixing, in general, in the case of heat fixing, the toner to be fixed must be softened or melted by the heat of the fixing machine, and further, the softened or melted toner receives pressure from the fixing machine and receives the fiber of the paper. The surface of the toner that has been indented or softened or melted is tacky, and therefore adheres with its adhesive strength. However, it is difficult to always maintain the set temperature because the fixing device is constantly exposed to overshoot at the time of temperature rise, temperature rise of the part not in contact with paper due to continuous paper passing of the part narrower than the width of the heating surface of fixing, In the worst case, the temperature may increase near 100 ° C. with respect to the set temperature.
Therefore, when such a temperature rise occurs, the viscosity of the conventional energy elastic resin is reduced corresponding to the temperature rise, the self-cohesion force of the toner is reduced, and hot offset or winding of the recording paper around the fixing heating surface is caused. Will occur.

In order to solve such a problem, in a toner using an energy elastic resin, a high molecular weight having a high viscosity is mixed even at a high temperature to prevent a decrease in viscosity.
However, there is a problem with this method. On the other hand, the toner blended with a polymer has a too high viscosity at a low temperature, the toner leveling becomes worse, the smoothness of the surface of the fixed toner is lost, and gloss is not easily produced. There was a problem that. For this reason, conventional color toners take a form that does not contain a high-viscosity high molecular weight so that the melt viscosity after heating is extremely low and can be self-leveled. Although this has been dealt with by coating, the remaining oil on paper has become a problem, and an immediate solution has been desired.

Conventional color toners have taken a form in which a high molecular weight having a high viscosity is not blended as much as possible so that the melt viscosity after heating is extremely low and can be self-leveled.
However, a toner using a resin having a low molecular weight and a Mw of about 10,000 does indeed have a remarkable decrease in melt viscosity, and it is easy to obtain a smooth surface and high gloss by self-leveling, but conversely, the viscosity rapidly increases as the temperature rises. The occurrence of hot offset and wrapping that are too low has been a problem. Conversely, when a large amount of polymer is formulated in the toner constituent resin, the viscosity of the toner does not decrease significantly with increasing temperature, but this time the viscosity does not decrease and the surface of the fixed toner is smoothed. The properties were not obtained and the gloss was low.

By the way, although not in the toner field, JP-A-2002-60449 of Cited Reference 1 and JP-A 2003-292719 of Cited Reference 2 describe a rubber component (soft Segment) and a constrained component (hard segment) that flows at high temperatures and prevents plastic deformation at normal temperatures and has a reinforcing effect on the rubber component. For example, in styrene-based elastomers, styrene blocks aggregate to form hard segments. Butadiene or isoprene block acts as a soft segment as a matrix, and olefin elastomers have an alloy structure in which rubber such as EPDM is dispersed in a resin such as PP. Because injection Thermoplastic processing such as is possible, but it is limited by the flow start temperature of the hard segment, and the upper limit temperature that can be used for thermoplastic elastomers is generally lower than that of crosslinked rubber. It is known to give a cross-linked structure to improve the properties of, for example, to cause elongation of a polyurethane-based elastomer molded product, to add a polyisocyanate-based cross-linking agent at the time of melting to form an allophanate cross-link or a biuret cross-link after molding, It is also known to obtain an elastomer having rubber elasticity comparable to that of a crosslinked rubber in a wide temperature range by post-crosslinking a thermoplastic elastomer comprising a silicon-based crosslinking material, a crosslinking catalyst and a hydrolyzable silane compound with moisture, On the other hand, methyl methacrylate is used as a hard segment, Acrylic acid block copolymer having a soft segment such as butyl crylate can be used as a thermoplastic elastomer because the acrylic block body is excellent in heat resistance, and by appropriately selecting the system constituting the block body, It gives a softer elastomer than other thermoplastic elastomers such as styrene-based block copolymers, and in this case, it is described that the acrylic block was known to have excellent heat resistance. However, these technologies are aimed at improving the toughness of molded products, and are not related to toner, they are in different fields, and there are no technical tips regarding anti-hot offset resistance measures in toner image fixing. Not given.
In order to meet the demands for colorization of images in recent years, toners, particularly color toners, must be easily meltable so as to sufficiently melt each other to form an intermediate color between the two toners after fixing. It is desirable that the surface is glossy and easily meltable. However, on the other hand, the occurrence of hot offset, which causes ghost images due to winding of copy sheets and transfer of residual toner images to the next run paper, is a major problem in toner image fixing in electrophotography. In order to prevent this, it is known to impart repellency to the surface of the intermediate transfer member by silicon oil or fluorohydrocarbon, etc., and to improve the contact angle (for example, Japanese Patent Application Laid-Open No. 2004-29207 of Patent Document 3). No. JP-A-2005-55500, etc.).
As for the improvement related to the binder resin of the toner, Japanese Patent Application Laid-Open No. 6-301239 discloses a styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene, which is a modified styrene block. Styrene block copolymers (SIS), or SBS hydrogenated styrene-ethylene butylene-styrene block copolymers (SES) or styrene-ethylene propylene-styrene block copolymers (SEPS) are disclosed. The block body is only one type of carbon black graft copolymer as a toner pigment (black toner colorant) with improved dispersibility in a binder resin.
The present inventors previously proposed a toner containing 10% by weight or more of cyclized rubber based on the total binder resin (Japanese Patent Application Laid-Open No. 2002-231411), and cyclized polyisoprene or cyclized polybutadiene. It is proposed that a polyester resin, an epoxy resin, or a styrene-acrylic resin may be further mixed with a resin obtained by mixing a resin component having a double bond as described above and a cyclic olefin polymer (see Patent Document 7). No. 2003-35971).
However, after that, it was found that the properties of the cyclized rubber used in the techniques described in Patent Documents 6 and 7 using the cyclized rubber deteriorate with time.
As a result of intensive investigation, the reason why the properties of the conventional cyclized cis 1,4-polyisoprene resin deteriorates is that the cyclized cis 1,4-polyisoprene resin is an entropy elastic resin, and this entropy elasticity attenuates over time. I came to the conclusion that it was the cause.
The reason why the entropy elasticity of the conventional cyclized cis 1,4-polyisoprene resin deteriorates while the cyclized cis 1,4-polyisoprene resin of the present invention exhibits strong entropy elasticity is investigated, but is still completely Not sure. However, in theory, oxygen in the air causes oxygen to penetrate into the double bond portion, and cis 1,4-polyisoprene is cleaved at the double bond portion or radicalized by oxygen attacking the double bond portion. It is reasonable to presume that the double bond is relatively reduced by re-polymerization.
In addition, by adding about 1% of an antioxidant such as IRGANOX 1010 (manufactured by Ciba Geigy) to the cyclized cis 1,4-polyisoprene early in the polymerization, the entropy elasticity of the cyclized cis 1,4-polyisoprene deteriorates. It can be inferred from the fact that this is suppressed.
For example, the resin shown in FIG. 4 and the resin shown in FIG. 5 are resins of the same lot, but FIG. 4 contains an antioxidant and FIG. 5 does not contain an antioxidant and has passed 3 months. is there. In addition, even if it was resin without an antioxidant and was preserve | saved by nitrogen substitution, even if 3 months passed, it did not change with viscoelasticity similar to FIG.
The present invention relates to a further improvement of the techniques described in Patent Documents 6 and 7, and particularly provides a technique suitable for color copying that can prevent hot offset well by applying these techniques.

JP 2002-60449 A JP 2003-292719 A JP 2004-29207 A JP 2005-55500 A JP-A-6-301239 JP 2002-231411 A JP 2003-35971 A

  Accordingly, an object of the present invention is to provide a toner that does not cause hot offset or wrapping without applying a large amount of oil and that can obtain a stable gloss.

As a result of studying to solve these problems, the present inventor previously proposed a toner containing 10% by weight or more of cyclized rubber based on the total binder resin (Japanese Patent Laid-Open No. 2002-231411), and Further, a polyester resin, an epoxy resin, or a styrene-acrylic resin may be further mixed with a resin obtained by mixing a resin component having a double bond such as cyclized polyisoprene or cyclized polybutadiene with a cyclic olefin polymer. This was proposed (Japanese Patent Laid-Open No. 2003-35971 of Patent Document 7).
However, after that, it was found that the properties of the cyclized rubber used in the techniques described in Patent Documents 6 and 7 using the cyclized rubber deteriorate with time.
As a result of intensive investigation, the reason why the properties of the conventional cyclized cis 1,4-polyisoprene resin deteriorates is that the cyclized cis 1,4-polyisoprene resin is an entropy elastic resin, and this entropy elasticity attenuates over time. I came to the conclusion that it was the cause.
The reason why the entropy elasticity of the conventional cyclized cis 1,4-polyisoprene resin deteriorates while the cyclized cis 1,4-polyisoprene resin of the present invention exhibits strong entropy elasticity is investigated, but is still completely Not sure. However, in theory, oxygen in the air causes oxygen to penetrate into the double bond portion, and cis 1,4-polyisoprene is cleaved at the double bond portion or radicalized by oxygen attacking the double bond portion. It is reasonable to presume that the double bond is relatively reduced by re-polymerization.
In addition, by adding about 1% of an antioxidant such as IRGANOX 1010 (manufactured by Ciba Geigy) to the cyclized cis 1,4-polyisoprene early in the polymerization, the entropy elasticity of the cyclized cis 1,4-polyisoprene deteriorates. It can be inferred from the fact that this is suppressed.
For example, the resin shown in FIG. 4 and the resin shown in FIG. 5 are resins of the same lot, but FIG. 4 contains an antioxidant, and FIG. 5 shows that three months have passed without containing the antioxidant. It should be noted that even if a resin without an antioxidant is stored after substitution with nitrogen, this deterioration mode may be the main cause because it remains the same viscoelasticity as in FIG. 4 even after 3 months. There is no doubt.
Furthermore, it has been found from the above examination that the effect of the invention is largely due to the entropy elasticity, and the effect is greatly influenced by the degree of the entropy elasticity.
Therefore, it is not sufficient to simply discuss the resin structure in the prior application, and the present invention is based on the fact that the degree of entropy elasticity of the resin that does not depend on thermal energy elasticity is very important.
That is, the above-mentioned problems are (1) “a toner using an entropy elastic resin, and the entropy elastic resin has a change in storage elastic modulus and loss elastic modulus within a temperature of 100 to 200 ° C. within 250 times each. toner ", characterized in that is of,
(2) “The toner according to item (1), wherein the entropy elastic resin is a thermoplastic elastomer”;
( 3 ) "The toner according to (1) above, wherein the entropy elastic resin has a Tg of 40 to 70 ° C",
( 4 ) "The toner according to any one of (1) to ( 3 ) above, wherein the entropy elastic resin exhibits two or more peaks in a molecular weight distribution spectrum", Is achieved.

Furthermore, as a result of investigations for improving the toner quality, the present inventor has succeeded in improving the performance of the toner by combining the energy elastic resin with the entropy elastic resin not depending on the thermal energy elasticity. This does not depend on thermal energy elasticity other than the combination of low and high molecular weights of ordinary energy elastic resins (thermal energy resins; resins that are hard at room temperature and whose hard segment is a factor that melts upon heating dominates viscoelasticity). By combining the entropy elastic resin, it is possible to finely adjust the heat characteristics and viscoelasticity of the toner, and it is possible to cope with a wide range of usage environments. Furthermore, since the entropy elastic resin has so-called rubber characteristics and is difficult to break, the pulverization productivity is not so good in producing the pulverized toner, but it can be improved by mixing the energy elastic resin.
Therefore, the above-mentioned problem is any one of the above-mentioned (1) to ( 4 ), characterized in that it is composed of a resin system mixed with ( 5 ) “energy elastic resin and entropy elastic resin” of the present invention. Toner described in ","
( 6 ) "The toner according to item ( 5 ), wherein the energy elastic resin has a viscosity lowering starting point of 100 to 140 ° C",
( 7 ) "The toner according to item ( 5 ), wherein the energy elastic resin has a Tg of 40 to 80 ° C",
( 8 ) "The toner according to item ( 5 ), wherein the energy elastic resin exhibits two or more peaks in a molecular weight distribution spectrum",
( 9 ) “A so-called petroleum resin is used as the energy elastic resin, a so-called cyclized cis-1,4 polyisoprene is used as the entropy elastic resin, and 20 as a low-molecular component in the content of the petroleum resin. The toner according to ( 5 ), wherein Mw of ˜95% is 4000 to 20000, and Mw as a polymer component corresponding thereto is 200,000 to 1,000,000.
( 10 ) "The toner according to item ( 9 ), which is a copolymer containing a styrene block in a cyclized cis-1,4-polyisoprene resin structure",
( 11 ) "The toner according to ( 9 ) or ( 10 ) above, wherein the cyclized cis-1,4-polyisoprene and styrene are diblock or triblock",
( 12 ) The above-mentioned ( 9 ) to ( 11 ), wherein the cyclized cis-1,4-polyisoprene resin structure has a styrene single chain in a polyisoprene weight ratio of 0.4 to 3%. The toner according to any one of the items
( 13 ) "The toner according to any one of ( 9 ) to ( 12 ) above, wherein the polystyrene block is shorter than the polyisoprene block",
( 14 ) "The toner according to any one of (1) to ( 13 ) above, which contains 1 to 40% wax as a constituent of the toner",
( 15 ) "Wax is a wax derived from plants such as carnauba, rice, esparto, candelilla, fossil such as montan, paraffin, polymerized olefin wax, ester, amide, ketone derivative Or a toner according to the item ( 14 ), which is a mixture of at least one of them.

  As will be apparent from the following detailed and specific invention, according to the present invention, a toner that does not cause hot offset or wrapping and has a stable gloss, particularly a toner suitable for color copying is provided. It has an extremely excellent effect.

Hereinafter, the present invention will be described in more detail.
[Entropy elastic resin]
The “entropic elasticity” in the present invention is different from elasticity due to internal plasticity such as plastomer, and a representative one is rubber. The property of this rubber is that the elasticity does not depend on temperature. The elasticity of rubber is such that a long polymer chain moves freely above the glass transition point and is relatively rounded rather than stretched. Probably because it is easy to take. Even if it is stretched or shrunk by external force, when the force is removed, it will return to its original state of motion and its shape will also return. Since the elasticity of rubber is not thermal energy, it is called entropy elasticity.
Such movement of polymer chains is also called “random walk” or “random walk” and is discussed in statistical mechanics.
This is shown in FIG.
(A) is a full state, (b) is a state in which it is completely pulled and stretched in a straight line. Assuming that both ends of the molecule are A and B, in the extended state (b), the shape that the molecule can take is 1. If both ends A and B are close as shown in (a), various forms can be taken as shown in (c) and (d). When the rubber molecules are shrunk, various shapes are possible and the degree of freedom is large.

Ω：自由度、Ｓ：エントロピー（熱量単位としての値はマイナスつまり吸熱）：比例定数ｋ：「ボルツマン定数」

Ω: degree of freedom, S: entropy (value as calorific value is negative, ie, endothermic): proportional constant k: “Boltzmann constant”

  Therefore, it can be said that entropy elasticity is so-called rubber elasticity, and is a property that deforms due to stress and returns to its original state when the stress is removed. Since the entropy elasticity hardly depends on the temperature, it can be said to be ideal for the formation of the rubber region of the toner. However, even in the case of entropy elasticity, the force that returns to the original state after fixing operation may be too large in the case of full entropy elasticity. Therefore, in the present invention, general energy elasticity (thermal It is also proposed how to use it in combination with a resin with a dynamic energy elasticity).

FIG. 2 shows a general classification of polymer resin materials.
When the polymer material is divided into an entropy elastic elastomer and a (thermal) energy elastic plastomer, the “entropic elastic resin” in the present invention is a rubber and a thermoplastic elastomer.
The “entropy elastic resin” in the present invention is “rubber” and “thermoplastic elastomer” in the same figure, and either may be used, but if it is rubber, it will be too elastic and will return to its original state after fixing. Is more preferable.

FIG. 3 is a diagram showing a simple molecular structure of rubber and thermoplastic elastomer.
A thermoplastic elastomer as an entropy elastic resin includes a hard portion (elliptical portion in the right figure) having a small temperature dependency, and is constrained by this portion and exhibits rubber elasticity. In addition, so-called rubber exhibits rubber elasticity by being constrained at a molecular crosslinking point (small circle portion in the left figure). Therefore, since the thermoplastic elastomer exhibits elasticity depending on the degree of freedom of the unconstrained portion, the temperature dependence of the viscoelasticity is small and large elasticity is obtained, and since it is not cross-linked, it can be deformed by pressure. The part that is not restrained is always in a liquid state with a stable viscosity, and this state is leveled with the viscosity of the energy elastic resin, so that it is possible to obtain a glossy toner having high leveling and no hot offset. .
In the present invention, a polymer resin that is a derivative of a cis-1,4-diene monomer can be preferably used as the “entropic elastic resin”.

The (thermal) energy elastic resins described later are the so-called “thermoplastic resin” and “partially crosslinked thermoplastic resin” in the figure, and are excluded because they do not undergo plastic deformation due to heat when they become thermosetting resins. Since the viscosity is determined by the size of the entangled molecular weight, the viscosity change due to the temperature increases, and when the temperature is high, the extreme viscosity is drastically reduced and hot offset occurs. At low temperatures, the viscosity is extremely high and not glossy.
As described above, as shown in the present invention, a combination of “energy elastic resin” and “entropy elastic resin” described later enables toner with high gloss and a wide offset resistance region.

The storage elastic modulus (E ′) and loss elastic modulus (E) of the “entropic elastic resin” in the present invention may be any elastic change within 100 times at a temperature of 100 to 200 ° C. FIG. 5 shows viscoelasticity in the state shown in FIG.
As shown in FIG. 4, the viscoelasticity is stable despite the temperature rise, and is close to a substantially constant value.

On the other hand, the entropy elastic resin having a somewhat (thermal) energy elastic component starts to decrease in viscosity at a high temperature portion as shown in FIG.
If the energy elastic component further increases, the viscosity drop at the high temperature part becomes significant as shown in FIG.
Further, when the energy elastic component is further increased, the viscosity at the high temperature part is too low and exceeds 100 times as shown in FIG. 7, which is not preferable.

  The Tg of the entropy elastic resin in the present invention is preferably 40 to 70 ° C., more preferably 50 to 65 ° C. in view of the storage stability of the toner. Further, since the entropy elastic resin molecular weight of the present invention is two or more, the entropy elasticity can be finely adjusted according to each temperature. Further, a plurality of entropy elasticity degrees may be used.

[Energy elastic resin]
Examples of the “energy elastic resin” that can be used in the present invention include the following.
For example, polyalkylene resins such as polyethylene and polypropylene, and chlorinated paraffin are not suitable as the “energy elastic resin” in the present invention. 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 An aromatic petroleum resin, an alkyd resin, a modified alkyd resin, and the like can be used. These can be used alone or in combination, but are not particularly limited thereto.
Specific petroleum resins include TOPAS COC (Ticona), Appel (Mitsui Chemicals), Zeonex (Nippon Zeon), Arton (JSR) and the like.

The “energy elastic resin” in the present invention preferably has a viscosity lowering starting point of 100 to 140 ° C. When the temperature exceeds 140 ° C., the fixing property is adversely affected. Yes, it may be undesirable. 110-130 degreeC is more preferable.
Comparison of storage elastic modulus of one example of “energy elastic resin” in the present invention (how to obtain “energy elastic resin” at both high and low temperatures; in the present invention, a dynamic viscoelasticity measuring apparatus manufactured by UBM, model Rheogel- E4000 was used, and a temperature change at a rate of 2 deg / min (in the present invention, storage modulus (E ′), loss modulus (E)) and Tg were not lowered, ) The storage elastic modulus and loss elastic modulus at 100 ° C. and 200 ° C. when obtained, or when there is no data up to 200 ° C., extrapolate two straight line portions at the bending point of the graph and store the elastic modulus at the intersection. 8 and 9 show the ratio, loss elastic modulus and temperature).

Furthermore, it is preferable that Tg of energy elastic resin is 40-80 degreeC.
In this case, there is a case where a problem occurs in the fixing property at 80 ° C. or higher, and a problem is caused in the storage property at 40 ° C. or lower. More preferably, it is 50-65 degreeC.

  Here, “Tg” in the present invention is measured by DSC-200 and TA-station-SSC-500 manufactured by SEIKO under the conditions of a heating rate of 10 deg / min and an excitation frequency of 100 Hz.

  The energy elastic resin in the present invention is preferably 2 or more peaks in the molecular weight distribution curve because the energy elastic amount can be adjusted as finely as the entropy elastic resin. Of course, two or more kinds of resins having different energy elasticity may be mixed.

Here, the molecular weight in the present invention is a value measured by the following measuring procedure. That is, it is based on styrene by GPC.
The sample was adjusted to cyclohexane at a concentration of 0.1%, and the mobile phase eluent was cyclohexane, and the measurement was performed at an injection amount of 10 μl, a flow rate of 1.0 ml / min, a column H type (Tosoh), and a column temperature of 35 ° C.

  Such physical properties of the “energy elastic resin” in the present invention are preferably measured, but not necessarily, before kneading with the “entropic elastic resin”. After kneading with the “entropic elastic resin”, a troublesome operation for separating components that may be in an inclusion state is required.

  In the present invention, although not limited to the following configuration, a so-called petroleum resin is used as the energy elastic resin, and a so-called cyclized cis-1,4-polyisoprene is used as the entropy elastic resin. The toner is prepared in a system in which 20 to 95% of Mw as a low molecular component in the resin content is 4000 to 20000, and Mw as a high molecular component corresponding to this is 200,000 to 1,000,000. Also good.

Furthermore, in this case, if the copolymer contains a styrene block in the structure of the cyclized cis-1,4-polyisoprene resin (entropy elastic resin), the styrene block in the polymer structure acts as a hard component and is more entropy elastic. It becomes easy to pull out.
Specifically, a structure in which cyclized cis-1,4-polyisoprene and styrene are diblock or triblock is preferable. Further, if the cyclized cis 1,4-polyisoprene resin structure contains 0.4 to 3% of a styrene single chain in a polyisoprene weight ratio, the hard part is more efficient and the performance is easily extracted. However, the polystyrene block must be shorter than the polyisoprene block, and if it is reversed, the entropy elasticity will be lost.

  In the present invention, it is possible to contain 1 to 40% of wax as a component of the toner, and the wax is derived from plants such as carnauba, rice, esparto, and candelilla, or derived from fossils such as montan and paraffin. Or a polymerized olefin wax, or an ester, amide, or ketone derivative, or a mixture of at least one of them can be used to bring out the toner release performance.

In addition, carbon black or a color pigment may be kneaded and dispersed in the resin component as described above if necessary, and naturally a charge control agent can be used in combination.
Further, after powdering, additives such as silica, titanium, strontium and the like may be added in order to adjust the fluidity of the toner.
As in Example 1 to be described later, a toner having clear entropy elasticity is very good as a toner characteristic, and if it is entropy elasticity as in Example 2, there is no problem. As in Comparative Example 1, the effect of entropy elasticity deterioration has not been expected at all, and the limit is the entropy elasticity of Example 3. Therefore, the entropy elasticity may be within a temperature range of 100 to 200 ° C., and the change in the storage elastic modulus and loss elastic modulus of the entropy elastic resin may be within 250 times, preferably within 150 times.

In order to describe the present invention in more detail, examples are shown below.
[Example 1]
90 parts of [entropic elastic resin 1 (cyclized rubber)] of the temperature-viscoelastic properties (measured with RBM, EBM manufactured by BM) shown in FIG. 4, 8 parts of carnauba wax having a melting point of 82 ° C., melting point of 150 ° C. 6 parts of polypropylene wax manufactured by Sanyo Chemical Co., Ltd., 10 parts of carbon black (Columbia Carbon) and 1 part of CCA (Zinc Salicylate manufactured by Hodogaya Chemical) were mixed and kneaded at 130 ° C. for 1 hour with a kneader [Toner 1 ] Were investigated.
FIG. 11 shows the storage elastic modulus of the manufactured [Toner 1].
A toner having the above viscosity was obtained, and the viscosity was stable up to 200 ° C., so that the gloss was stable at 5 to 20% without occurrence of hot offset.

The “entropy elastic resin 1” can be obtained as follows.
Anionic polymerization is mentioned as a method for synthesizing cis 1,4-polyisoprene.
Cyclohexane and isoprene monomer are mixed while being pressurized in an autoclave, and butyllithium is added as an initiator for reaction.
To stop the reaction, water was added to the solution and the resulting polymer was re-precipitated in methanol and collected by vacuum drying.

[Cyclization of cis 1,4-polyisoprene]
An example of a method for producing cyclized isoprene is as follows. In the Fisher method, 5% of concentrated sulfuric acid is kneaded into rubber and heated at 130 ° C. for 15 hours to obtain cyclized isoprene. In addition, there are methods using organic sulfonic acid, tin chloride, iron chloride, non-metal halides, halogenated first and second tin acids, etc. as cyclizing agents, and various resinous plastic materials can be produced. As shown in the following formula, an isomerization phenomenon is caused by the action of an oxidizing chemical, and the specific gravity is increased and the degree of unsaturation is decreased to obtain substances having completely different properties. It is possible to create it by such a method. The degree of cyclization of the resin thus prepared can be measured by an infrared absorption spectrum.
This [entropic elastic resin 1] has a polystyrene-equivalent molecular weight distribution spectrum as shown in FIG. 13, and has a weight average molecular weight (Mw) of 133,000 and Tg of 55 ° C.
The degree of cyclization can be determined by judgment based on the difference in the infrared absorption spectrum of isoprene before and after the cyclization reaction for synthesizing the cyclized isoprene-based polymer.

[Example 2]
90 parts of [entropic elastic resin 2 (cyclized rubber)] of the temperature-viscoelastic properties (measured with Rheogel-E4000 manufactured by UBM) shown in FIG. 5, 8 parts of carnauba wax having a melting point of 82 ° C., melting point of 150 ° C. 6 parts of a polypropylene wax manufactured by Sanyo Chemical Co., Ltd., 10 parts of carbon black (Columbia Carbon) and 1 part of CCA (Zinc Salicylate manufactured by Hodogaya Chemical) were mixed and kneaded at 130 ° C. for 1 hour with a kneader [Toner 2 ] Were investigated.
The storage modulus of the manufactured [Toner 2] has almost no change from the viscoelastic curve (FIG. 11) of [Toner 1] and has a stable viscosity up to 200 ° C., so that no hot offset occurs and gloss is 5 Stable with ~ 20%.

[ Reference Example 1 ]
[Entropy elastic resin 3 (cyclized rubber)] having the temperature-viscoelastic properties (measured with Rhegel-E4000 manufactured by UBM) shown in FIG. 6 and 8 parts of carnauba wax having a melting point of 82 ° C and Sanyo having a melting point of 150 ° C “Toner 3” obtained by mixing 6 parts of a polypropylene wax made by Kasei Co., Ltd., 10 parts of carbon black (made of Columbian Carbon) and 1 part of CCA (made of zinc salicylate by Hodogaya Chemical) and kneading at 130 ° C. for 1 hour with a kneader. The characteristics were investigated.
The storage elastic modulus of the produced [Toner 3] is shown in FIG.
A toner having a viscosity as shown in the figure was obtained, and the viscosity was stable up to 200 ° C., so that the gloss was stable at 5 to 30% without occurrence of hot offset.

[Comparative Example 1]
[Entropy elastic resin 4 (cyclized rubber)] having temperature-viscoelastic properties (measured with UBM Rheogel-E4000) shown in FIG. 7 and 8 parts of carnauba wax having a melting point of 82 ° C., Sanyo having a melting point of 150 ° C. “Toner 4” obtained by mixing 6 parts of polypropylene wax made by Kasei Co., Ltd., 10 parts of carbon black (made of Columbian Carbon) and 1 part of CCA (made of zinc salicylate by Hodogaya Chemical) and kneading at 130 ° C. for 1 hour with a kneader. The characteristics were investigated.
FIG. 15 shows the storage elastic modulus of the manufactured “Toner 4”.
A toner having a viscosity as shown in the figure was obtained, and the viscosity suddenly decreased from around 100 ° C., and the fixing roller was wound around the entire area up to 200 ° C.

[Example 3 ]
[Entropy elastic resin 5 (cyclized rubber)] (same as [Entropy elastic resin 1]) of the temperature-viscoelastic characteristics (measured with Rhegel-E4000 manufactured by BM) shown in FIG. (Temperature-viscoelastic properties of FIG. 10, “energy elastic resin A (see FIG. 16)” having a peak at Mw = 10000 and “energy elastic resin B (see FIG. 17)” having a peak at Mw = 500,000, respectively. 1: 9 mixed to give two peaks of molecular weight, Tg65 ° C) is mixed to make a total of 90 parts, and 8 parts carnauba wax with a melting point of 82 ° C and Sanyo with a melting point of 150 ° C 6 parts of a polypropylene wax made by Kasei Co., 10 parts of carbon black (made of Columbian Carbon) and 1 part of CCA (made of zinc salicylate by Hodogaya Chemical) It was characterized in obtained by kneading "Toner 5" between a kneader.
The storage elastic modulus of the manufactured “toner 5” is shown in FIG.
A viscous toner as shown in the figure was obtained, and the viscosity was stable up to 200 ° C., so that the gloss was stable at 5 to 20% without occurrence of hot offset.

Anionic polymerization is mentioned as a method for synthesizing the cis 1,4-polyisoprene used.
Cyclohexane and isoprene monomer are mixed while being pressurized in an autoclave, and butyllithium is added as an initiator for reaction.
To stop the reaction, water was added to the solution and the resulting polymer was re-precipitated in methanol and collected by vacuum drying.

[Cyclization of cis 1,4-polyisoprene]
An example of a method for producing cyclized isoprene is as follows. In the Fisher method, 5% of concentrated sulfuric acid is kneaded into rubber and heated at 130 ° C. for 15 hours to obtain cyclized isoprene. In addition, there are methods using organic sulfonic acid, tin chloride, iron chloride, non-metal halides, halogenated first and second tin acids, etc. as cyclizing agents, and various resinous plastic materials can be produced. As shown in the following formula, an isomerization phenomenon is caused by the action of an oxidizing chemical, and the specific gravity is increased and the degree of unsaturation is decreased to obtain substances having completely different properties. It is possible to create it by such a method. The degree of cyclization of the resin thus prepared can be measured by an infrared absorption spectrum.
This [entropic elastic resin 5] has a polystyrene-equivalent molecular weight distribution spectrum as shown in FIG. 13, and has a weight average molecular weight (Mw) of 133,000 and Tg of 55 ° C.
The degree of cyclization can be determined by judgment based on the difference in the infrared absorption spectrum of isoprene before and after the cyclization reaction for synthesizing the cyclized isoprene-based polymer.

[Example 4 ]
A copolymer containing a styrene block in a cyclized cis-1,4-polyisoprene resin structure. Specifically, a cyclized cis-1,4-polyisoprene and styrene are diblock and cyclized cis1,4-poly The isoprene resin structure contains a styrene single chain in an amount of 0.4 to 3% by weight ratio of polyisoprene, and the temperature-viscoelastic property “entropy elastic resin 6” shown in FIG. 19 (Mw = 111,000, Mw = 240,000 has two peaks of molecular weight, a weight average molecular weight (Mw) of 175,000, and Tg of 55 ° C. (The molecular weight of such two peaks is the [entropic elasticity of the molecular weight distribution spectrum shown in FIG. Resin A] and [Entropy Elastic Resin B] in the molecular weight distribution spectrum shown in FIG. 21 are obtained by mixing two types having different molecular weights), [Energy Elastic Resin 1], etc. 8 parts of carnauba wax with a melting point of 82 ° C, 6 parts of polypropylene wax with a melting point of 150 ° C, 10 parts of carbon black (made by Columbia Carbon), and 1 part of CCA (made of zinc salicylate Hodogaya Chemical) The properties of [Toner 6] obtained by kneading with a kneader at 130 ° C. for 1 hour were examined. As a result, the viscosity was stable up to 200 ° C., so that the gloss was stabilized at 5 to 20% without occurrence of hot offset.
In addition, while [Toner 5] of Example 4 showed a decrease in gloss at 190 to 200 ° C., stable gloss (FIG. 12) was obtained with [Toner 6] of Example 5.

Such an [entropic elastic resin 6] can be obtained as follows.
Anionic polymerization is mentioned as a method for synthesizing styrene-cis 1,4-polyisoprene.
Cyclohexane and styrene monomer are mixed while pressurizing in an autoclave, and butyllithium is added as an initiator to react. Since this reaction system is a living polymerization, the reaction ends are alive even when the styrene monomer is exhausted. At this point, when the isoprene monomer is added, the reaction occurs again, and the isoprene chain begins to grow to form a styrene block. .
In addition, since a small amount of styrene monomer remains during isoprene polymerization, a small amount of styrene monomer enters the isoprene chain.
The above is the case of the diblock, but in the case of the triblock, it is formed by adding the styrene monomer after the isoprene monomer is further lost, and thus a multistage repetitive copolymerization can be formed.
To stop the reaction, water was added to the solution and stirred. The resulting polymer was reprecipitated in methanol and collected by vacuum drying.

[Cyclization of cis 1,4-polyisoprene-styrene copolymer]
An example of a method for producing cyclized isoprene is as follows. In the Fisher method, 5% of concentrated sulfuric acid is kneaded into rubber and heated at 130 ° C. for 15 hours to obtain cyclized isoprene. In addition, there are methods using organic sulfonic acid, tin chloride, iron chloride, non-metal halides, halogenated first and second tin acids, etc. as cyclizing agents, and various resinous plastic materials can be produced. As shown in the following formula, an isomerization phenomenon is caused by the action of an oxidizing chemical, and the specific gravity is increased and the degree of unsaturation is decreased to obtain substances having completely different properties. It is possible to create it by such a method. The degree of cyclization of the resin thus prepared can be measured by an infrared absorption spectrum.
The degree of cyclization can be determined by judgment based on the difference in the infrared absorption spectrum of isoprene before and after the cyclization reaction for synthesizing the cyclized isoprene-based polymer.

[Example 5 ]
[Entropy elastic resin 7] (cyclized cis 1,4 polyisoprene-styrene copolymer) 50 parts, [Energy elastic resin 2] (TOPAS COC; manufactured by Ticona Corporation, weight average molecular weight (Mw) 10,000, Tg 65 ° C.) 40 Parts, 8 parts of carnauba wax (Toyo Petrolite), 6 parts of polypropylene wax (Sanyo Kasei), 10 parts of carbon black (Columbia Carbon), CCA (Zinc Salicylate from Hodogaya Chemical) One part was mixed and kneaded with a kneader at 130 ° C. for 1 hour to obtain “Toner 7”. The characteristics of “Toner 7” were examined. As a result, the viscosity was stable up to 200 ° C., so that the gloss was stable at 5 to 20% without occurrence of hot offset.

It is a schematic diagram explaining the behavior concept of "entropy elastic resin" in this invention. It is the figure which showed the classification | category of the general polymeric resin material. It is the figure which showed the characteristic on the simple molecular structure of "rubber" and "thermoplastic elastomer". It is the figure which showed the temperature-viscoelastic characteristic (storage elastic modulus and loss elastic modulus) of [Entropy elastic resin 1] of Example 1 (also used in Example 3 ). FIG. 6 is a diagram showing temperature-viscoelastic properties of [entropic elastic resin 2] used in Example 2. It is the figure which showed the temperature-viscoelastic property of [entropy elastic resin 3] used for the reference example 1. FIG. It is the figure which showed the temperature-viscoelastic property of [entropy elastic resin 4] used for the comparative example 1. FIG. It is the figure which showed the comparison (determination method) of the storage elastic modulus of energy elastic resin in this invention. It is another figure which showed the comparison (how to determine) of the storage elastic modulus of energy elastic resin in this invention. It is the figure which showed the characteristic of [energy elastic resin 1] of Example 3 use. 6 is a graph showing the storage elastic modulus of [Toner 1] used in Example 1. FIG. FIG. 6 is a diagram showing the gloss of [Toner 6] used in Example 4 . 1 is a molecular weight distribution spectrum diagram of [entropy elastic resin 1] (= [entropy elastic resin 5]) used in Examples 1 and 3. FIG. FIG. 6 is a graph showing a change in temperature-storage elastic modulus of [Toner 3] used in Reference Example 1 . 6 is a graph showing a change in storage elastic modulus of [Toner 4] of Comparative Example 1. FIG. 6 is a molecular weight distribution spectrum diagram of a raw material component [energy elastic resin A] of [energy elastic resin 1] for [toner 5] of Example 3. FIG. It is the molecular weight distribution spectrum figure of the raw material component [energy elastic resin B] of the same [energy elastic resin 1]. 6 is a graph showing a change in storage elastic modulus of [Toner 5] used in Example 3. FIG. FIG. 6 is a diagram showing the characteristics of [Toner 6] used in Example 4 . FIG. 6 is a molecular weight distribution spectrum diagram of a raw material component [entropy elastic resin A] of [entropy elastic resin 7] for the [toner 6]. It is the molecular weight distribution spectrum figure of the raw material component [entropy elastic resin B] of [entropy elastic resin 7] for the same [toner 6].

Claims (15)

A toner using an entropy elastic resin, wherein the entropy elastic resin has a change in storage elastic modulus and loss elastic modulus within a temperature of 100 to 200 ° C., each within 250 times. toner.   The toner according to claim 1, wherein the entropy elastic resin is a thermoplastic elastomer.   The toner according to claim 1, wherein the entropy elastic resin has a Tg of 40 to 70 ° C. The toner according to any one of claims 1 to 3 , wherein the entropy elastic resin exhibits two or more peaks in a molecular weight distribution spectrum. The toner according to any one of claims 1 to 4, characterized in that the energy elastic resin and entropy elastic resin is composed of mixed resin system. The toner according to claim 5 , wherein the energy elastic resin has a viscosity reduction starting point of 100 to 140 ° C. 6. The toner according to claim 5 , wherein the energy elastic resin has a Tg of 40 to 80 ° C. 6. The toner according to claim 5 , wherein the energy elastic resin exhibits two or more peaks in a molecular weight distribution spectrum. A so-called petroleum resin is used as the energy elastic resin, a so-called cyclized cis-1,4 polyisoprene is used as the entropy elastic resin, and 20 to 95% as a low molecular component in the content of the petroleum resin. 6. The toner according to claim 5 , wherein Mw is from 4,000 to 20,000, and Mw as a polymer component corresponding thereto is from 200,000 to 1,000,000. The toner according to claim 9 , which is a copolymer containing a styrene block in a cyclized cis-1,4-polyisoprene resin structure. The toner according to claim 9 or 10 , wherein the cyclized cis-1,4-polyisoprene and styrene are diblock or triblock. The toner according to any one of claims 9 to 11 , wherein the styrene single chain is 0.4 to 3% by weight ratio of polyisoprene in the cyclized cis-1,4-polyisoprene resin structure. The toner according to any one of claims 9 to 12, characterized in that the shorter polystyrene blocks from polyisoprene block. The toner according to any one of claims 1 to 13, characterized in that it contains 1-40% of a wax as a constituent of the toner. Whether the wax is a plant-derived wax such as carnauba, rice, esparto, candelilla, fossil such as montan, paraffin, polymerized olefin wax, ester, amide, ketone derivative, The toner according to claim 14 , wherein the toner is a mixture of at least one of them.

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