Source: https://patents.google.com/patent/US5180649?oq=5251294
Timestamp: 2018-03-24 14:44:42
Document Index: 201847167

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US5180649A - Toner having crosslinkages and method of fixing same - Google Patents
Toner having crosslinkages and method of fixing same Download PDF
US5180649A
US5180649A US07611096 US61109690A US5180649A US 5180649 A US5180649 A US 5180649A US 07611096 US07611096 US 07611096 US 61109690 A US61109690 A US 61109690A US 5180649 A US5180649 A US 5180649A
US07611096
Hiroshi Yusa
Tsuyoshi Takiguchi
Koichi Tomiyama
Tetsuhito Kuwashima
A toner for developing electrostatic images is constituted from a binder resin, and a metal salt or a metal complex. Through the various interaction between the components, the toner is provided with unique viscoelastic properties including: a dynamic modulus G'120-200 at 120°-200° C. of 2×103 or higher to below 5×105 [dyne/cm2 ] as measured in the frequency range of 1×10-2 -1 (Hz); a loss modulus G"120-200 at 120°-200° C. of 2×103 or higher to below 5×105 [dyne/cm2 ] as measured in the frequency range of 1×10-2 -1 (Hz); a dynamic modulus G'200 at 200° C. and a frequency f satisfying an approximated linear relationship according to the least squares method of: logG'200 =a·log·f+log b, wherein a denotes a positive number of 0.25 or smaller and b denotes a constant; and a ratio (G'200)/(G'120) of below 0.25 wherein (G'200) denotes a dynamic modulus at 200° C. and (G'120) denotes a dynamic modulus at 120° C. respectively at a frequency of 1 (Hz).
JP-A 56-16144 has proposed a toner comprising a binder resin having at least a maximum in each of the molecular weight ranges of 103 14 8×104 and 105 -2×106 in the molecular weight distribution according to GPC (gel permeation chromatography). The toner exhibits excellent performances in respects of pulverizability, anti-offset characteristic, fixability, anti-filming or anti-melting characteristic on a photosensitive member and image forming characteristic but further improvement in anti-offset characteristic and fixability is desired.
a dynamic modulus G'120-200 at 120-200° C. of 2×103 or higher to below 5×105 [dyne/cm2 ] as measured in the frequency range of 1×10-2 -1 (Hz);
a loss modulus G"120-200 at 120-200° C. of 2×103 or higher to below 5×105 [dyne/cm2 ] as measured in the frequency range of 1×10-2 -1 (Hz);
a dynamic modulus G'200 at 200° C. and a frequency f satisfying an approximated linear relationship according to the least squares method of:
logG'.sub.200 =a·log·f+log b,
a ratio (G'200)/(G'120) of below 0.25 wherein (G'200) denotes a dynamic modulus at 200° C. and (G'120) denotes a dynamic modulus at 120° C. respectively at a frequency of 1 (Hz).
a ratio (G'200)/(G'120) of below 0.25 wherein (G'200) denotes a dynamic modulus at 200° C. and (G'120) denotes a dynamic modulus at 120° C. respectively at a frequency of 1 (Hz);
FIG. 1 is a graph showing the frequency-dependence (0.01 Hz-1 Hz) of the viscoelasticity at 120° C. of the toner according to Example 1.
FIG. 2 is a graph showing the frequency-dependence (0.01 Hz-1 Hz) of the viscoelasticity at 200° C. of the toner according to Example 1.
FIGS. 3 and 4 are graphs showing changes with time in viscoelasticity at 200° C., and 0.1 Hz and 1 Hz, respectively, of the toner according to Example 1.
FIG. 5 is a graph showing the frequency-dependence (0.01 Hz-1 Hz) of the viscoelasticity at 120° C. of the toner according to Example 5.
FIG. 6 is a graph showing the frequency-dependence (0.01 Hz-1 Hz) of the viscoelasticity at 200° C. of the toner according to Example 5.
FIGS. 7 and 8 are graphs showing changes with time in viscoelasticity at 200° C., and 0.1 Hz and 1 Hz, respectively, of the toner according to Example 5.
log G'.sub.200 =a·log·f+log b,
The thermal characteristic of a toner is significantly related to the fixability. For exhibiting a fixability, a toner is required to be softened so as to be sufficiently deformed when it is passed through hot rollers under pressure but not softened excessively so as not to cause a high-temperature offset. Further, the elasticity modulus of the toner is required not to cause too large a change according to a change in temperature so as to provide stable fixing and anti-offset characteristics. As the toner according to the present invention has a dynamic modulus G'(or G1)120-200 at 120-200° C. and a loss modulus G"(or G2)120-200 at 120-200° C. of respectively in the range of 2×103 to below 5×105 dyne/cm2 as measured in the frequency f range of 1×10-2 -1 Hz, a good fixability is exhibited without causing high-temperature offset at the time of fixing. Further, as the value a in the equation showing an approximated linear relationship is a positive number of 0.25 or smaller, the toner shows a moderate change in elasticity modulus according to a change in temperature at 200° C. or higher, so that it shows stable fixing and anti-offset characteristics even if there is some fluctuation in temperature along the rollers at the time of fixation.
The dynamic modulus and loss modulus of the toner according to the present invention does not substantially change with time at 200° C. so that, even if the toner recovered by cleaning by a fixing device cleaning member is subjected to heat from the fixing rollers for a long time, the recovered toner or developer does not cause a problem of leaking out from the cleaning member.
In case where a toner showing a G'120-200 below 2×103 [dyne/cm2 ] is used, the anti-offset characteristic is insufficient, and in case where a toner showing a G'120-200 exceeding 5×105 [dyne/cm2 ] is used, the low-temperature fixability is insufficient.
The toner according to the present invention has a ratio (G'200 /G'120) of below 0.25 (and preferably 0.05 or above) based on the dynamic moduli (G'120) at 120° C. and (G'200) at 200° C. at the same frequency (particularly at 1 Hz) in the range of 1×10-2 -1 Hz, and because of this characteristic in combination with the above-mentioned viscoelastic properties, the toner exhibits sufficient low-temperature fixability, anti-offset characteristic and anti-blocking characteristic in combination.
In order for the toner of the present invention to have a dynamic modulus G'120-200 of 2×103 to below 5×105 as measure at 120-200° C. in the frequency range of 1×10-2 [Hz]-1 [Hz], it is preferred to use a binder resin satisfying the above features.
If a low-molecular weight polymer or copolymer having dicarboxylic units is crosslinked with a metal ion, the anti-blocking characteristic of the toner can be improved without increasing the Tg of the polymer or copolymer. As the Tg need not be increased in order to improve the anti-blocking characteristic, it is possible to render the dynamic modulus and loss modulus measured at 120° C. to be below 5×105 dyne.cm2.
In case where a polymer or copolymer having a high Tg is used to increase the anti-blocking characteristic, the dynamic modulus and loss modulus at 120° C. become 5×105 dyne.cm2 or above, and it becomes difficult to accomplish low-temperature fixation.
Further, as crosslinkages having various bonding strengths are present in the polymer or copolymer, the dynamic modulus and loss modulus at 200° C. can be maintained at 2×103 dyne.cm2 or higher, and the frequency-dependence of the modulus G'200 to 200° C. measured in the frequency range of 1×10-2 -1 [Hz] can be made extremely small.
As the toner according to the present invention contains crosslinkages showing various bonding strengths in the binder resin as described above, the dynamic modulus and loss modulus at 200° C. thereof shows substantially no change with time. Herein, "substantially no change with time" means that, when the toner is held at 200° C. for a period of 1 hour, the measured values of the dynamic modulus and loss modulus during the period are within the range of 0.8-1.8 times, preferably 0.9-1.5 times, those measured at the initial stage.
A=(B×f×5.611)/S,
0.5-1.0 g of a toner sample is weighed (W1 g) and placed in a cylindrical filter paper (e.g., No. 86R available from Toyo Roshi K.K.) and then subjected to extraction with 100 to 200 ml of solvent THF by using a Soxhlet's extractor for 6 hours. The soluble content extracted with the solvent THF is recovered by evaporation and dried for several hours at 100° C. under vacuum to measure a weight (W2 g) of the THF-soluble content. On the other hand, the weight (W3 g) of the components, such as the magnetic material and/or pigment, other than the resin component in the toner is separately measured. Then, the THF-insoluble content is given by the following equation:
THF-insoluble content (%)=[W.sub.1 -(W.sub.2 +W.sub.3)]/[W.sub.1 -W.sub.3 ]×100
A column is stabilized in a heat chamber at 40° C., tetrahydrofuran (THF) solvent is caused to flow through the column at that temperature at a rate of 1 ml/min., and 50-200 μl of a sample resin solution in THF at a concentration of 0.05-0.6 wt. % is injected. The identification of sample molecular weight and its molecular weight distribution is performed based on a calibration curve obtained by using several monodisperse polystyrene samples and having a logarithmic scale of molecular weight versus count number. The standard polystyrene samples for preparation of a calibration curve may be those having molecular weights of, e.g., 6×102, 2.1×103, 4×103, 1.75×104, 5.1×104, 1.1×105, 3.9×105, 8.6×105, 2×106 and 4.48×106 available from, e.g., Pressure Chemical Co. or Toyo Soda Kogyo K.K. It is appropriate to use at least 10 standard polystyrene samples. The detector may be an RI (refractive index) detector.
For accurate measurement of molecular weights in the range of 103 -4×106, it is appropriate to constitute the column as a combination of several commercially available polystyrene gel columns. A preferred example thereof may be a combination of μ-styragel 500, 103, 104 and 105 available from Waters Co.; a combination of Shodex KF-80M, 802, 803, 804 and 805; or a combination of TSK gel G1000H, G2000H, G2500H, G3000H, G4000H, G5000H, G6000H, G7000H and GMH available from Toyo Soda K.K.
For measurement, a 1%-NaCl aqueous solution as an electrolytic solution is prepared by using a reagent-grade sodium chloride. For example, ISOTON®-II (available from Coulter Scientific Japan K.K.) may be used therefor. Into 100 to 150 ml of the electrolytic solution, 0.1 to 5 ml of a surfactant, preferably an alkylbenzenesulfonic acid salt, is added as a dispersant, and 2 to 20 mg of a sample is added thereto. The resultant dispersion of the sample in the electrolytic liquid is subjected to a dispersion treatment for about 1-3 minutes by means of an ultrasonic disperser, and then subjected to measurement of particle size distribution in the range of 2-40 microns by using the above-mentioned Coulter counter Model TA-II with a 100 micron-aperture to obtain a volume-basis distribution and a number-basis distribution. From the results of the volume-basis distribution and number-basis distribution, parameters characterizing the magnetic toner of the present invention may be obtained.
The polymerization was further continued and completed under reflux of cumene (146-156° C.), followed by removal of cumene. The thus obtained non-crosslinked styrene copolymer showed a main peak at a molecular weight of 5,000 and a glass transition temperature (Tg) of 60° C. The thus obtained non-crosslinked styrene copolymer in an amount of 30 wt. parts was dissolved in the following monomer mixture to form a polymerizable mixture.
170 wt. parts of water containing 0.1 wt. part of partially saponified polyvinyl alcohol was added to the above polymerizable mixture to form a suspension liquid. Into a reaction vessel containing 15 wt. parts of water and aerated with nitrogen. The above suspension liquid was added and subjected to 6 hours of suspension polymerization at 70-95° C. After the reaction, the product was separated by filtration, dewatered and dried to obtain a resin composition containing a styrene-n-butyl acrylate-monobutyl maleate copolymer and also a styrene-n-butyl acrylate-maleic acid-maleic anhydride copolymer. The resultant resin composition showed a THF-insoluble content of 40 wt. %, a Tg of 59° C., a JIS acid value (A) of 18.4 and a ratio (A/B) of 0.90 to the total acid value (B), and contained a THF-soluble content giving a GPC chart showing a peak at a molecular weight of about 5500 and a shoulder at a molecular weight of about 3.4×104.
About 0.5 g of the resin composition was accurately weighed (W1 g) and placed in a cylindrical filter paper (28×100 mm, "No. 86R", available from Toyo Roshi K.K.) and then subjected to extraction with 200 ml of solvent THF for 6 hours by using a Soxhlet's extractor. Each extraction cycle with THF by the Soxhlet's extractor took about 4 minutes The THF-soluble content extracted with THF was recovered by evaporation of the THF, dried under vacuum at 100° C. and then weighed (W2 g). The calculation was made according to the following equation:
THF insoluble content (%)=[W.sub.1 -W.sub.2 ]/W.sub.1 ×100.
The above ingredients were added dropwise in 4 hours to 200 wt. parts of cumene which had been heated to the reflux temperature. The solution polymerization was further completed under reflux of cumene (146-156° C.), followed by removal of cumene. The resultant styrene copolymer showed a peak at a molecular weight of 5200 on the GPC chart and a Tg of 62° C.
170 wt. parts of water containing 0.1 wt. part of partially saponified polyvinyl alcohol was added to the above mixture solution to form a suspension liquid. Into a reaction vessel containing 15 wt. parts of water and aerated with nitrogen, the above suspension liquid was added and subjected to 6 hours of suspension polymerization at 10-95° C. After the reaction, the product was separated by filtration, dewatered and dried to obtain a resin composition containing a crosslinked styrene-n-butyl acrylate-monobutyl maleate copolymer. The thus-obtained resin composition contained 55 wt. % of a THF-insoluble content, showed a Tg of 54° C., a JIS acid value (A) of 13.0 and a ratio (A/B) of 0.97 to the total acid value (B), and the THF-soluble content gave a GPC chart showing a peak at a molecular weight of about 6000 and a shoulder at a molecular weight of about 3.2×104.
The above ingredients were added dropwise in 4 hours to 200 wt. parts of xylene which had been heated to the reflux temperature. The solution polymerization was further completed under reflux of xylene (138-144° C.), followed by removal of xylene. The resultant non-crosslinked styrene copolymer showed a peak at a molecular weight of 5500 on the GPC chart and a Tg of 63° C.
170 wt. parts of water containing 0.1 wt. part of partially saponified polyvinyl alcohol was added to the above mixture solution to form a suspension liquid. Into a reaction vessel containing 15 wt. parts of water and aerated with nitrogen, the above suspension liquid was added and subjected to 6 hours of suspension polymerization at 70-95° C. After the reaction, the product was separated by filtration, dewatered and dried to obtain a resin composition containing a crosslinked styrene-n-butyl acrylate-monobutyl maleate copolymer. The thus-obtained resin composition contained 30 wt. % of a THF-insoluble content, showed a Tg of 57° C., a JIS acid value (A) of 30.5 and a ratio (A/B) of 0.81 to the total acid value (B), and the THF-soluble content gave a GPC chart showing peaks at molecular weights of about 6000 and about 3.6×104.
The above ingredients were added dropwise in 4 hours to 200 wt. parts of cumene which had been heated to the reflux temperature. The solution polymerization was further completed under reflux of cumene (146-156° C.), followed by removal of cumene. The resultant styrene copolymer showed a peak at a molecular weight of 4000 on the GPC chart and a Tg of 67° C.
170 wt. parts of water containing 0.1 wt. part of partially saponified polyvinyl alcohol was added to the above mixture solution to form a suspension liquid. Into a reaction vessel containing 15 wt. parts of water and aerated with nitrogen, the above suspension liquid was added and subjected to 6 hours of suspension polymerization at 70-95° C. After the reaction, the product was separated by filtration, dewatered and dried to obtain a resin composition containing a polystyrene and a non-crosslinked styrene-n-butyl acrylate copolymer. The thus-obtained resin composition was soluble in THF, gave a GPC chart showing peaks at molecular weights of about 4500 and about 3.0×104, and showed a JIS acid value (A) of 0.6.
Into a reaction vessel containing 15 wt. parts of water and aerated with nitrogen, the above suspension liquid was added and subjected to 6 hours of suspension polymerization at 70-95° C. After the reaction, the product was separated by filtration, dewatered and dried to obtain a crosslinked styrene-n-butyl acrylate-monobutyl maleate copolymer. The thus-obtained copolymer gave a GPC chart showing a main peak at a molecular weight of about 17,000 and substantially no peak below a molecular weight of 15,000.
The copolymer also showed a Tg of 60° C., a JIS acid value (A) of 16.6, a ratio (A/B) of about 1 to the total acid value (B), and a THF-insoluble content of 30 wt. %.
The copolymer showed a THF-insoluble content of 5 wt. %, peaks at molecular weights of about 17,000 and about 80×104 on the GPC chart, a Tg of 60° C., a JIS acid value (A) of 8.6 and a ratio (A/B) of 0.66 to the total acid value (B).
The above ingredients were sufficiently blended in a blender and melt-kneaded through a two-axis kneading extruder set at 130° C. The resultant kneaded product showed a lower melt index than corresponding kneaded product which was prepared under the same condition except that the complex [I]-2 was not added.
The viscoelastic properties of the magnetic toner were measured at 120° C. and 200° C., and the results thereof are shown in FIGS. 1 and 2, respectively. As shown in these figures, the dynamic modulus G' and loss modulus G" were within the range of 2×103 -5×105 dyne/cm2 from 120° C. to 200° C., and the ratio G'120 /G'200 was below 40. Further, the viscoelastic properties were not substantially changed with time at 200° C. as shown in FIGS. 3 and 4. The viscoelastic data of the toner are also shown in Table 1 appearing hereinafter together with those of other Examples.
The fixability evaluation was performed as follows. The test apparatus was placed in an environment of normal temperature and normal humidity (temperature: 23° C., humidity: 60%). After the apparatus and the fixing device therein were fully adapted to the environment, a power was supplied. Immediately after the waiting time was up, a pattern of 200 micron-wide transverse lines (line width: 200 microns, spacing: 200 microns) was printed on a first sheet, which was used for evaluation of the fixability. The fixing was effected by setting the surface temperature of a fluorine resin-coated hot fixing roller at 180° C. The fixability was evaluated by rubbing the printed image with a lens cleaning paper ("Dusper"®, made by OZU Paper Co. Ltd.) for 5 reciprocations under a weight of 100 g and then evaluating the degree of peeling of the toner image in terms of a decrease (%) in reflection density.
×: Practically not acceptable
×: Conspicuous stain and practically not acceptable (offsetting)
×: Conspicuous stain and practically unacceptable
TABLE 1__________________________________________________________________________Formulation     Organic          Viscoelastic dataBinder    metal             G'.sub.200 /G'.sub.120                                         Changeresin     complex          G'.sub.120Max *               G'.sub.200Min *                    a  at 1 Hz                             G".sub.120Max *                                   G".sub.200Min *                                         with time__________________________________________________________________________Ex. 1    Syn. Ex. 1     [I]-2          4.0 × 10.sup.5               1.2 × 10.sup.4                    0.17                       0.07  3.2 × 10.sup.5                                   4.5 × 10.sup.3                                         Almost No    100 parts     1 partEx. 2    Syn. Ex. 2     [II]-1          1.2 × 10.sup.5               1.3 × 10.sup.4                    0.22                       0.23  1.0 × 10.sup.5                                   9.0 × 10.sup.3                                         "    100 parts     1 partEx. 3    Syn. Ex. 3     [I]-2          4.5 × 10.sup.5               1.5 × 10.sup.4                    0.14                       0.16  3.5 × 10.sup.5                                   1.2 × 10.sup.4                                         "    100 parts     1 partEx. 4    Syn. Ex. 1     [I]-2          2.0 × 10.sup.5               4.1 × 10.sup.4                    0.14                       0.20  1.8 × 10.sup.5                                   3.4 × 10.sup.4                                         "    100 parts     0.5 part     [II]-1     0.5 partComp.    Comp. Syn.     [I]-2          1.9 × 10.sup.5               3.1 × 10.sup.2                    0.35                       0.01  1.8 × 10.sup.5                                   2.0 × 10.sup.2                                         "Ex. 1    Ex. 1 1 part    100 partsComp.    Comp. Syn.     [I]-2          1.8 × 10.sup.5               1.0 × 10.sup.3                    0.32                       0.24  1.5 × 10.sup.5                                   9.5 × 10.sup.2                                         "Ex. 2    Ex. 2 1 part    100 partsComp.    Comp. Syn.     [I]-2          2.1 × 10.sup.5               5.8 × 10.sup.2                    0.37                       0.22  1.0 × 10.sup.5                                   5.1 × 10.sup.2                                         YesEx. 3    Ex. 3 1 part    100 parts__________________________________________________________________________ *G'.sub.120Max, G'.sub.200Min, G".sub.120Max, G".sub.200Min : Respectively, the maximum or minimum data in the frequency range of 10.sup.-2 - 1 Hz.
TABLE 2______________________________________                           Hot fixing                  Pulveriz-                           roller stainFixability   Anti-offset                  ability* (after 5000 sheets)______________________________________Example 1   ∘            ∘                      ∘                             ∘2       ∘            ∘                      ∘                             ∘3       ∘            ∘                      ∘                             ∘4       ∘            ∘                      ∘                             ∘Comp.   Δ  x         ∘                             xExample 12       x        Δ   x      Δ3       x        Δ   x      ∘Δ______________________________________ *Pulverizability of kneaded product
The above ingredients were sufficiently blended in a blender and melt-kneaded through a two-axis kneading extruder set at 130° C. The kneaded product was cooled, coarsely crushed by a cutter mill, finely pulverized by means of a pulverizer using jet air stream, and classified by a fixed-wall type wind-force classifier to obtain a classified powder product. Ultra fine powder and coarse powder were simultaneously and precisely removed from the classified powder by means of a multi-division classifier utilizing a Coanda effect (Elbow Jet Classifier available from Nittetsu Kogyo K.K.), thereby to obtain a magnetic toner having a volume-average particle size of 6.5 microns.
The viscoelastic properties of the magnetic toner were measured at 120° C. and 200° C., and the results thereof are shown in FIGS. 5 and 6, respectively. As shown in these figures, the dynamic modulus G' and loss modulus G" were within the range of 2×103 -5×105 dyne/cm2 from 120° C. to 200° C., and the ratio G'120 /G'200 was below 40. Further, the viscoelastic properties were not substantially changed with time at 200° C. as shown in FIGS. 7 and 8. The viscoelastic data of the toner are also shown in Table 4 appearing hereinafter together with those of other Examples.
TABLE 3__________________________________________________________________________Particle size distribution of toner    % by number      % by volume             % by number                      Volume-average                               (% by number)/    of particles      of particles             of particles                      particle size                               (% by volume) oftoner    of ≦5 μm      of ≧12.7 μm             of 6.35-10.08 μm                      (μm)  particles of ≦5__________________________________________________________________________                               μmEx. 5    49.2   0      22.6     6.5      2.56   49.4   0      22.9     6.6      2.67   49.1   0      23.0     6.6      2.58   49.1   0      22.8     6.6      2.59   30.1   1.4    45.5     7.9      3.8Comp.    49.0   0      22.9     6.6      2.5Ex. 45   49.4   0      22.7     6.5      2.66   49.2   0      22.5     6.5      2.5__________________________________________________________________________
TABLE 4__________________________________________________________________________Formulation     OrganicBinder    metal          Viscoelastic dataresin     complex          G'.sub.120MAX                G'.sub.200 Min                      G'.sub.120Max /G'.sub.200Min                               a__________________________________________________________________________Ex. 5    Syn. Ex. 1     [I]-2          2.0 × 10.sup.5                1.7 × 10.sup.4                      12       0.16    100 parts     0.5 partEx. 6    Syn. Ex. 2     [II]-1          1.2 × 10.sup.5                1.2 × 10.sup.4                      10       0.19    100parts     0.8 partEx. 7    Syn. Ex. 3     [I]-2          4.5 × 10.sup.5                1.4 × 10.sup.4                      32       0.13    100 parts     0.5 partEx. 8    Syn. Ex. 1     [I]-1          2.0 × 10.sup.5                3.8 × 10.sup.4                      5.2      0.13    100 parts     0.4 part     [II]-1     0.4 partEx. 9    Syn. Ex. 1     [I]-2          2.0 × 10.sup.5                1.8 × 10.sup.4                      11       0.16    100 parts     0.5 partComp.    Comp. [I]-2          1.8 × 10.sup.5                2.9 × 10.sup.2                      620      0.35Ex. 4    Syn. Ex. 1     0.5 part    100 partsComp.    Comp. [I]-2          1.8 × 10.sup.5                1.0 × 10.sup.3                      180      0.30Ex. 5    Syn. Ex. 2     0.5 part    100 partsComp.    Comp. [I]-2          2.0 × 10.sup.5                5.7 × 10.sup.2                      350      0.35Ex. 6    Syn. Ex. 3     0.5 part    100 parts__________________________________________________________________________
TABLE 5__________________________________________________________________________          Pulver-               Roller   Dot reproducibilityFixability    Anti-offset          ization *1               stain *2                   Dmax *3                        80 μm                             50 μm__________________________________________________________________________Ex. 5    ∘    ∘          ∘               ∘                   1.37 ∘                             ∘6   ∘    ∘          ∘               ∘                   1.32 ∘                             ∘7   ∘    ∘          ∘               ∘                   1.33 ∘                             ∘8   ∘    ∘          ∘               ∘                   1.32 ∘                             ∘9   ∘    ∘          ∘               ∘                   1.35 ∘                             ∘ΔComp.    Δ    x     ∘               x   1.36 ∘                             ∘Ex. 45   x    Δ          x    Δ                   1.35 ∘                             ∘6   x    Δ          x    ∘Δ                   1.32 ∘                             ∘__________________________________________________________________________ *1: Pulverizability of kneaded product. *2: Hot fixing roller stain (after 5000 sheets) *3: Image density Dmax at the initial stage (after 20 sheets)
1. A heat and pressure fixable toner for developing electrostatic images, comprising: a binder resin and a metal salt or a metal complex; wherein the toner has:
wherein the binder resin comprises a copolymer or a mixture thereof comprising polymerized units of a carboxyl group-containing monomer and having crosslinkages including a metallic crosslinkage and a polymeric crosslinkage.
2. The toner according to claim 1, which contains a magnetic material.
8. The toner according to claim 1, wherein the toner shows a dynamic modulus and a loss modulus measured while it is held at 200° C. for a period of one hour, which are within the range of 0.8-1.8 times the corresponding values measured at the initial stage of the period.
9. The toner according to claim 1, wherein the toner shows a dynamic modulus and loss a modulus measured while it is held at 200° C. for a period of one hour, which are within the range of 0.9-1.5 times the corresponding values measured at the initial stage of the period.
29. A fixing method comprising fixing a toner image on a sheet by applying heat and pressure,
wherein the toner comprises a binder resin and a metal salt or a metal complex;
wherein the toner has:
a ratio (G'200)/G'120) of below 0.25 wherein (G'200) denotes a dynamic modulus at 200° C. and (G'120) denotes a dynamic modulus at 120° C. respectively at a frequency of 1 (Hz); and
30. The method according to claim 29, including fixing the toner on a sheet by a hot pressure roller.
38. The method according to claim 29, wherein the toner shows a dynamic modulus and a loss modulus measured while it is held at 200° C. for a period of one hour, which are within the range of 0.8-1.8 times the corresponding values measured at the initial stage of the period.
39. The method according to claim 29, wherein the toner shows a dynamic modulus and a loss modulus measured while it is held at 200° C. for a period of one hour, which are within the range of 0.9-1.5 times the corresponding values measured at the initial stage of the period.
US07611096 1989-11-09 1990-11-09 Toner having crosslinkages and method of fixing same Expired - Lifetime US5180649A (en)
JP28988189 1989-11-09
JP29179689 1989-11-09
JP1-289881 1989-11-09
JP1-291796 1989-11-09
US5180649A true US5180649A (en) 1993-01-19
ID=26557785
US07611096 Expired - Lifetime US5180649A (en) 1989-11-09 1990-11-09 Toner having crosslinkages and method of fixing same
US (1) US5180649A (en)
EP (1) EP0427272B1 (en)
CA (1) CA2029468C (en)
DE (2) DE69028372D1 (en)
ES (1) ES2091217T3 (en)
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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:KUKIMOTO, TSUTOMU;YUSA, HIROSHI;TAKIGUCHI, TSUYOSHI;ANDOTHERS;REEL/FRAME:005547/0981