Source: https://patents.google.com/patent/US4833057?oq=6246862
Timestamp: 2018-05-21 11:21:01
Document Index: 457214085

Matched Legal Cases: ['arts           50', 'arts           50', 'arts          50', 'arts          50', 'arts           50', 'arts           50']

US4833057A - Toner composition for the electrophotography - Google Patents
Toner composition for the electrophotography Download PDF
US4833057A
US4833057A US07110695 US11069587A US4833057A US 4833057 A US4833057 A US 4833057A US 07110695 US07110695 US 07110695 US 11069587 A US11069587 A US 11069587A US 4833057 A US4833057 A US 4833057A
US07110695
Hisatomo Sato
Masaaki Shin
Kazuo Hisamatsu
Shoji Kawasaki
MITSUI TOATSU CHEMICALS Inc 2-5 KASUMIGASEKI 3-CHOME CHIYODA-KU TOKYO 100 JAPAN A CORP OF JAPAN
Disclosed is a toner composition for the electrophotography, which comprises as a main component a urethane-modified polyester resin obtained by reacting a polyester resin with an isocyanate compound, in which the mole-equivalent ratio between the hydroxyl group of the polyester resin and the isocyanate group of the isocyanate compound is within a specific range and the glass transition temperature of the obtained resin is within a specific range.
The present invention relates to a toner composition for the electrophotography.
In the electrophotography, the copying speed is an important problem. Increase of the copying speed can be tentatively attained if the copying machine is designed so that the copying speed of the machine per se is high. However, this alone is insufficient for attaining high-speed reproduction while maintaining a good quality of a copied image. Namely, for this purpose, it is necessary to improve the properties of developer materials, especially a toner.
We made research with a view to solving these problems and as the result, it was found that a urethane-modified polyester obtained by reacting a polyester resin with an isocyanate compound has a good fixing property at a low temperature and a good offset resistance at a high temperature and this modified polyester resin is especially excellent in the form of a mixture with a polymer having a relatively low molecular weight. We have now completed the present invention based on this finding. In accordance with the present invention, there is provided a toner composition for the electrophotography, which comprises as a main component a urethane-modified polyester resin (C) obtained by reacting a polyester resin (A) having a number average molecular weight of 1000 to 15000 with an isocyanate compound (B) in an amount of 0.05 to 0.95 mole-equivalent per mole of the hydroxyl group of the polyester resin (A), said urethane-modified polyester resin (C) having a glass transition temperature of 40° to 80° C. Furthermore, in accordance with the present invention, there is provided a toner composition for the electrophotography, which comprises a resin mixture (E) comprising a urethane-modified polyester resin (C) obtained by reacting a polyester resin (A) having a number average molecular weight of 1000 to 15000 with an isocyanate compound (B) in an amount of 0.05 to 0.95 mole-equivalent per mole of the hydroxyl group of the polyester resin (A), said urethane-modified polyester resin (C) having a glass transition temperature of 40° to 80° C., and a polymer (D) having a number average molecular weight of 1000 to 10000, the (C)/(D) weight ratio being from 30/70 to 95/5 and the glass transition temperature of the resin mixture (E) being 40° to 80° C.
The polyester resin (A) referred to in the present invention is obtained by polycondensation of a polycarboxylic acid and a polyhydric alcohol. As the polycarboxylic acid, there can be mentioned aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and hexahydrophthalic anhydride, aliphatic unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid and citraconic acid, aromatic dibasic acids such as phthalic anhydride, phthalic acid, terephthalic acid and isophthalic acid, and lower alkyl esters thereof. Among these polycarboxylic acids, an aromatic dibasic acid and/or a lower alkyl ester thereof is preferred.
Known high-temperature polycondensation and solution polycondensation processes can be adopted for the polycondensation. For example, the polycondensation temperature is 200° to 250° C. and the polycondensation time is 3 to 20 hours.
The urethane-modified polyester resin (C) can be prepared, for example, according to the following process. Namely, the isocyanate compound (B) is added collectively or dividedly to the polyester resin (A) alone or a solution containing the polyester resin (A) at a temperature of 80° to 150° C., and the reaction is carried out at this temperature for several hours to obtain the urethane-modified polyester resin.
The glass transition temperatures of the urethane-modified polyester resin (C) and the resin mixture (E) are 40° to 80° C., preferably 50° to 70° C. A glass transition temperature lower than 40° C. is not preferred because the blocking resistance is degraded, and a glass transition temperature exceeding 80° C. is not preferred because the fixing property of the toner is degraded.
A most popular process for the preparation of the toner composition for the electrophotography according to the present invention comprises mixing the urethane-modified polyester resin (C) or resin mixture (E) pulverized to a particle size of about 0.5 to about 2 mm with carbon, adding an acrylic resin, a styrene resin, an epoxy resin, maleic acid-modified rosin, a magnetic powder such as ferrite or magnetite, a small amount of a charge-controlling agent and a wax according to need, blending the mixture by a Henschel mixer, melt-kneading the mixture at a temperature of 100° to 180° C. by a kneader or the like and pulverizing and classifying the formed mass to obtain particles having a particle size of 5 to 20 μm. The amount of the urethane-modified polyester resin (C) or the resin mixture (E) is ordinarily 50 to 90% by weight when the magnetic powder is not used and is generally 10 to 99% by weight when the magnetic powder is used.
EXAMPLES 1 THROUGH 9 [Examples A1 through A9 of Production of Polyester Resin (A)]
A four-necked flask having a capacity of 10 liters, which was equipped with a reflux cooler, a water separator, a nitrogen-introducing pipe, a thermometer and a stirrer, was charged with amounts shown in Table 1 of a polycarboxylic acid and a polyhydric alcohol and 0.05% by weight of dibutyl tin oxide as the dehydration catalyst, and dehydration copolycondensation was carried out at an inner temperature of 240° C. while introducing nitrogen into the flask.
[Examples C1 through C9 of Production of Urethane-Modified Polyester Resin (C)]
A four-necked flask having a capacity of 10 liters, which was equipped with a reflux cooler, a nitrogen-introducing pipe, a thermometer and a stirrer, was charged with amounts shown in Table 1 of the polyester resin (A) and xylene. The polyester resin (A) was dissolved in xylene, and an amount shown in Table 1 of an isocyanate compound (B) was divided into four parts and added dividedly in four times at intervals of 1 hour at an inner temperature of 120° C. in a nitrogen current. Reaction was carried out at this temperature for 1 hour. Then, a solvent-separating device was attached to the flask, and the inner temperature was gradually elevated and xylene was distilled off under atmospheric pressure. A pressure-reducing device was attached to the flask and volatile components were completely distilled off at an inner temperature of 190° C. under an inner pressure of 10 mmHg to obtain a urethane-modified polyester resin (C) having properties shown in Table 1.
[Examples 1 through 9 of Production of Toner]
Each of the so-obtained urethane-modified polyester resins C1 through C9 was roughly pulverized to a particle size of 0.5 to 2 mm by a hammer mill, and 5 parts by weight carbon black, MA-100 (supplied by Mitsubishi Kasei Kogyo K.K.), 2 parts by weight of Spiron Black TRH (supplied by Hodogaya Kagaku K.K.) as the charge-controlling agent, 2 parts by weight of a polypropylene wax, Viscol 550P (supplied by Sanyo Kasei Kogyo K.K.) and 3 parts by weight of a bisamide type wax, Armowax EBS (supplied by Lion-Armer Co.) were dispersed and mixed into 100 parts by weight of the resin (C) by a Henschel mixer. The mixture was melt-kneaded at 160° C. by a twin screw extruder, PCM30 (supplied by Ikegai Tekko K.K.) to obtain a bulky toner composition.
TABLE 1__________________________________________________________________________Example No.            1   2    3   4    5   6    7   8    9__________________________________________________________________________ Polyester Resin (A)   A1  A2   A3  A4   A5  A6   A7  A8   A9KB300K         (1)             (parts)                  454 387  482 464  387 566  752 805  593Diethylene glycol (parts)                  140          143      171  218 228  172Neopentyl glycol  (parts)  169           1691,6-hexane diol   (parts)       165Trimethylol propane             (parts)                    4.4  18  21Glycerol          (parts)                                  10Isophthalic acid  (parts)                  398 415  423          498  631 664  498Terephthalic acid (parts)           407  415Amount of removed water             (parts)                  86  90   92  88   90  108  137 144  144Acid value (mgKOH/g)          (2)     <1  <1   <1  <1   <1  <1   <1  <1   <1Hydroxyl value (mgKOH/g)          (3)     30  31   31  30   31  34   45  51   46Mn             (4)     6300                      6100 6200                               6300 6100                                        6400 6200                                                 6100 6200Mw             (5)     15100                      14600                           14900                               15000                                    15000                                        17300                                             19200                                                 24800                                                      18500Mw/Mn          (6)     2.4 2.4  2.4 2.4  2.5 2.7  3.1 4.1  3.0 Urethane-Modified Polyester Resin (C)                  C1  C2   C3  C4   C5  C6   C7  C8   C9 Polyester resin  (parts)                  1000                      1000 1000                               1000 1000                                        1000 1000                                                 1000 1000Xylene            (parts)                  1000                      1000 1000                               1000 1000                                        1000 1000                                                 1000 1000MDI            (7)             (parts)                  53.5                      54.6 53.8                               52.9 54.6                                        45.5 42.9                                                 45.5 44.1NCO/OH         (8)     0.8 0.8  0.8 0.8  0.8 0.6  0.43                                                 0.4  0.43Mn             (4)     12000                      11000                           12500                               12000                                    11800                                        12000                                             11000                                                 11500                                                      11000Mw             (5)     78000                      77000                           78000                               75000                                    77000                                        300000                                             320000                                                 320000                                                      310000Mw/Mn          (6)     6.5 7.0  6.2 6.3  6.5 25   29  28   28Tg             (9)             (°C.)                  62.3                      61.4 60.9                               61.5 60.5                                        60.3 61.5                                                 60.7 61.3TonerBlocking resistance          (10)    ⊚                      ⊚                           ⊚                               ⊚                                    ⊚                                        ⊚                                             ⊚                                                 ⊚                                                      .circleincircle                                                      .Pulverizability          (11)    ○                      ○                           ○                               ○                                    ○                                        ○                                             ○                                                 ○                                                      ○Heat resistance          (12)    ⊚                      ⊚                           ⊚                               ⊚                                    ⊚                                        ⊚                                             ⊚                                                 ⊚                                                      .circleincircle                                                      .Lower limit of fixing          (13)    150 148  150 150  150 150  148 150  150temperature (°C.)Offset-initiating          (14)    250 250  250 250  250 250< 250<                                                 250< 250<temperature (°C.)Image density  (15)    dense                      dense                           dense                               dense                                    dense                                        dense                                             dense                                                 dense                                                      denseFogging        (16)    ⊚                      ⊚                           ⊚                               ⊚                                    ⊚                                        ⊚                                             ⊚                                                 ⊚                                                      .circleincircle                                                      .Resistance against          (17)    ⊚                      ⊚                           ⊚                               ⊚                                    ⊚                                        ⊚                                             ⊚                                                 ⊚                                                      .circleincircle                                                      .migration of polyvinylchloride plasticizer__________________________________________________________________________
According to the same procedures as described in Examples 1 through 9, polyester resins (A) A10 through A21 and urethane-modified polyester resins (C) C10 through C21, and the properties of these resins are shown in Table 2.
TABLE 2__________________________________________________________________________Example No.    10  11  12  13  14  15  16  17  18  19  20  21__________________________________________________________________________ Polyester Resin (A)          A10 A11 A12 A13 A14 A15 A16 A17 A18 A19 A20 A21KB300K    (parts)          465 626 297 622 547 549 619 537 690 644 680 341Diethylene glycol     (parts)          143 193 92  192 169 166 179 152 200 187 197 99Neopentyl glycol     (parts)1,6-hexane diol     (parts)Trimethylol propane     (parts)                  4.3 14  17  16  15  16  8.0Glycerol  (parts)Isophthalic acid     (parts)          299 465 249 531 498 365 398 432 564 531 581 299Terephthalic acid     (parts)Amount of removed     (parts)          65  101 54  115 108 79  86  89  122 115 126 65waterAcid value     <1  <1  <1  <1  <1  <1  <1  5   <1  <1  <1  <1(mgKOH/g)Hydroxyl value 156 93  47  37  23  90  97  90  58  51  37  33(mgKOH/g)Mn             1200              2000                  4000                      5100                          8200                              2200                                  2300                                      2500                                          4300                                              5200                                                  8500                                                      10000Mw             2400              4400                  9200                      11700                          19700                              6000                                  7100                                      11000                                          13300                                              16100                                                  21000                                                      34000Mw/Mn          2.0 2.2 2.3 2.3 2.4 2.7 3.1 4.4 3.1 3.1 2.5 3.4Urethane-Modified          C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21Polyester Resin (C)Polyester resin     (parts)          1000              1000                  1000                      1000                          1000                              1000                                  1000                                      1000                                          1000                                              1000                                                  1000                                                      1000Xylene    (parts)          1000              1000                  1000                      1000                          1000                              1000                                  1000                                      1000                                          1000                                              1000                                                  1000                                                      1000MDI       (parts)          330 197 91.1                      68.4                          51.2                              160 128 89.8                                          64.6                                              53.4                                                  34.8                                                      29.4NCO/OH         0.95              0.95                  0.87                      0.83                          0.78                              0.80                                  0.59                                      0.44                                          0.50                                              0.47                                                  0.42                                                      0.40Mn             10000              12300                  12000                      12300                          12500                              11500                                  10000                                      11000                                          12500                                              12000                                                  12500                                                      12800Mw             50000              75000                  72000                      76000                          78000                              320000                                  290000                                      300000                                          330000                                              340000                                                  330000                                                      360000Mw/Mn          5.0 6.1 6.0 6.2 6.2 28  29  27  26  28  26  28Tg (°C.)          58.5              61.9                  62.1                      61.8                          61.5                              60.7                                  60.2                                      58.5                                          60.5                                              62.3                                                  61.3                                                      60.5TonerBlocking resistance          ⊚              ⊚                  ⊚                      ⊚                          ⊚                              ⊚                                  ⊚                                      ⊚                                          ⊚                                              ⊚                                                  ⊚                                                      .circleincircle                                                      .Pulverizability          ○              ○                  ○                      ○                          ○                              ○                                  ○                                      ○                                          ○                                              ○                                                  ○                                                      ○Heat resistance          X   X   Δ                      Δ                          ⊚                              X   X   X   Δ                                              Δ                                                  ⊚                                                      .circleincircle                                                      .Lower limit of fixing          146 150 150 150 150 150 150 150 150 150 150 150temperature (°C.)Offset-initiating          190 210 220 225 250 220 220 220 240 245 250<                                                      250<temperature (°C.)Image density  dense              dense                  dense                      dense                          dense                              dense                                  dense                                      dense                                          dense                                              dense                                                  dense                                                      denseFogging        X   X   Δ                      Δ                          ⊚                              X   X   X   Δ                                              Δ                                                  ⊚                                                      .circleincircle                                                      .Resistance against          ⊚              ⊚                  ⊚                      ⊚                          ⊚                              ⊚                                  ⊚                                      ⊚                                          ⊚                                              ⊚                                                  ⊚                                                      .circleincircle                                                      .migration of poly-vinyl chlorideplasticizer__________________________________________________________________________
Polyester resins (A) A22 through A25 were prepared by using amounts shown in Table 3 of a polyhydric alcohol and a polycarboxylic acid according to the same procedures as described in Examples 1 through 9, and the properties of the obtained polyester resins (A) are shown in Table 3.
TABLE 3__________________________________________________________________________Example No.        22   23   24   25__________________________________________________________________________Polyester Resin (A)              A22  A23  A24  A25KB300K (parts)     626  297  454  358Diethylene glycol (parts)              193  92   140  110Isophthalic acid (parts)              465  249  398  332Amount of removed water (parts)              101  54   86   72Acid value         <1   <1   <1   <1Hydroxyl value     93   47   30   19Mn                 2000 4000 6300 9700Mw                 4400 9200 15100                             24000Urethane-Modified Polyester Resin (C)              C22  C23  C24  C25Polyester resin (A) (parts)              1000 1000 1000 1000Xylene (parts)     1000 1000 1000 1000Desmodur R (18) (parts)              101  47   26   8.3NCO/OH             0.25 0.23 0.2  0.1Properties of Resin (C)Mn                 4200 5600 8000 11000Mw                 135000                   138000                        145000                             130000Mw/Mn              32   25   18   12Tg (°C.)    60.5 61   59.7 59.7Properties of TonerBlocking resistance              ⊚                   ⊚                        ⊚                             ⊚Pulverizability    ⊚                   ⊚                        ○                             ○Heat resistance    X    Δ                        ⊚                             ⊚Fixing temperature 135  143  145  150Offset-initiating temperature              230  250  250< 250<Image density      dense                   dense                        dense                             denseFogging            X    Δ                        ⊚                             ⊚Resistance against migration of              ⊚                   ⊚                        ⊚                             ⊚polyvinyl chloride plasticizer__________________________________________________________________________
EXAMPLES 26 THROUGH 36 [Examples D1 through D5 for Production of Polymer (D)]
Polymers (D) D1 through D4 were synthesized from amounts shown in Table 4 of a polyhydric alcohol and a polycarboxylic acid and 0.5% by weight of dibutyl tin oxide according to the same process as the process for the preparation of the polyester resin (A) described in Examples 1 through 9. The properties of the obtained polymers (D) are shown in Table 4.
[Examples E1 through E4 of Production of Resin Mixture (E)]
A separable flask having a capacity of 10 liters was charged with an amount shown in Table 5 of the urethane-modified polyester resin (C) C1, C7 or C24 synthesized in Example 1, 7 or 24, an amount shown in Table 5 of the polymer (D) D1, D2, D3, D4 or D5 shown in Table 4 and 100 parts by weight of xylene, and the resins were dissolved in xylene at an inner temperature of 120° C. and xylene was distilled off in the same manner as described in Examples 1 through 9. Then, the mixture was subjected to a high-temperature treatment at 190° C. under 10 mmHg. Thus, resin mixtures (E) E1 through E11 were obtained.
[Examples 26 through 36 of Production of Toner]
Toners 26 through 36 were prepared by using the resin mixtures (E) E1 through E11 according to the same procedures as described in Examples 1 through 9.
TABLE 4______________________________________Polymer (D)       D1     D2     D3   D4   D5______________________________________Composition of Polymer (D)KB-300K (parts)   1376   1307   1342 1445 1238Isophthalic acid (parts)Terephthalic acid (parts)             930    883    777  802  --Dimethyl terephthalate (parts)             --     --     --   --   873n-butyl orthotitanate (parts)             --     --     --   --   1.25COOH/OH           1.4    1.3    1.2  1.15 --COOCH.sub.3 /OH   --     --     --   --   1.25Amount of removed water             144    137    140  151(parts)Amount of removed ethanol             --     --     --   --   230(parts)Properties of Polymer (D)OH value (mgKOH/g)             <1     <1     <1   <1   <1Mn                1100   2160   3200 3900 2950Mw                2310   4540   7060 8970 6790Tg (°C.)   40.0   51.5   56.3 57.8 56.0______________________________________
TABLE 5__________________________________________________________________________Example No.     26  27   28  29  30   31  32  33   34  35  36__________________________________________________________________________ Resin mixture (E)           E1  E2   E3  E4  E5   E6  E7  E8   E9  E10 E11Urethane-ModifiedPolyester Resin (C)      No.  C1  C1   C1  C1  C1   C1  C1  C1   C1  C7  C24      parts           50  50   50  50  50   30  40  60   70  50  50Polymer (D)      No.  D1  D2   D3  D4  D5   D5  D5  D5   D5  D5  D5      parts           50  50   50  50  50   70  60  40   30  50  50Properties ofResin MixtureMn              2020               3660 5050                        5890                            4740 3810                                     4230                                         5390 6250                                                  4770                                                      3860Mw              37200               38300                    39550                        40500                            39400                                 26400                                     32900                                         46000                                              52500                                                  168400                                                      72400Mw/Mn           18  10   7.8 6.9 8.3  6.9 7.8 8.5  8.4 35.3                                                      18.8Tg (°C.) 51.3               56.8 59.2                        60.0                            59.1 57.7                                     58.2                                         59.5 60.2                                                  61.3                                                      61.6Properties of TonerBlocking resistance           ○               ⊚                    ⊚                        ⊚                            ⊚                                 ⊚                                     ⊚                                         ⊚                                              ⊚                                                  ⊚                                                      .circleincircle                                                      .Pulverizability ⊚               ⊚                    ⊚                        ⊚                            ⊚                                 ⊚                                     ⊚                                         ⊚                                              ⊚                                                  ⊚                                                      .circleincircle                                                      .Lower limit of fixing           122 133  137 139 136  134 136 138  140 137 134temperature (°C.)Offset resistance           215 220  220 220 220  200 210 225  230 250<                                                      240Heat resistance ⊚               ⊚                    ⊚                        ⊚                            ⊚                                 ⊚                                     ⊚                                         ⊚                                              ⊚                                                  ⊚                                                      .circleincircle                                                      .Image density   dense               dense                    dense                        dense                            dense                                 dense                                     dense                                         dense                                              dense                                                  dense                                                      denseFogging         ⊚               ⊚                    ⊚                        ⊚                            ⊚                                 ⊚                                     ⊚                                         ⊚                                              ⊚                                                  ⊚                                                      .circleincircle                                                      .Resistance against migration           ⊚               ⊚                    ⊚                        ⊚                            ⊚                                 ⊚                                     ⊚                                         ⊚                                              ⊚                                                  ⊚                                                      .circleincircle                                                      .of polyvinyl chloride plasticizer__________________________________________________________________________
[Examples E12 through E23 of Production of Resin Mixture (E)]
A separable flask having a capacity of 10 liters was charged with amounts shown in Table 6 of one of the urethane-modified polyester resins (C) C10 through C21 synthesized in Examples 10 through 21 and the polymer (D) D5 shown in Table 4 and 100 parts by weight of xylene. The resins were dissolved in xylene at an inner temperature of 120° C. and xylene was distilled off according to the same procedures as described in Examples 1 through 9, and the residue was subjected to a high-temperature treatment at 190° C. under 10 mmHg. Thus, resin mixtures (E) E12 through E23 were obtained. The properties of the obtained resin mixtures (E) E12 through E23 are shown in Table 6.
[Examples 37 through 48 of Production of Toner]
By using the resin mixtures (E) E12 through E23, toners 37 through 48 were prepared in the same manner as described in Examples 1 through 9.
TABLE 6__________________________________________________________________________Example No.    37  38  39  40  41  42  43  44  45  46  47  48__________________________________________________________________________ Resin Mixture (E)          E12 E13 E14 E15 E16 E17 E18 E19 E20 E21 E22 E23Urethane-ModifiedPolyester Resin (C)     No.  C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21     parts          50  50  50  50  50  50  50  50  50  50  50  50Polymer (D)     No.  D5  D5  D5  D5  D5  D5  D5  D5  D5  D5  D5  D5     parts          50  50  50  50  50  50  50  50  50  50  50  50Properties ofResin MixtureMn             4500              4800                  4700                      4800                          4800                              4700                                  4600                                      4700                                          4800                                              4700                                                  4800                                                      4800Mw             28000              41000                  39000                      41000                          42000                              163000                                  148000                                      153000                                          168000                                              173000                                                  168000                                                      183000Mw/Mn          6.2 8.5 8.3 8.5 8.8 34.7                                  32.2                                      32.6                                          35.0                                              36.8                                                  35.0                                                      38.1Tg (°C.)          57.3              59.0                  59.1                      58.4                          58.5                              58.0                                  58.1                                      57.5                                          58.3                                              59.7                                                  58.5                                                      58.3Properties of TonerBlocking resistance          ⊚              ⊚                  ⊚                      ⊚                          ⊚                              ⊚                                  ⊚                                      ⊚                                          ⊚                                              ⊚                                                  ⊚                                                      .circleincircle                                                      .Pulverizability          ⊚              ⊚                  ⊚                      ⊚                          ⊚                              ⊚                                  ⊚                                      ⊚                                          ⊚                                              ⊚                                                  ⊚                                                      .circleincircle                                                      .Fixing temperature          135 136 136 136 136 135 135 136 136 135 135 136(°C.)Offset-initiating          160 170 180 195 220 230 230 230 235 240 250<                                                      250<temperatureHeat resistance          X   X   Δ                      Δ                          ⊚                              X   X   X   Δ                                              Δ                                                  ⊚                                                      .circleincircle                                                      .Image density  dense              dense                  dense                      dense                          dense                              dense                                  dense                                      dense                                          dense                                              dense                                                  dense                                                      denseFogging        X   X   Δ                      Δ                          ⊚                              X   X   X   Δ                                              Δ                                                  ⊚                                                      .circleincircle                                                      .Resistance against migration          ⊚              ⊚                  ⊚                      ⊚                          ⊚                              ⊚                                  ⊚                                      ⊚                                          ⊚                                              ⊚                                                  ⊚                                                      .circleincircle                                                      .of polyvinyl chlorideplasticizer__________________________________________________________________________
EXAMPLES 48 THROUGH 58 [Examples D6 through D10 of Production of Polymer (D)]
A 4-necked flask having a capacity of 10 liters, which was equipped with a reflux cooler, a nitrogen-introducing pipe, a thermometer and a monomer-dropping device, was charged with an amount shown in Table 7 of xylene, and the temperature was elevated to a level sufficient to reflux xylene.
Under reflux of xylene (the inner temperature was 140° C.), amounts shown in Table 7 of monomers and a polymerization initiator were continuously dropped from the monomer-dropping device over a period of 4 hours while introducing nitrogen gas into the flask.
After termination of the dropwise addition, the inner temperature was maintained at 140° C. for 2 hours. After it was confirmed that the non-volatile content in the solution was higher than 99% of the theoretical value, the reaction mixture was cooled and diluted with xylene in an amount shown in Table 7 to completely terminate the reaction.
[Examples E23 through E33 of Production of Resin Mixture (E)]
A separable flask having a capacity of 10 liters was charged with an amount shown in Table 8 of one of the urethane-modified polyester resins (C) C1, C7 and C24 obtained in Examples 1, 7 and 24 and an amount shown in Table 8 as the solid of one of the polymers (D) D6 through D10 having the properties shown in Table 7. A solution was formed at an inner temperature of 120° C., and in the same manner as described in Examples 1 through 9, xylene was distilled off and the residue was treated at a high temperature under reduced pressure. Thus, resin mixtures (E) E23 through E33 were prepared. The properties of the obtained resin mixtures (E) E23 through E33 are shown in Table 8.
[Examples 48 through 58 of Production of Toner]
Toners 48 through 58 were prepared from the resin mixtures (E) E23 through E33 in the same manner as described in Examples 1 through 9.
TABLE 7______________________________________Polymer (D)    D6     D7     D8    D9    D10______________________________________Polymerization Solvent          150    150    100   80    60Xylene (parts)Vinyl MonomersStyrene (parts)          40     40     40    40    40Methyl methacrylate          57     45     33    22    33(parts)Ethyl acrylate (parts)          3      15     27    --    272-Ethylhexyl methacrylate          --     --     --    33    --(parts)Methacrylic acid (parts)          --     --     --    5     --Polymerization Initiator          8.0    5.0    2.5   2.0   1.0t-butyl peroctoate (parts)Dilution SolventXylene (parts) 50     50     100   120   140Polymerization 140    140    140   140   140temperature (°C.)Properties of CopolymerMn             2200   3100   4300  6200  9500Mw             4900   7400   10000 15000 23000Mw/Mn          2.4    2.4    2.3   2.4   2.4Tg (°C.)          57.8   60.4   58.0  59.0  61.5______________________________________
TABLE 8__________________________________________________________________________Example No.     48  49   50  51  52   53  54  55   56  57  58__________________________________________________________________________ Resin Mixture (E)           E23 E24  E25 E26 E27  E28 E29 E30  E31 E32 E33Urethane-ModifiedPolyester Resin (C)      No.  C1  C1   C1  C1  C1   C1  C1  C1   C1  C7  C24      parts           50  50   50  50  50   70  60  40   30  50  50Blending Resin (D)      No.  D6  D7   D8  D9  D10  D7  D7  D7   D7  D7  D7      parts           50  50   50  50  50   30  40  60   70  50  50Properties ofResin MixtureMn              3700               4900 6300                        8200                            10600                                 6400                                     5600                                         4400 4000                                                  5000                                                      4000Mw              38500               40000                    41000                        44000                            48000                                 53000                                     46000                                         33000                                              27000                                                  159000                                                      73000Mw/Mn           10  8.2  6.5 5.4 4.5  8.3 8.2 7.5  6.8 32  18Tg (°C.) 60.0               61.3 60.0                        61.5                            61.8 62.0                                     61.8                                         61.5 61.4                                                  60.5                                                      60.8Properties of TonerBlocking resistance           ⊚               ⊚                    ⊚                        ⊚                            ⊚                                 ⊚                                     ⊚                                         ⊚                                              ⊚                                                  ⊚                                                      .circleincircle                                                      .Pulverizability ⊚               ⊚                    ⊚                        ⊚                            ⊚                                 ⊚                                     ⊚                                         ⊚                                              ⊚                                                  ⊚                                                      .circleincircle                                                      .Fixing temperature           132 137  142 145 150  142 139 135  135 137 136(°C.)Offset-initiating           220 220  220 220 225  230 220 210  200 250<                                                      240temperatureHeat resistance ⊚               ⊚                    ⊚                        ⊚                            ⊚                                 ⊚                                     ⊚                                         ⊚                                              ⊚                                                  ⊚                                                      .circleincircle                                                      .Image density   dense               dense                    dense                        dense                            dense                                 dense                                     dense                                         dense                                              dense                                                  dense                                                      denseFogging         ⊚               ⊚                    ⊚                        ⊚                            ⊚                                 ⊚                                     ⊚                                         ⊚                                              ⊚                                                  ⊚                                                      .circleincircle                                                      .Resistance against migrationof polyvinyl chlorideplasticizer__________________________________________________________________________
By using the resin mixture (E) E10 prepared in Example 35, a positively chargeable toner 59 was prepared in the same manner as described in Example 35 except that 2 parts of Nigrosine Base EX (C.I. Solvent Black 7; supplied by Hodogaya Kagaku K.K.) was used as the charge-controlling agent instead of Spiron Black TRH.
TABLE 9______________________________________Example No.             59______________________________________Resin Mixture (E) No.   E10Blocking Resistance     ⊚Pulverizability         ⊚Heat Resistance         ⊚Lower Limit of Fixing Temperature (°C.)                   136Offset Initiation Temperature (°C.)                   250<Image Density           denseFogging                 ⊚Resistance against Migration of Polyvinyl                   ⊚Chloride Plasticizer______________________________________
(10) The blocking resistance was determined with the naked eye based on the degree of agglomeration caused when the formed toner was allowed to stand still for 24 hours in an environment maintained at a temperature of 50° C. and a relative humidity of 60%, according to the following scale:
(12) The toner melt-kneaded at a temperature of 160° C. for an average residence time of 2 minutes by a twin screw extruder (Model PCM-30 supplied by Ikegai Tekko K.K.) was dissolved in acetone and the insoluble components other than the urethane-modified resin (C) or (E) were removed by centrifugal sedimentation. The molecular weight of the obtained urethane-modified resin (C) or (E) was measured by GPC.
(13) Lowest surface temperature of the heat-fixing roll necessary for attaining a toner layer weight residual ratio of at least 80% when the toner layer on a solid black portion of 2 cm×2 cm on the formed image was rubbed 50 times with a rubber eraser under a load of 125 g/cm2 by using a Gakushin type friction fastness tester (supplied by Daiei Kagaku Seiki Seisakusho K.K.).
(17) A commercially available polyvinyl chloride sheet (containing 50% by weight of dioctyl phthalate; supplied by Mitsui Toatsu Kagaku K.K.) was piled on a solid black portion of 5 cm×5 cm and the assembly was allowed to stand still at 50° C. for 24 hours under a load of 20 g/cm2. Then, the sheet was peeled at room temperature, and migration of the toner to the polyvinyl chloride film was evaluated with the naked eye according to the following scale:
1. A heat-fixable toner composition for the electrophotography, which comprises as a main component a urethane-modified polyester resin (C) obtained by reacting a polyester resin (A) having a number average molecular weight of 6000 to 15000 with an isocyanate compound (B) in an amount of 0.05 to 0.95 mole-equivalent per mole of the hydroxyl group of the polyester resin, said resin (C) having a glass transition temperature of 40° to 80° C.
3. A heat-fixable toner composition for the electrophotography, which comprises as a main component a resin mixture (E) comprising a urethane-modified polyester resin (C) obtained by reacting a polyester resin (A) having a number average molecular weight of 1000 to 15000 with an isocyanate compound (B) in an amount of 0.05 to 0.95 mole-equivalent per mole of the hydroxyl group of the polyester resin (A), said resin (C) having a glass transition temperature of 40° to 80° C., and a polymer (D) having a number average molecular weight of 1000 to 10000, the (C)/(D) weight ratio being in the range of from 30/70 to 95/5 and the glass transition temperature of said resin mixture (E) being 40° to 80° C.
US07110695 1986-01-30 1987-01-30 Toner composition for the electrophotography Expired - Lifetime US4833057A (en)
JP1679986 1986-01-30
JP5369086 1986-03-13
JP61-53690 1986-03-13
JP61-59571 1986-03-19
JP5957186 1986-03-19
JP61-59570 1986-03-19
JP5957086 1986-03-19
JP61-16799 1986-04-30
US4833057A true US4833057A (en) 1989-05-23
ID=27456654
US07110695 Expired - Lifetime US4833057A (en) 1986-01-30 1987-01-30 Toner composition for the electrophotography
US (1) US4833057A (en)
EP (1) EP0256136B1 (en)
DE (2) DE3789924D1 (en)
WO (1) WO1987004811A1 (en)
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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MISAWA, AKIRA;SATO, HISATOMO;ISHIKAWA, KEIICHI;AND OTHERS;REEL/FRAME:004803/0325