Abstract:
A polyester resin for a toner capable of being stably prepared without an occurrence of an abrupt crosslinking reaction is provided. This polyester resin has a crosslinked structure and is derived from (a) at least one member selected from the group consisting of tribasic and tetrabasic carboxylic acid components and trihydric and tetrahydric alcohol components, (b) an aromatic or alicyclic diol component, at least one of the hydroxyl groups of which is a secondary hydroxyl group, (c) optionally other diol component, and (d) a dicarboxylic acid component, wherein the contents of the units of the component (a) and the units of the component (b) satisfy the requirement represented by the following formula (1): 
     
       (8m+20n)a-(80m+80n)≦b≦(8m+20n)a-(12m+30n)    (1) 
     
     wherein m represents the molar fraction of the tribasic carboxylic acid component and trihydric alcohol component units in the units derived from the component (a), n represent the molar fraction of the tetrabasic carboxylic acid component units and tetrahydric alcohol component units in the units derived from the component (a), the sum of m and n is equal to 1, and a and b represent the molar ratios (mole %) of the units of the component (a) and the units of the component (b) based on the total of the carboxylic acid components, respectively.

Description:
BACKGROUND OF THE INVENTION 
     (1) Field of the Invention 
     The present invention relates to a polyester resin for a toner usable for developing an electrostatic charged image and a magnetic latent image in electrophotography, electrostatic recording, electrostatic printing and the like. 
     (2) Description of the Related Art 
     For forming an image in electrophotography, electrostatic printing or the like, a method is adopted in which an image to be recorded is converted to an electronic latent image such as an electrostatic charged image or an electroconductive image on the surface of an electrostatic recording material, the latent image is developed and formed with a charged toner, and the formed toner image on the surface of the electrostatic recording material is transferred and fixed on a paper sheet or a recording film. This image-forming method is advantageous in that the copying operation can be performed at a high speed, the fixing stability of the image on the surface of the recording material is good, and the apparatus used can be manipulated very easily. Accordingly, this image-forming method is widely utilized in the fields of copying machines, laser printers and the like. 
     For example, for a formation of images by electrophotography, the surface of a roller composed of a photoconductive photosensitive material is subjected to a charging treatment, an electrostatic latent image formed by light exposure to rays reflected from the surface of an original is formed with a toner, the obtained toner image is transferred to a paper sheet or the like, and the transferred toner image is fixed to the paper sheet by compression under heating. 
     As the binder resin for the toner, there are used a styrene/acrylic resin, a polyester resin, an epoxy resin and the like, but recently a polyester resin has attracted attention as a binder resin having an excellent fixing property, giving a good image, and having a good resistance to plasticizers which are conventionally used for polyvinyl chloride and other resins. 
     As important properties required for the toner, there can be mentioned the fixing property and the non-offset property. A process for providing a toner having an excellent fixing property and non-offset property, by giving a crosslinked structure to a binder resin by using a trifunctional or higher polyfunctional monomer, has been proposed. A typical instance of the polyester resin for a toner having a crosslinked structure is disclosed in the specification of U.S. Pat. No. Re. 31,072. 
     This polyester resin having the crosslinked structure is inevitably prepared through a crosslinking reaction. The crosslinking reaction is different from the polycondensation reaction for a usual linear polyester resin in that the crosslinking reaction is abruptly advanced and a gel is readily formed. Accordingly, the control of the reaction is a very serious problem. In the specification of U.S. Pat. No. 4,849,495, the present inventors have proposed a process for the preparation of a crosslinked polyester in which the polycondensation reaction is carried out under a high vacuum of 150 Torr or less, the vacuum degree is gradually reduced from the point of a start of the crosslinking reaction, and the advance of the crosslinking reaction is thus controlled. Nevertheless, it has been found that, when this preparation process is conducted on an industrial scale, the gelation control sometimes becomes difficult according to the composition of monomers. Namely, it has been found that, in the industrial preparation of a crosslinked polyester, the ease of the control of the gelation depends greatly on the composition of monomers. 
     SUMMARY OF THE INVENTION 
     The present inventors carried out an investigation with a view to solving the above-mentioned problem, and as a result, found that if a trivalent or tetravalent monomer (so-called crosslinking agent) and an aromatic or alicyclic diol component having a low esterification reactivity, at least one of hydroxyl groups of which is a secondary hydroxyl group, are used at a specific fixing ratio, a polyester resin having a crosslinked structure can be stably prepared. The present invention was completed based on this finding. 
     Therefore, a primary object of the present invention is to provide a polyester resin for a toner, which can be stably prepared without an occurrence of an abrupt crosslinking reaction. 
     In accordance with the present invention, there is crosslinked structure, which is derived from (a) at least one member selected from the group consisting of tribasic and tetrabasic carboxylic acid components and trihydric and tetrahydric alcohol components, (b) an aromatic or alicyclic diol component, at least one of the hydroxyl groups of which is a secondary hydroxyl group, (c) optionally other diol component, and (d) a dicarboxylic acid component, wherein the contents of the units of the component (a) and the units of the component (b) satisfy the requirement represented by the following formula (1): 
     
         (8m+20n)a-(80m+80n)≦b≦(8m+20n)a-(12m+30n)    (1) 
    
     wherein m represents the molar fraction of the tribasic carboxylic acid component and trihydric alcohol component units in the units derived from the component (a), n represent the molar fraction of the tetrabasic carboxylic acid component units and tetrahydric alcohol component units in the units derived from the component (a), the sum of m and n is equal to 1, and a and b represent the molar ratios (mole %) of the units of the component (a) and the units of the component (b) based on the total of the carboxylic acid components, respectively. 
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The tribasic or tetrabasic carboxylic acid component used in the present invention is not particularly critical. For example, there can be mentioned trimellitic acid, toluene-tricarboxylic acid, cyclohexane-tricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-butane-tricarboxylic acid, 1,2,5-hexane-tricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylene-carboxylpropane, tetra(methylenecarboxyl)methane, 1,2,7,8-octane-tetracarboxylic acid and pyromellitic acid, and anhydrides and lower alkyl esters thereof. These polybasic carboxylic acid components can be used alone or in the form of mixtures of two or more thereof. 
     The trihydric or tetrahydric alcohol component used in the present invention is not particularly critical. For example, there can be mentioned glycerol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, 1,1,1-trimethylolbutane, pentaerythritol, 1,1,2,2-tetramethylolethane and 1,1,3,3-tetramethylolpropane. These polyhydric alcohol components can be used alone or in the form of mixtures of two or more thereof. 
     The dicarboxylic acid component used in the present invention is not particularly critical. For example, there can be mentioned terephthalic acid, isophthalic acid, phthalic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, malonic acid and glutaric acid, and anhydrides and lower alkyl esters thereof. These dicarboxylic acid components can be used alone or in the form of mixtures of two or more thereof. 
     The aromatic or alicyclic diol component, at least one of hydroxyl groups of which is a secondary hydroxyl group, used in the present invention is not particularly critical. For example, there can be mentioned polyoxypropylene(k)-2,2-bis(4-hydroxyphenyl)propane (k represents the number of moles of propyleneoxy units), cyclohexanediol, hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S. These diol components can be used alone or in the form of a mixture of two or more thereof. 
     The other diol component used in the present invention is not particularly critical. For example, there can be mentioned ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol and polyoxyethylene(1)-2,2-bis(4-hydroxyphenyl)propane (1 represents the number of moles of ethyleneoxy units). These diol components can be used alone or in the form of mixtures of two or more thereof. 
     The most important feature of the present invention is that the contents of units of (a) the trivalent or tetravalent polycarboxylic acid component and/or the trihydric or tetrahydric polyhydric alcohol component and units of (b) the aromatic or alicyclic diol component, at least one of hydroxyl groups of which is a secondary hydroxyl group, should satisfy the requirement represented by the above-mentioned formula (1). 
     If the quantity of units of the component (b) is smaller than the range defined by the formula (1), the crosslinking reaction speed is too high and it becomes difficult to stop the crosslinking reaction. If the quantity of units of the component (b) exceeds the range defined by the formula (1), the reactivity is too low and the reaction does not arrive at the crosslinking point. The quantities of the other diol component (c)(optional component) and the dicarboxylic acid component (d) are appropriately selected according to the quantities of the components (a) and (b) defined by the above-mentioned formula (1). 
     Preferably, the glass transition temperature (Tg) of the polyester resin of the present invention is 50° to 75° C. If the Tg is lower than 50° C., the blocking resistance of the toner is easily lowered, and if the Tg exceeds 75° C., the fixing property of the toner often becomes poor. 
     Preferably, the acid value of the resin of the present invention is not larger than 15 mg-KOH/g. If the acid value exceeds 15 mg-KOH/g, the moisture resistance of the toner often becomes poor. 
     The polyester resin of the present invention can be prepared according to procedures customarily adopted for the production of usual polyester resins. For example, the esterification or ester-exchange reaction is first carried out and continued until the distillation of water or a lower alcohol stops. For this reaction, a known ester-exchange catalyst can be used according to need. Then the polycondensation reaction is carried out under a vacuum of 150 Torr or less, and the reaction is concluded when the reaction mixture arrives at the desired degree of crosslinking. For this reaction, a known polycondensation catalyst can be used according to need. 
     In the instant specification, by &#34;the crosslinking point&#34; is meant the point at which the viscosity of the reaction mixture abruptly increases during the polycondensation reaction, and &#34;the resin having a crosslinked structure&#34; means a resin which has arrived at the crosslinking point. 
     The present invention will now be described in detail with reference to the following examples, that by no means limit the scope of the invention. 
     In the examples, the acid value of the polyester resin was determined by dissolving the sample in benzyl alcohol and titrating the solution with KOH, and the glass transition temperature Tg was determined as the crossing point of the base line of the chart obtained when the measurement was carried out at a temperature-elevating rate of 5° C./min, by using a differential scanning calorimeter and the tangential line of the heat absorption curve in the vicinity of Tg. 
    
    
     EXAMPLE 1 
     An autoclave having a distillation column and a capacity of 2 litters was charged with terephthalic acid, isophthalic acid, trimellitic anhydride, ethylene glycol, polyoxypropylene-(2,3)-2,2-bis(4-hydroxyphenyl)propane and neopentyl glycol according to the recipe shown in Table 1 (the total amount was 1 kg), and antimony trioxide was added in an amount of 500 ppm (by weight) based on the acid components and the esterification reaction was carried out. At the point at which the distillation of water formed by the reaction stopped, the esterification reaction was concluded. At this point, the stirring torque was 0.3 kg-cm at 100 rpm. Then the polycondensation was carried out at an inner temperature of 240° C. under a vacuum of 3 Torr, the viscosity of the reaction mixture began to increase, and when the torque reached 3.0 kg-cm, the vacuum state was released by nitrogen gas to return the pressure to atmospheric pressure. Stirring was continued while maintaining the inner temperature at 240° C., and although stirring was continued for 30 minutes, the torque was kept almost 3.0 kg-cm. Namely, in the resin of the present example, the crosslinking reaction was not violently advanced but could be stopped at a desired degree of crosslinking. The composition, Tg and acid value of the obtained resin are shown in Table 1. 
     
                       TABLE 1______________________________________             Charged                    Amount in             Amount Resin______________________________________Acid Componentstrimellitic anhydride (molar parts)               11       11terephthalic acid (molar parts)               89       89isophthalic acid (molar parts)               10       10Alcohol ComponentsBPPO*.sup.1 (molar parts)               55       55ethylene glycol (molar parts)               50       42neopentyl glycol (molar parts)               25       20m                    1n                    0a                   10b                   50Physical Properties of ResinTg (°C.)     63acid value (mg-KOH/g)                5______________________________________ Note *.sup.1 polyoxypropylene(2,3)-2,2-bis(4-hydroxyphenyl)propane (same will apply hereinafter in Tables 2, 4, 6 and 8) 
    
     EXAMPLES 2 THROUGH 5 
     According to the charged recipe shown in Table 2, the reaction was carried out in the same manner as described in Example 1. The obtained results are shown in Tables 2 and 3. In each of Examples 2 through 5, the crosslinking reaction could be stopped. 
     
                                           TABLE 2__________________________________________________________________________              2          3          4          5              Charged                   Amount                         Charged                              Amount                                    Charged                                         Amount                                               Charged                                                    AmountExample No.        Amount                   in Resin                         Amount                              in Resin                                    Amount                                         in Resin                                               Amount                                                    in__________________________________________________________________________                                                    ResinAcid Componentstrimellitic anhydride (molar parts)              10   10    14   14    --   --    --   --pyromellitic anhydride (molar parts)              --   --    --   --     3    3     5    5terephthalic acid (molar parts)              90   90    70   70    60   60    90   90isophthalic acid (molar parts)              --   --    10   10    37   37     5    5adipic acid (molar parts)              --   --     6    6    --   --    --   --Alcohol ComponentsBPPO               15   15    45   45    10   10    25   25hydrogenated bisphenol A (molar parts)              15   15     5    5    --   --    --   --ethylene glycol (molar parts)              90   70    60   54    125  116   65   59diethylene glycol (molar parts)              --   --    --   --     5    4    --   --BPEO*.sup.1        20   20    10   10    --   --    25   25m                   1          1         0          0n                   0          0         1          1a                  10         14         3          5b                  30         50         10         25Physical Properties of ResinTg (°C.)    58         65         51         61acid value (mg-KOH/g)               3         14         5          12__________________________________________________________________________ Note *.sup.1 polyoxyethylene(2,3)2,2-bis(4-hydroxyphenyl)propane (same will apply hereinafter in Table 10) 
    
     
                       TABLE 3______________________________________Example 2  torque increased to 3.5 kg-cm over a      period of 5 minutes after returning of the      pressure to atmospheric pressure, but      torque was then kept at this level for      30 minutes.Example 3  after returning of the pressure to      atmospheric pressure, torque was kept      almost 3.0 kg-cm for 30 minutesExample 4  same as in Example 3Example 5  after returning the pressure to      atmospheric pressure, torque increased to      3.8 kg-cm over a period of 10 minutes, but      torque was then kept at this value______________________________________ 
    
     EXAMPLES 6 THROUGH 8 
     The reaction was carried out according to the recipe shown in Table 4 in the same manner as described in Example 1 except that zinc acetate in an amount of 200 ppm (based on weight of the acid components) and dibutyl tin oxide in an amount of 400 ppm (based on the weight of the acid components) were used as the catalyst. The results are shown in Tables 4 and 5. In each of Examples 6 through 8, the crosslinking reaction could be stopped. 
     
                                           TABLE 4__________________________________________________________________________              6         7         9              Charged                   Amount                        Charged                             Amount                                  Charged                                       AmountExample No.        Amount                   in Resin                        Amount                             in Resin                                  Amount                                       in Resin__________________________________________________________________________Acid Componentsterephthalic acid (molar parts)              50   50   100  100  90   90isophthalic acid (molar parts)              50   50   --   --    5    5cyclohexane-dicarboxylic acid (molar parts)              --   --   --   --    5    5Alcohol Componentspentaerythitol (molar parts)               4    4    6    6   --   --trimethylol propane (molar parts)              --   --   --   --   15   15BPPO               40   40   65   65   60   60hydrogenated bisphenol A (molar parts)              --   --   10   10   10    9cyclohexanediol (molar parts)              10    7   --   --   --   --ethylene glycol (molar parts)              71   54   30   18   45   40triethylene glycol (molar parts)              --   --   10   10   --   --m                  0         0         1n                  1         1         0a                  4         6         15b                  47        75        69Physical Properties of ResinTg (°C.)    64        67        71acid value (mg-KOH/g)              2         5         6__________________________________________________________________________ 
    
     
                       TABLE 5______________________________________Example 6  after returning of the pressure to atmospheric      pressure, torque was kept about 3.0 kg-cm for      30 minutesExample 7  after returning of the pressure to atmospheric      pressure, torque increased to 3.5 kg-cm over a      period of 10 minutes but torque was then kept      constantExample 8  after returning of the pressure to atmospheric      pressure, torque was kept almost 3.0 kg-cm for      30 minutes______________________________________ 
    
     COMPARATIVE EXAMPLES 1 THROUGH 3 
     The reaction was carried out in the same manner as described in Example 1 except that the starting materials were charged in amounts shown in Table 6. In Comparative Example 1, the reaction did not arrive at the crosslinking point. In Comparative Examples 2 and 3, the crosslinking reaction could not be stopped. 
     
                                           TABLE 6__________________________________________________________________________              1         2         3Comparative        Charged                   Amount                        Charged                             Amount                                  Charged                                       AmountExample No.        Amount                   in Resin                        Amount                             in Resin                                  Amount                                       in Resin__________________________________________________________________________Acid Componentstrimellitic anhydride (molar parts)               6    6   19   19   --   --pyromellitic acid (molar parts)              --   --   --   --    8    8terephthalic acid (molar parts)              85   85   51   51   70   70isophthalic acid (molar parts)               9    9   30   30   --   --adipic acid (molar parts)              --   --   --   --   22   22Alcohol ComponentsBPPO (molar parts) 45   45   65   65   25   25hydrogenated bisphenol A (molar parts)               5    4    5    5   --   --ethylene glycol (molar parts)              70   56   40   35   100  901,4-butanediol (molar parts)              10    8   --   --   10    7m                  1         1         0n                  0         0         1a                  6         19        8b                  50        70        25Physical Properties of ResinTg (°C.)    --        61        53acid value (mg-KOH/g)              --        24        14__________________________________________________________________________ 
    
     
                       TABLE 7______________________________________Comparative     polycondensation was conducted for 10 hours,Example 1 but viscosity of reaction mixture did not     increaseComparative     after returning of the pressure to atmosphericExample 2 pressure, torque increased to 7.0 kg-cm over a     period of 10 minutes and viscosity rose, and     hence, stirring was stopped and resin was     taken out from reaction vesselComparative     after torque increased 1.0 kg-cm, viscosityExample 3 rose abruptly and reaction was not stopped     even by returning the pressure to atmospheric     pressure and stopping stirring, and viscosity     of resin became too high and recovery of resin     from reaction vessel was very difficult______________________________________ 
    
     COMPARATIVE EXAMPLES 4 THROUGH 6 
     The reaction was carried out in the same manner as described in Example 4 except that the starting materials were charged in amounts shown in Table 8. The results are shown in Tables 8 and 9. In Comparative Examples 4 and 5, the reaction did not arrive at the crosslinking point. In Comparative Example 6, the crosslinking reaction could not be stopped. 
     
                                           TABLE 8__________________________________________________________________________              4         5         6Comparative        Charged                   Amount                        Charged                             Amount                                  Charged                                       AmountExample No.        Amount                   in Resin                        Amount                             in Resin                                  Amount                                       in Resin__________________________________________________________________________Acid Componentsterephthalic acid (molar parts)              60   60   50   50   60   60isophthalic acid (molar parts)              40   40   50   50   40   40Alcohol Componentspentaerythritol (molar parts)               2    2    5    5   --   --trimethylolpropane (molar parts)              --   --   --   --   13   13BPPO (molar parts) 25   25   90   90   15   15hydrogenated bisphenol A (molar parts)               5    5   --   --   --   --ethylene glycol (molar parts)              70   53   25   13   77   69triethylene glycol (molar parts)              18   18   --   --   --   --neopentyl glycol (molar parts)              --   --   --   --   10    8m                  0         0         1n                  1         1         0a                  2         5         13b                  30        90        15Physical Properties of ResinTg (°C.)    --        --        57acid value (mg-KOH/g)              --        --        6__________________________________________________________________________ 
    
     
                       TABLE 9______________________________________Comparative     although polycondensation was conducted forExamples  10 hours, viscosity of reaction mixture did4 and 5   not riseComparative     after torque exceeded 1.0 kg-cm, viscosityExample 6 rose abruptly and reaction could not be     stopped even by returning the pressure to     atmospheric pressure and stopping stirring,     and viscosity of resin became too high and     recovery of product from reaction vessel was     very difficult______________________________________ 
    
     EXAMPLES 9 AND 10 
     The reaction was carried out according to the charged recipe shown in Table 10, in the same manner as described in Example 1. The results are shown in Tables 10 and 11. In each of Examples 9 and 10, the crosslinking reaction could be stopped. 
     
                       TABLE 10______________________________________      9           10        Charged  Amount   Charged                                 AmountExample No.  Amount   in Resin Amount in Resin______________________________________Acid Componentstrimellitic ahydride        18       18        7      7(molar parts)terephthalic acid        72       72       53     53(molar parts)isophthalic acid        10       10       40     40(molar parts)Alcohol ComponentsBPPO (molar parts)        60       60       40     40hydrogenated bis-         5        5       --     --phenol A(molar parts)ethylene glycol        65       60       80     74(molar parts)BPEO (molar parts)        10       10       --     --m             1            1n             0            0a            18            7b            65            40Physical Propertiesof ResinTg (°C.)        61            66acid value   4.8           5.2(mg-KOH/g)______________________________________ 
    
     
                       TABLE 11______________________________________Example 9   after returning the presence to atmospheric   pressure, torque increased to 3.7 kg-cm over a period   of 10 minutes, but torque was then kept almost con-   stant for 30 minutesExample 10   after returning the pressure to atmospheric pressure,   torque was kept at about 3.0 kg-cm for 30 minutes______________________________________ 
    
     As apparent from the foregoing detailed description, the polyester resin for a toner according to the present invention is a resin having a crosslinked structure, which has a combination of a good fixing property and a good non-offset property, and this polyester resin can be stably prepared without the occurrence of an abrupt crosslinking reaction.