CN1032009C - Composition having toner particeles for electrophotography - Google Patents

Abstract

The present invention relates to a toner composition for electrophotography, which is characterized in that urethane modified polyester resin is prepared by that isocyanate compounds react with polyester resin; the mol equivalent rate of the hydroxy of the polyester resin to the isocyanate group of the isocyanate compound is defined; the glass transition temperature of the obtained resin is in a specific range. The composition has the advantages of favorable fixity at low temperature and favorable properties of resisting displacement at high temperature; especially, the mixture of the composition and the polymers with low molecular weight has favorable properties.

Description

Toner composition for electrophotography

The present invention relates to a toner composition for electrophotography.

In electrophotography, printing speed is an important issue. If the machine itself is designed to print quickly, it can generally handle it, but in order to achieve fast printing while ensuring the printing screen, it alone cannot solve the problem. That is, it is necessary to improve the properties of the phase developing material used, especially the properties of the toner therein.

However, conventional toners may not be able to meet the requirements of high-speed printing. The reason is as follows. During fast printing, the toner particles on the printing paper receive less heat from the heat-fixing roller than at low speeds, and the speed at which the printing paper absorbs heat from the heat-fixing roller increases. As a result, the thermal The surface temperature of the fixing roller drops sharply, deteriorating the fixing of the toner. Therefore, it is required to be able to fix with lower heat, and it is required that dislocation does not occur at the fixing temperature and fixing speed, but it is really difficult to achieve it with the toner composed of traditional styrene-based adhesive resin and carbon black. this goal.

As a solution to this problem, for example, there is a method of applying silicone oil to the fixed roller to prevent displacement. Although this method is used, if the dislocation preventing liquid is not added at regular intervals, the dislocation phenomenon will gradually occur, and eventually the dislocation will be completely trapped. Therefore, in order to prevent the deterioration of the image quality, it is necessary to frequently add silicone oil or the like, that is, it is necessary to perform so-called maintenance work which takes a lot of labor. Moreover, the thermal aging products of the oil will contaminate the interior of the printer, which is a big problem in practice.

Japanese Unexamined Patent Publication No. 49-101031 describes a method of crosslinking a part of an adhesive resin to improve dislocation resistance. In this method, the cross-linking reaction formed by vinyl monomer is a chain reaction caused by free radical reaction, which is difficult to control. And, even if it can prevent the dislocation phenomenon at high temperature to a certain extent, because of the increase of the minimum fixing temperature at the same time, it makes it difficult to fix at low heat. If it is required to achieve fast printing, the fixing temperature has to be changed Increase the temperature, but increase the fixed temperature, there are various problems such as the capacity of the printer's electrical appliances cannot be increased and the aging of the printing paper is caused. Therefore, it is difficult to achieve fast printing with this method.

In addition, JP-A-59-50448 discloses a toner in which a nitrogen-containing unsaturated resin in the main chain of the component is copolymerized with an ethylene monomer resin. This resin is also produced by radical polymerization, so it has the same problem as JP-A-49-101031.

The object of the present invention is to provide a toner composition for electrophotography which can print quickly with low heat and always provide stable high-quality pictures without requiring maintenance.

The inventors of the present invention conducted intensive research in order to accomplish the above-mentioned problems, and as a result found that the urethane-modified polyester resin obtained by reacting isocyanate in the polyester resin has good fixability at low temperature and good dislocation resistance at high temperature, especially It is the fact that particularly superior properties are seen in mixtures thereof with lower molecular weight polymers, which led to the completion of the present invention. That is, the present invention is a toner for electrophotography, characterized in that 0.05-0.95 molar equivalent of isocyanate compound (B) is reacted with polyester resin (A) having 1 molar equivalent of hydroxyl group and having a number average molecular weight of 1000-15000 Obtain a urethane modified polyester resin (C), the resin (C) has a glass transition temperature of 40-80°C, an electrophotographic toner composition with this as the main component, and 0.05-0.95 mole The equivalent isocyanate compound (B) reacts with a polyester resin (A) having a number average molecular weight of 1000-15000 with 1 molar equivalent of hydroxyl groups, and the resulting urethane modified polyester resin (C), the resin (C) The glass transition temperature is 40-80 ℃, and contains the polymer (D) that the number average molecular weight is 1000-10000, is 30: 70-95: 5 to mix by (C): (D) weight ratio, and its glass transition temperature It is a resin mixture (E) at 40-80°C, and a toner composition for electrophotography containing (E) as a main component.

The best form for carrying out the invention:

The polyester resin (A) in the present invention is a condensation polymer of polyvalent carboxylic acid and polyvalent alcohol. The polyvalent carboxylic acids mentioned here, for example, aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, hexahydrophthalic anhydride, cis Butenedioic acid, maleic anhydride, fumaric acid, methylene succinic acid, citraconic acid and other aliphatic unsaturated dibasic acids, and phthalic anhydride, phthalic acid, terephthalic acid , isophthalic acid and other aromatic dibasic acids and their lower alkyl esters, among which aromatic dibasic acids and/or their lower alkyl esters are the most preferred.

The polyvalent alcohols mentioned here include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexanediol , neopentyl glycol, diethylene glycol, dipropylene glycol, hydrogenated bisphenol A, bisphenol A ethylene oxide addition, bisphenol A propylene oxide addition, etc., as well as glycerin, tri Trihydric alcohols such as methylolpropane and trimethylolethane. Among them, bisphenol A propylene oxide adduct is the best.

The polycondensation method generally adopts the well-known high-temperature polycondensation method, solution polycondensation method, etc., for example, the polycondensation temperature is 200-250° C., and the polymerization time is 3-20 hours.

The use ratio of polycarboxylic acid and polyol, the ratio of the hydroxyl group of the latter to the carboxyl group of the former is generally 0.8-1.4. In addition, the number average molecular weight of the polyester resin (A) is 1000-15000. When the number average molecular weight of (A) is less than 1000, the dislocation resistance of the resulting urethane-modified polyester (C) decreases, and if it is greater than 15000, the viscosity of the polyester resin (A) reacts with the polyisocyanate (B) Significantly higher, which is not good for manufacturing. Furthermore, the fixability of the urethane-modified resin (C) is lowered, which is also not preferable. The heat resistance of the obtained urethane modified polyester resin (C) in the range of 6,000-10,000 with a number average molecular weight of 6,000-10,000 is very excellent. In the production of toner, the molecular weight hardly decreases during high-temperature melting and kneading, and the dislocation resistance Good, and there is no blurring in the picture, the quality is particularly good. If the number average molecular weight is less than 6000, the molecular weight of the urethane-modified resin (C) decreases during melt-kneading, and fogging tends to occur, thereby lowering dislocation resistance.

图中，R₁表示从H-，CH₃-，CH₃CH₂-中任选的一种基，R₂表表示从-(CH₂)₆-， 中任选的一种或数种基(但同一式中R₂相同也可，不相同也可)。In addition, the polyisocyanate (B) in the present invention includes, for example, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylbenzene diisocyanate, Diisocyanates such as methyl diisocyanate and polyisocyanates with 3-6 functional groups shown in the following items (1)-(5) can be exemplified as follows:

In the figure, R ₁ represents an optional group from H-, CH ₃ -, CH ₃ CH ₂ -, R ₂ represents from -(CH ₂ ) ₆ -, One or several optional groups (but in the same formula, R ₂ may be the same or not).

The usual amount of isocyanate compound (B) is in the range of 0.05-0.95 molar equivalent to 1 molar equivalent of hydroxyl polyester resin (A). If the amount of isocyanate compound (B) is less than 0.05 molar equivalent, the dislocation resistance of the toner will be reduced, and if it exceeds 0.95 molar equivalent, the viscosity will be significantly increased during the reaction, sometimes causing urethane modified polyester resin (C ) of gelling, the quality is not good.

The appropriate range of the amount of isocyanate compound (B) is 0.3-0.95 molar equivalents from dislocation resistance requirements when diisocyanate is used, and the optimum range is 0.4-0.9 molar equivalents. When using 3-6 functional isocyanate, it is required in terms of dislocation resistance and ease of manufacture, the suitable range is 0.05-0.3 molar equivalent, and the optimum range is 0.1-0.25 molar equivalent.

The urethane-modified polyester resin (C) can be prepared as follows. For example, put the isocyanate compound (B) into the polyester resin (A) alone or in a solution containing the polyester resin (A) once or in several batches at 80-150° C. available in hours.

In the present invention, the urethane-modified polyester resin (C) can be used alone, but if the polymer (D) with a number average molecular weight of 1000-10000 is used in combination with it, there will be problems in the toner production process. The crushability of the polymer can be improved, and the fixability at low temperature can also be improved. More preferably, the polymer (D) can be, for example, a polyester resin or an ethylene-based copolymer.

The polyester resin that can be obtained by the same method as the polyester resin (A) about the polyester resin, the polycarboxylic acid and the polyhydric alcohol used are the same as those exemplified in the polyester resin (A), and some of them can also be mentioned here. The most preferred polyester resin is the condensation product of bisphenol A propylene oxide adduct and terephthalic acid (dimethyl). When using polyester resin, the molecular weight is best when the number average molecular weight is 1000-5000, more preferably when it is 2000-4000. If the number average molecular weight is less than 1000, the dislocation resistance of the toner obtained from the resin mixture (E) is unfavorably lowered, and if it exceeds 5000, the obtained toner is also unfavorable and has poor fixability.

As the ethylene-based polymer, the number-average molecular weight of 2,000-10,000 is preferably obtained by copolymerizing ethylene-based monomers, and it can usually be prepared by block polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the like.

The so-called vinyl monomers here include aromatic vinyl compounds such as styrene and α-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoacrylate, etc. Butyl, cyclohexyl acrylate, 2-ethylhexyl acrylate, octadecyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate ester, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octadecyl methacrylate, dodecyl methacrylate, acrylic acid, methyl Acrylic acid, (meth)acrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylonitrile, vinyl chloride, vinyl acetate, propionyl, methacrylonitrile, acrylic acid amide, Methacrylic acid amide, etc., the best vinyl copolymer is a copolymer of styrene and alkyl (meth)acrylate.

The molecular weight of the above-mentioned ethylene-based copolymer is preferably 2,000-10,000, most preferably 3,000-6,000. When it is less than 2000, the quality of the toner obtained from the resin compound (E) is not good, and its dislocation resistance and anti-clogging property are all reduced, but if it is more than 10000, the pulverization of the resin mixture (E) is reduced, and the quality is not good .

The content ratio of the urethane modified polyester resin (C) in the resin mixture (E) to the polymer (D) is 30:70-95:5 in terms of weight ratio (C):(D), and 40:60-70:30 is better. When the content of the urethane-modified polyester resin (C) is less than 30% by weight of the total of the two, the quality of the toner obtained with the resin mixture (E) is poor, and its dislocation resistance is lowered, while in When the content of the polymer (D) is less than 50% by weight of the total of both, the pulverizability of the toner deteriorates.

In addition, the glass transition temperature of the urethane-modified polyester resin (C) and the resin mixture (E) is 40-80°C, preferably 50-70°C. When the glass transition temperature is lower than 40°C, the anti-clogging performance of the toner deteriorates and the quality is not good, and if it exceeds 80°C, the fixing performance of the toner deteriorates and is also not good.

The resin mixture (E) can be produced, for example, as follows. Urethane-modified polyester resin (C) alone or a solution containing urethane-modified polyester (C), and polymer (D) alone or a solution containing polymer (D) as specified Proportion, stir and mix in a long-necked bottle, heat if necessary, and then, in order to remove excess solvent, residual monomer and odor caused by heat aging, high temperature and high vacuum treatment can be used. As a solvent, toluene, xylene, cyclohexanone, etc. can be used, for example.

As the most common method for preparing the toner composition for electrophotography of the present invention, for example, pulverize the urethane-modified polyester resin (C) or the above-mentioned resin mixture (E) into particle diameters of about 0.5-2mm particles, then add carbon black, if necessary, add acrylic resin, styrene resin, epoxy resin, maleated rosin, petroleum resin, colorant, ferrite, magnet and other magnetic Powder, and a small amount of charge regulator and wax are mixed with a Herschel mixer, etc., and then melted and kneaded with a kneader at 100-180°C, and the resulting bulk material is crushed and classified to obtain the particle size Particles of 5-20μm. The amount of urethane-modified polyester resin (C) or resin mixture (E) in the toner is generally 50-99wt% when no magnetic powder is added, and generally 10-99wt% when magnetic powder is added.

The toner obtained from the composition of the present invention includes a single-component series toner containing magnetic powder, or a two-component series toner mixed with a carrier, all of which are excellent products. It can always give a high-quality picture with stable quality, and it does not require special maintenance, and it is indeed a toner suitable for fast printing.

Next, while explaining the production examples of the polyester resin (A), the urethane-modified polyester resin (C) and the resin mixture (E) used in the present invention, the electrophotography color development obtained by using them will be described. Examples of properties of the agents are given to illustrate the invention in more detail. In addition, parts are parts by weight unless otherwise specified.

Example 1-9

(Production Examples A1-A9 of Polyester Resin (A))

On the 10l 4-necked long-necked flask, a reflux cooler, a water separator, a nitrogen introduction pipe, a thermometer and a stirring device are installed, and polycarboxylic acids and polyhydric alcohols in the weight ratio shown in Table 1 are added, and 0.05wt of catalyzer is added. % dibutyltin oxide, nitrogen gas is passed into the flask, and the dehydration polycondensation reaction is carried out at a temperature of 240°C in the flask.

Cooling is carried out when the acid value reaches below 1 to obtain the polyester resin (A) with the properties shown in Table 1.

[Production examples C1-C9 of urethane-modified polyester resin (C)]

The polyester resin (A) and xylene in the weight ratio shown in Table 1 are added to a 10l 4-necked flask, and the flask is equipped with a reflux cooler, a nitrogen introduction pipe, a thermometer and a stirring device. When the internal temperature was 120°C, according to the weight ratio shown in Table 1, the isocyanate compound was divided into four parts, added into the flask four times per hour, and then reacted at the same temperature for 1 hour. Then install a solvent separation device on the long-necked bottle, gradually increase the temperature in the bottle, distill off the xylene under normal pressure, and then install a decompression device, and completely distill off the volatile group at the temperature in the bottle of 190°C and the internal pressure of 10mmHg. Points, just get the urethane modified polyester resin (C) with the properties shown in Table 1.

(Toner Production Examples 1-9)

After the urethane modified polyester resin (C) C1-C9 obtained in this way is coarsely crushed into particles with a particle diameter of 0.5-2mm with a hammer mill, the carbon black MA 5 parts by weight of -100 (manufactured by Mitsubishi Chemical Industry Co., Ltd.), 2 parts by weight of "Speron Black TRH" (manufactured by Hodogaya Chemical Co., Ltd.) as a charge regulator, polypropylene-based wax, "Viscoel 550P" (manufactured by Sanyo Chemical Industry Co., Ltd.) 2 parts, bisamide wax "Amora EBS" (manufactured by Leon Arma Corporation) 3 parts, dispersed and mixed in a Herschel mixer, at 1600 ° C Next, melt kneading on a two-axis kneading machine PCM30 (manufactured by Ikegai Iron Works Co., Ltd.) to obtain a block-shaped toner composition.

The composition was coarsely pulverized with a hammer mill, then finely pulverized with a jet mill (IDSZ type manufactured by Nihon Mazik, Japan), and then classified with an airflow classifier (DS-2 type manufactured by Niu Mazik, Japan), Toner particles having an average particle diameter of 10 μm (3% by weight of 5 μm or less and 2% by weight of 20 μm or more) were obtained. Taking the weight of the toner particles as 100 parts, 0.4 parts of hydrophobic silica fine powder R-972 (manufactured by Nippon Adosier Co., Ltd.) was added and mixed therein to obtain test toners 1-9.

4 parts by weight of the toner was mixed with 96 parts of ferrite carrier F-150 (manufactured by Nippon Iron Powder Co., Ltd.) to obtain a two-component developer.

Table 1 shows the fixing properties of the printing test by changing the temperature of the heat roller using a commercially available magnetic printing machine (Toshiba Leodoray 8411).

Table 1 also shows the picture characteristics when printing up to 50,000 sheets and the anti-vinyl chloride plasticizer migration of the toner after fixing.

Table 1 also shows the thermal stability of the resin in the kneading process during the production of the toner composition, the pulverizability of the toner when finely pulverized, and the anti-clogging performance of the obtained toner.

As is understood from the results in Table 1, due to the use of the toner obtained according to the present invention, a good picture can be provided in a sufficiently wide temperature range necessary for fast printing.

In addition, the toner is also excellent in clogging resistance, heat resistance and migration resistance of vinyl chloride plasticizers, and its pulverization property is also good, so that it does not pose a practical problem.

Table 1 Example 1 2 3 4 5 6 7 8 9 Polyester resin (A) KB300K (1) (parts by weight) diethylene glycol (parts by weight) neopentyl glycol (parts by weight) 1.6-hexanediol (parts by weight) trimethylol propane (parts by weight) glycerin (parts by weight) Isophthalic acid (parts by weight) terephthalic acid (parts by weight) dehydration (parts by weight) acid value (mg KOH/g) ²⁾ hydroxyl value (mg KOH/g) ³⁾ Mn 4) Mw 5 )Mw/Mn6) A145414039886＜1306300151002.4 A238716941590＜1316100146002.4 A348216542392＜1316200149002.4 A446414340788＜1306300150002.4 A538716941590＜1316100150002.5 A65661714.4498108＜1346400173002.7 A775221818631137＜1456200192003.1 A880522821664144＜1516100248004.1 A959317210498144＜1466200185003.0

Table 1 (continued) Example 1 2 3 4 5 6 7 8 9 Urethane modified polyester resin (C) Polyester resin (A) (parts by weight) xylene (parts by weight) MDI (7) (parts by weight) NCO/OH (8) Mn (4) Mw (5) Mw/Mn (6) TTg (9 ) (℃) C11000100053.50.812000780006.562.3 C21000100054.60.811000770007.061.4 C31000100053.80.812500780006.260.9 C41000100052.90.812000750006.361.5 C51000100054.60.811800770006.560.5 C61000100045.50.6120003000002560.3 C71000100042.90.43110003200002961.5 C81000100045.50.4115003200002860.7 C91000100044.10.43110003100002861.3 toner Anti-clogging (10) Pulverization (11) Heat resistance (12) Lower limit fixed temperature (°C) (13) Dislocation initiation temperature (°C) (14) Screen concentration (15) Fog (16) Anti-vinyl chloride plasticity Agent Migration (17) ◎○◎150250 concentrated◎◎ ◎○◎148250 concentrated◎◎ ◎○◎150250 concentrated◎◎ ◎○◎150250 concentrated◎◎ ◎○◎150250 concentrated◎◎ ◎○◎150250＜Concentrated◎◎ ◎○◎148250＜Concentrated◎◎ ◎○◎150250＜Concentrated◎◎ ◎○◎150250＜Concentrated◎◎

Example 10-21

With the same method shown in embodiment 1-9, prepare polyester resin (A) A10-A21 and urethane modified polyester resin (C) C10-C21, the property of these resins is shown in table 2.

Here, using the obtained urethane-modified polyester resin (C) C10-C21, toners 10-21 were prepared in the same manner as shown in Examples 1-9, and the performance test results are shown in Table 2 .

As can be seen from Table 2, no matter which toner is used, the anti-clogging property and anti-vinyl chloride plasticizer migration property are excellent. The crushability is also good, which can ensure that there is no problem in practical use. However, the heat resistance, dislocation resistance and fogging degree vary with the molecular weight of the polyester resin (A) used, and the performance changes. If the molecular weight decreases, the heat resistance will deteriorate, and as a result, the dislocation resistance of the toner will deteriorate. , At the same time, it may be due to the poor dispersion of carbon black and charging regulator, which may cause the deterioration of the degree of fogging.

From the results in Table 1 and Table 2, it can be seen that when the urethane-modified resin (C) obtained from the polyester resin (A) with a molecular weight of 6000 or more is used, in the kneading process of toner production, the resin There is almost no heat aging and no reduction in molecular weight, so it can maintain its anti-displacement performance and good image quality.

Table 2 Example 10 11 12 13 14 15 16 17 18 19 20 twenty one Polyester resin (A) KB300K (parts by weight) diethylene glycol (parts by weight) neopentyl glycol (parts by weight) 1.6-hexanediol (″) trimethanol propane (″) glycerin (parts by weight) isophthalic acid (parts by weight) Number) terephthalic acid (parts by weight) dehydration amount (parts by weight) acid value (mg KOH/g) hydroxyl value (mg KOH/g) MnMwMw/Mn A1046514329965＜1156120024002.0 A11626193465101<193200044002.2 A122979224954＜147400092002.3 A13622192531115＜1375100117002.3 A14547169498108＜1238200197002.4 A155491664.336579＜190220060002.7 A166191791439886＜197230071003.1 A175371521743289＜1902500110004.4 A1869020016564122<1584300133003.1 A1964418715531115＜1515200161003.1 A2068019716581126＜1378500210002.5 A21341998.029965＜13310000340003.4

Table 2 (continued) Example 10 11 12 13 14 15 16 17 18 19 20 twenty one Urethane modified polyester resin (C) Polyester resin A (parts by weight) xylene (parts by weight) MDI (parts by weight) NCO/OHMnMwMw/Mn C10100010003300.9510000500005.058.5 C11100010001970.9512300750006.161.9 C121000100091.10.8712000720006.062.1 C131000100068.40.8312300760006.261.8 C141000100051.20.7812500780006.261.5 C15100010001600.80115003200002860.7 C16100010001280.59100002900002960.2 C171000100089.80.44110003000002758.5 C181000100064.60.50125003300002660.5 C191000100053.40.47120003400002862.3 C201000100034.60.42125003300002661.3 C211000100029.40.40128003600002860.5 toner Anti-clogging property Pulverization property Heat resistance Lower limit fixed temperature (°C) Dislocation initiation temperature (°C) Screen concentration is suppressed Anti-vinyl chloride plasticizer migration property ◎○×146190 thick×◎ ◎○×150210 thick×◎ ◎○△150220 thick△◎ ◎○△150225 thick△◎ ◎○◎150250 concentrated◎◎ ◎○×150220 thick×◎ ◎○×150220 thick×◎ ◎○×150220 thick×◎ ◎○△150240 thick△◎ ◎○△150245 thick△◎ ◎○◎150250＜Concentrated◎◎ ◎○◎150250＜Concentrated◎◎

Example 22-25

With the same manufacture method of the polyester resin (A) shown in embodiment 1-9, with the polyhydric alcohol and polycarboxylic acid of the shown in table 3 parts by weight, prepare polyester resin (A) A22-A25, gained Table 3 shows the properties of the polyester resins (A) A22-A25.

Next, use polyester resin (A) A22-A25 and isocyanate, with the same method as the manufacturing method of urethane modified polyester resin (C) shown in embodiment 1-9, prepare urethane modified Permanent polyester resin (C) C22-C25, the property of gained resin C is shown in table 3.

Using urethane-modified polyester resins (C) C22-C25, toners 22-25 were prepared in the same manner as in Examples 1-9, and Table 3 shows the results of performance tests on them.

As can be seen from Table 3, no matter what kind of toner it is, its fixable temperature range is very wide, and it is suitable for fast printing, and its anti-clogging property and anti-vinyl chloride plasticizer performance are also good.

In addition, its crushability is also good, so there is no problem in practical use. In terms of heat resistance, toner-22 and 23 were severely aged, and compared with toner-24 and 25, their misalignment resistance was also inferior, and the picture was blurred. Toner-24, 25 has excellent heat resistance and picture characteristics.

table 3 Example twenty two twenty three twenty four 25 Polyester resin (A) KB300K (parts by weight) diethylene glycol (parts by weight) isophthalic acid (parts by weight) dehydration (parts by weight) acid value hydroxyl value MnMw A22626193465101＜19320004400 A232979224954＜14740009200 A2445414039886＜130630013700 A2535811033272＜119970024000 Urethane modified polyester resin Polyester resin (A) (parts by weight) xylene (parts by weight) isocyanate (18) (parts by weight) NCO/OH C22100010001010.25 02310001000470.23 C2410001000260.2 C25100010008.30.1 Properties of Resin (C) MnMwMw/MnTg(°C) 42001350003260.5 56001380002561 80001450001859.7 110001300001259.7 Toner performance Anti-clogging property Pulverization property Heat resistance Fixed temperature dislocation Onset temperature Screen concentration covered Anti-vinyl chloride plasticizer Migration ◎◎×135230 thick×◎ ◎◎△143250 thick△◎ ◎○◎145250＜Concentrated◎◎ ◎○◎160250＜Concentrated◎◎

Example 26-36

(Production Examples D1-D5 of Polymer (D))

With the method identical with the manufacture method of the polyester resin (A) shown in embodiment 1-9, by the polyhydric alcohol shown in table 4 parts by weight, polycarboxylic acid and 0.05wt% dibutyl tin oxide synthetic polymerization Substances (D) D1-D4, Table 4 shows the properties of the obtained polymer (D).

In addition, in the above-mentioned production method, dehydration reaction is not used, but demethanol reaction is used for condensation, dibutyltin oxide is not used, and 0.05 wt% n-butyl orthotitanate is used as the transesterification catalyst, and the others are the same. The method synthetic polymer (D) D5, the property of gained polymer (D) is shown in table 4.

(Production Examples E1-E11 of Resin Mixture (E))

By the parts by weight shown in table 5, the synthetic urethane modified polyester resin (C) C1, C7, C24 and polymer (D) D1 shown in table 4 in embodiment 1,7,24 -D5, add 10l separable flask together with 100 parts by weight of xylene, after dissolving and mixing at 120°C in the bottle, distill off xylene in the same way as shown in Examples 1-9 , and then treated at a high temperature of 190° C. and 10 mmHg to obtain resin mixtures (E) E1-E11.

The properties of the resin mixtures (E)E1-E11 obtained here are shown in Table 5.

(Toner Production Examples 26-36)

Using resin mixtures (E) E1-E11, toners 26-36 were prepared in the same manner as shown in Examples 1-9.

Table 5 shows the results of tests conducted with Toners 26-36.

Toner 26 has no problem in practical use, but its anti-clogging property is somewhat insufficient, and other properties such as fixability and image characteristics are good, and it is also excellent in heat resistance. In addition, compared with the toners obtained in Examples 1-25, toners 26-36 have good crushability, easy production of toners, and high yields. In addition, they have low fixing temperature and sufficiently wide fixability. Temperature range, has very good properties for fast printing.

Table 4 Polymer (D) D1 D2 D3 D4 D5 Composition of polymer (D) KB-300K (parts by weight) isophthalic acid (parts by weight) terephthalic acid (parts by weight) dimethyl terephthalate (parts by weight) n-butyl orthotitanate (parts by weight) COOH/OHCOOCH ₃ /OH dehydration amount (weight parts) demethanolization amount (weight parts) 1376 1307 1342 1445 1238930 883 777 802 — — — — 873 — — — — 1.251.4 1.3 1.2 1.15 — — — — — 1.25144 137 140 151 — — — — 230 Properties of Polymer (D) OH value (mgKOH/g) MnMwTg (℃) <1 <1 <1 <1 <11100 2160 3200 3900 29502310 4540 7060 8970 679040.0 51.5 56.3 57.8 56.0

table 5 Example 26 27 28 29 30 31 32 33 34 35 36 Resin mixture (E) E1 E2 E3 E4 E5 E6 E7 E8 E9 E10 E11 Urethane modified NO polyester resin (C) parts by weight C1 C1 C1 C1 C1 C1 C1 C1 C1 C7 C2450 50 50 50 50 30 40 60 70 50 50 N polymer (D) parts by weight D1 D2 D4 D5 D5 D5 D5 D5 D5 D5 D5 D550 50 50 50 50 70 60 40 30 50 50 Properties of MnMw resin mixture Mw/MnTg(℃) 2020 3660 5050 5890 4740 3810 4230 5390 6250 4770 386037200 38300 39550 40500 39400 26400 32900 46000 52500 168400 7240018 10 7.8 6.9 8.3 6.9 7.8 8.5 8.4 35.3 18.851.3 56.8 59.2 60.0 59.1 57.7 58.2 59.5 60.2 61.3 61.6 Anti-clogging property, crushing color, lower limit fixed temperature (℃) agent, dislocation resistance, heat resistance, screen density, anti-vinyl chloride plasticizer migration ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 122 133 137 139 136 134 136 138 140 137 134215 220 220 220 220 200 210 225 230 450 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

(Resin mixture (E) production example E12-E23)

With the urethane modified polyester resin (C) C10-21 synthesized in the embodiment 10-21, and the polymer (D) D5 shown in the table 4, by the parts by weight shown in the table 6, and Add in the 10l divisible long-necked flask together with the xylene of 100 parts by weight, after dissolving and mixing at 120 ℃ of temperature in the bottle, distill off the xylene in the same method as shown in Examples 1-9, then, with 190 ℃, 10mmHg high temperature treatment to get the resin mixture (E) E12-E23.

The properties of the resin mixtures (E) E12-E23 obtained here are shown in Table 6.

(Toner Production Examples 37-38)

Using resin mixtures (E) E12-E23, toners 37-48 were prepared in the same manner as in Examples 1-9.

Table 6 shows the results of tests conducted with Toners 37-48.

In terms of anti-clogging, pulverization and anti-vinyl chloride plasticizer migration, no matter which toner shows excellent performance, but the heat resistance of toner 37-40 and 42-46 is not enough, the picture chaos, and its resistance to dislocation is reduced.

On the contrary, toners 41, 47 and toners 41, 47 and toners 41, 47 and 48. It has good heat resistance, a wide fixed range, and a good picture. It has excellent performance suitable for fast printing.

Table 6 Example 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 E23 Urethane modified polyester resin (C) № Parts by weight C1050 C1150 C1250 C1350 C1450 C1550 C1650 C1750 C1850 C1950 C2050 C2150 Polymer (D) № Parts by weight D550 D550 D550 D550 D550 D550 D550 D550 D550 D550 D550 D550 Properties of Resin Mixture MnMwMw/MnTg(°C) 4500280006.257.3 4800410008.559.0 4700390008.359.1 4800410008.558.4 4800420008.858.5 470016300034.758.0 460014800032.258.1 470015300032.657.5 480016800035.058.3 470017300036.859.7 480016800035.058.5 480018300038.158.3 Toner performance Anti-clogging, pulverization, fixed temperature (°C), dislocation, initial temperature, heat resistance, screen concentration, resistance to migration of vinyl chloride plasticizers ◎◎135160×Concentrated×◎ ◎◎136170×Concentrated×◎ ◎◎136180△Concentrated△◎ ◎◎136195△Concentrated△◎ ◎◎136220◎Concentrated◎◎ ◎◎135230×Concentrated×◎ ◎◎135230×Concentrated×◎ ◎◎136230×Concentrated×◎ ◎◎136235△Concentrated△◎ ◎◎135240△Concentrated△◎ ◎◎135250＜◎Concentrated◎◎ ◎◎136250＜◎Concentrated◎◎

Example 48-58

(Polymer (D) production example D6-D10)

Install a reflux cooler, a nitrogen gas introduction pipe, a thermometer and a monomer dropping device on a 10 l 4-necked flask, add xylene in parts by weight as shown in Table 7, and heat up until the xylene refluxes.

When the xylene was refluxing (140° C. in the bottle temperature), nitrogen gas was introduced into the long-necked bottle, and at the same time, the monomer and the polymerization initiator were dropped into the monomer and the polymerization initiator in the parts by weight shown in Table 7 from the monomer dropping device, and continuously dropped for 4 hours. .

After dropping, keep 140 DEG C in the bottle for 2 hours, cool after confirming that the non-volatile value in the solution is more than 99% of the theoretical value, dilute with xylene in parts by weight shown in Table 7, and stop the reaction completely.

Table 7 shows the properties of the polymer (D) obtained here obtained by removing volatiles such as xylene from the xylene solution of the polymer (D) at high temperature and under reduced pressure.

(Resin mixture (E) production example E23-33)

The urethane modified polyester resins (C) C1, C7, and C24 obtained in Examples 1, 7, and 24, and polymers (D) D6-D10 with properties shown in Table 7, as shown in Table 8 The parts by weight converted into the weight of the solid components are added in a 10l divisible flask, and after dissolving and mixing at a temperature of 120°C in the bottle, the xylene is distilled off in the same manner as shown in Examples 1-9, and then the Treat under reduced pressure to obtain the resin mixture (E) E23-E33.

Table 8 shows the properties of the resin mixtures (E) E23-E33 obtained here.

(Toner Production Examples 48-58)

In the same manner as shown in Examples 1-9, toners 48-55 were prepared using resin mixtures (E) E23-E33.

Table 8 shows the results of tests conducted with Toners 48-58. As can be seen from Table 8, no matter what kind of toner is used, it has a sufficiently wide fixed temperature range necessary for fast printing, and has excellent performance in terms of screen characteristics, anti-clogging properties, heat resistance and pulverization.

Table 7 Polymer (D) D6 D7 D8 D9 D10 Polymerization solvent Xylene (parts by weight) 150 150 100 80 60 vinyl monomer Styrene (parts by weight methyl methacrylate (parts by weight) ethyl acrylate (parts by weight) methacrylic acid 2 (parts by weight)—ethylhexyl methacrylic acid (parts by weight) 40573-- 404515-- 403327-- 4022-335 403327-- polymerization initiator Tert-butyl peroctanoate (t-buchiruba-oktoe-to) (parts by weight) 8.0 5.0 2.5 2.0 1.0 dilution solvent Xylene (parts by weight)polymerization temperature (°C) 50140 50140 100140 120140 140140 Copolymer properties MnMwMw/MnTg(°C) 220049002.457.8 310074002.460.4 4300100002.458.0 6200150002.459.0 9500230002.461.5

Table 8 Example 48 49 50 51 52 53 54 55 56 57 58 Resin mixture (E) E23 E24 E25 E26 E27 E28 E29 E30 E31 E32 E33 Urethane modified polyester resin (C) № Parts by weight C150 C150 C150 C150 C150 C170 C160 C140 C130 C150 C2450 Resin for mixing (D) № Parts by weight D650 D750 D850 D950 D1050 D730 D740 D760 D770 D750 D750 Properties of Resin Mixture MnMwMw/MnTg(°C) 3700385001060.0 4900400008.261.3 6300410006.560.0 8200440005.461.5 10600480004.561.8 6400530008.362.0 5600460008.261.8 4400330007.561.5 4000270006.861.4 50001590003260.5 4000730001860.8 Toner performance Anti-clogging property Pulverization Fixed temperature (°C) Dislocation initiation temperature Heat resistance Screen density covered Anti-vinyl chloride plasticizer migration ◎◎132220◎Concentrated◎◎ ◎◎137220◎Concentrated◎◎ ◎◎142220◎Concentrated◎◎ ◎◎145220◎Concentrated◎◎ ◎◎150225◎Concentrated◎◎ ◎◎142230◎Concentrated◎◎ ◎◎139220◎Concentrated◎◎ ◎◎135210◎Concentrated◎◎ ◎◎135200◎Concentrated◎◎ ◎◎137250＜◎Concentrated◎◎ ◎◎136240◎Concentrated◎◎

Example 59

With the resin mixture (E) E10 prepared in Example 35, the charge regulator does not use "Spyron" black TRH but uses aniline black series EX (C, I solvent black 7 produced by Hodogaya Chemical Co., Ltd.), parts by weight The number was 2, and a positively chargeable toner 59 was obtained in the same manner as in Example 35.

Using a commercially available printer SF-900 (manufactured by Sharp Co., Ltd.), the temperature of the fixed drum was changed, and the conditions for preparing a developer such as a carrier were evaluated in the same way as in Examples, and the results are shown below.

Table 9 Example 59 Resin mixture (E) № Anti-clogging property Pulverization property Heat resistance Lower limit fixed temperature (°C) Dislocation initiation temperature (°C) Picture concentration is suppressed Anti-vinyl chloride plasticizer migration E10◎◎◎136250＜Concentrated◎◎

As can be seen from Table 9, the positively charged toner 59 prepared from the resin mixture (E) E10, like the negatively charged toner 35, has a low lower limit fixed temperature suitable for fast printing and a wide Fixed temperature range, its resistance to clogging, pulverization, heat resistance and resistance to vinyl chloride plasticizer migration are also excellent, and can give a good quality picture.

The meanings of the notes in the table are as follows: 1) Bisphenol A—(2.2)—propylene oxide adduct (manufactured by Mitsui Topress Chemical Co., Ltd.) 2) JIS (Japanese Industrial Standard) K5400 method 3) Pyridine—Acetic anhydride method 4 ) is the number-average molecular weight obtained by gel permeation chromatography (GPC) with monodisperse standard polystyrene as the standard, tetrahydrofuran as the eluent, and a refractometer as the detector. 5) Weight average molecular weight obtained by the same method as 4). 6) Molecular weight distribution obtained by the same method as 4). 7) Diphenylmethane-4.4-diisocyanate. 8) Ratio of the isocyanate molar equivalent of the isocyanate (B) to the hydroxyl molar equivalent obtained from the hydroxyl value of the polyester resin (A). 9) Glass transition temperature determined by differential scanning calorimeter (DSC). 10) After placing the prepared toner in an environment with a temperature of 50°C and a humidity of 60% for 24 hours, visually observe the degree of powder aggregation, and judge according to the following marks.

◎: no condensation at all,

○: Slightly condensed, but the container is loosened by lightly shaking the container,

△: Even if the container is vibrated vigorously, there is no loose aggregate,

×: Completely agglomerated. 11) The yield of finely pulverized and classified particles with a particle size of 5-20 μm is as follows

determination.

◎: Yield over 90%,

○: Yield 80% - less than 90%,

△: Yield 70% - less than 80%,

×: The yield is less than 70%. 12) The mixing temperature of the biaxial kneading machine (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.)

The toner obtained by melting and kneading under the conditions of 160C and average residence time of 2 minutes,

Dissolved in acetone, the insoluble components other than resin (C) or (E) were centrifuged

After the separation, the fraction of the obtained urethane modified resin (C) or (E)

Quantities were determined by GPC.

The degree of reduction of the weight average molecular weight of the resin (C) or (E) after kneading

Compared with before mixing, the judgment is as follows:

◎: The decrease in weight average molecular weight is less than 5%,

○: The reduction in weight average molecular weight is 5% to less than 10%,

△: The decrease in weight average molecular weight is 10% to less than 20%,

×: The decrease in the weight average molecular weight is 20% or more. 13) Use Gakushin rubbing fastness tester (manufactured by Daiei Science Seiki Manufacturing Co., Ltd.),

With a load of 125g/ ^cm2 , make the black part of the bottom plate 2cm×2cm on the picture

After rubbing the toner with the sand rubber for 50 times, the weight residual rate of the toner layer exceeds

over 80% of the minimum heat-fixing drum surface temperature necessary. 14) The melted toner is attached to the heat-fixing liquid cartridge and starts to fix again on the printing paper.

The lowest heat-fixed roller surface temperature at which the so-called misalignment occurs. 15) Visually inspect the blackness of the black part of the bottom plate on the picture after printing 50,000 copies. 16) On the picture after printing 50,000 copies, visually inspect the toner attached to the background white ground

The degree of white ground pollution caused.

◎: No pollution,

○: There is little pollution,

△: There is considerable pollution,

×: Pollution is serious, 17) Commercially available polyvinyl chloride film (containing 50wt% dioctane phthalate, manufactured by Mitsui Topress Chemical Co., Ltd.

Co., Ltd.) superimposed on the black part of the bottom plate of 5cm×5cm, load

20g/cm ² , after 24 hours at 50°C, peel off the film at room temperature.

At this time, the migration state of the toner to the vinyl chloride film was measured, and the judgment was as follows:

◎: There is no migration of dye and toner at all,

○: Dye migration only,

△: Partial toner migration,

×: Most of the toner migrated. 18) Triphenylmethane triisocyanate manufactured by Sumitomo Bayer Co., Ltd. (in terms of solids).

Claims (4)

1. preparation method with urethane-modified vibrin (C) that is used for electrofax tinter of 40～80 ℃ of second-order transition temperatures, it is characterized in that making number-average molecular weight is 1000～15000 vibrin (A) and isocyanate compound (B) reaction, and the consumption of wherein said (B) is hydroxyl 0.05～0.95 molar equivalent of the said vibrin (A) of every molar equivalent.

2. the method for claim 1, the number-average molecular weight of wherein said vibrin (A) is 6000～15000.

3. the method for claim 1 wherein uses diisocyanate cpd as said isocyanic ester (B), and its consumption is hydroxyl 0.3～0.95 molar equivalent of every mole of said vibrin (A).

4. the method for claim 1, the polyisocyanate compounds that wherein uses 3～6 functional groups is as said isocyanate compound (B), and its consumption is hydroxyl 0.05～0.3 molar equivalent of every mole of said vibrin (A).