Ultralow-temperature fixing toner and preparation method thereof

Abstract

The invention discloses an ultralow-temperature fixing toner and a preparation method thereof. The ultralow-temperature fixing toner is prepared from the following raw materials in parts by weight: 60-100 parts of modified polybutylene terephthalate; 40 to 80 parts of PETG (polyethylene terephthalate glycol); 2-8 parts of a dispersant; 10 to 30 parts of carbon black; 1-3 parts of an antioxidant; the modified polybutylene terephthalate is prepared from the following raw materials: polybutylene terephthalate, starch, glycerol, sodium hexametaphosphate, calcium carbonate and calcium stearate. The present application has an effect of reducing the fixing temperature of the toner.

Description

Technical Field

[0001] The invention relates to the field of colorants, in particular to an ultra-low temperature fixing colorant and a preparation method thereof. Background Art

[0002] Thermal fixing is generally used for fixing images in copy machines, printers, and the like. Toner binders for electrophotography used in thermal fixing are required to be able to fix the toner even at low fixing temperatures (low-temperature fixability) and to have storage stability.

[0003] However, most toners on the market currently require higher temperatures to complete the fixing process, which not only increases energy consumption, but may also cause the equipment to overheat during the printing process, thereby affecting the equipment life and print quality.

[0004] Therefore, the development of toners that can be fixed under ultra-low temperature conditions has become an urgent need in the industry. Summary of the invention

[0005] In order to reduce the fixing temperature of a toner, the present application provides an ultra-low temperature fixing toner and a preparation method thereof.

[0006] In the first aspect, the present application provides an ultra-low temperature fixing toner using the following technical solution: A toner for ultra-low temperature fixing is made of the following raw materials in parts by weight: 60-100 parts of modified polybutylene terephthalate; 40-80 parts of PETG; 2-8 parts of dispersant; 10-30 parts of carbon black; and 1-3 parts of antioxidant. The modified polybutylene terephthalate is made of the following raw materials: polybutylene terephthalate, starch, glycerol, sodium hexametaphosphate, calcium carbonate and calcium stearate.

[0007] By adopting the above technical scheme, PETG and modified polybutylene terephthalate are used as carriers, carbon black is added as a pigment, and polybutylene terephthalate is modified to make the modified polybutylene terephthalate have good compatibility with PETG. The combination with carbon black with good stability is conducive to uniform dispersion of various components and reduces the minimum fixing temperature of the toner.

[0008] Preferably, the preparation method of the modified polybutylene terephthalate is: 80-120 parts by weight of starch, 10-30 parts by weight of glycerol, 10-20 parts by weight of polybutylene terephthalate and 5-15 parts by weight of sodium hexametaphosphate are mixed and stirred evenly, dried and crushed, then mixed and stirred with 50-90 parts by weight of calcium carbonate and 5-15 parts by weight of calcium stearate, and the modified polybutylene terephthalate is obtained after banburying and granulation.

[0009] By adopting the above technical scheme, glycerol and sodium hexametaphosphate make starch and polybutylene terephthalate more compatible, polybutylene terephthalate is interspersed into the starch chain segments, sodium hexametaphosphate makes the starch cross-linked, and calcium carbonate is filled on the surface of polyethylene terephthalate, thereby improving the toughness and processing stability of polybutylene terephthalate, which is beneficial to improving the stability of the toner, reducing the influence of the toner on the high temperature and high humidity environment, and allowing the toner to be fixed in a relatively low temperature environment.

[0010] Preferably, the weight ratio of the polybutylene terephthalate, starch, sodium hexametaphosphate and calcium stearate is (0.16-0.18):1:(0.11-0.15):(0.06-0.08).

[0011] By adopting the above technical scheme, when polybutylene terephthalate, starch, sodium hexametaphosphate and calcium stearate are in a specific weight ratio, the four work together to further reduce the minimum fixing temperature and adhesion of the toner, thereby improving the stability of the toner.

[0012] Preferably, the carbon black is modified carbon black, and the preparation method of the modified carbon black is: 10-20 parts by weight of barium sulfate and 20-30 parts by weight of carbon black are mixed, firstly ultrasonically dispersed with 200-300 parts by weight of hydrochloric acid solution, then 5-15 parts by weight of tetraethyl orthosilicate are added, after washing and drying, 2-8 parts by weight of KH-570 are added and heated and mixed, after drying, 5-15 parts by weight of epoxy resin and 1-3 parts by weight of trimethylethylenediamine are added and mixed and stirred, and the modified carbon black is obtained after curing.

[0013] By adopting the above technical scheme, barium sulfate is mixed with carbon black to effectively prevent pigment agglomeration, the toner acts on the coating surface to improve the mechanical strength of the coating, ethyl orthosilicate improves the adhesion between carbon black and epoxy resin, thereby improving the adhesion of the toner, and trimethylethylenediamine is used as a curing agent to adjust the curing speed of the epoxy resin, so that the epoxy resin and carbon black are more closely connected, which is beneficial to reducing the fixing temperature of the toner and the adhesion to the fixing roller.

[0014] Preferably, the weight ratio of the barium sulfate, carbon black and epoxy resin is (1.2-1.5):(2.6-2.8):1.

[0015] By adopting the above technical scheme, when barium sulfate, carbon black and epoxy resin are in a specific weight ratio, the three are coordinated together, barium sulfate and carbon black are evenly dispersed in the epoxy resin, and the curing agent initiates the polymerization of the epoxy resin with the barium sulfate and carbon black surfaces, which is beneficial to reduce the fixing temperature of the toner.

[0016] Preferably, the weight ratio of the modified polybutylene terephthalate, PETG and modified carbon black is (1.76-1.92):1:(0.36-0.48).

[0017] By adopting the above technical scheme, when the modified polybutylene terephthalate, PETG and modified carbon black are in a specific weight ratio, the modified carbon black is evenly dispersed in the components, improving the dispersibility of the toner, which is beneficial to reducing the fixing temperature and heat resistance stability of the toner.

[0018] Preferably, the dispersant includes one of polyethylene wax and zinc stearate.

[0019] Preferably, the antioxidant includes one of antioxidant 168 and antioxidant 1010 .

[0020] By adopting the above technical solution, selecting suitable dispersants and antioxidants helps to reduce the fixing temperature of the toner.

[0021] In the second aspect, the present application provides an ultra-low temperature fixing toner using the following technical solution: A method for preparing a toner for ultra-low temperature fixing comprises the following steps: mixing and stirring modified polybutylene terephthalate, PETG, a dispersant, an antioxidant and carbon black, and then melting and kneading and crushing to obtain the toner.

[0022] By adopting the above technical solution, it is advantageous to obtain a toner which is less affected by a high temperature and high humidity environment, has good stability and can be fixed at a low temperature.

[0023] Preferably, by adopting the above technical solution and selecting a suitable particle size range, it is beneficial to the melt flow of the toner on the one hand, and is beneficial to the uniform and stable attachment of the anti-adhesive additive on the peripheral side of the toner masterbatch on the other hand.

[0024] In summary, this application has the following beneficial technical effects: 1. PETG and modified polybutylene terephthalate are used as carriers, and carbon black is added as a pigment. By modifying polybutylene terephthalate, the modified polybutylene terephthalate has good compatibility with PETG. The combination of carbon black with good stability is conducive to the uniform dispersion of each component and the reduction of the minimum fixing temperature of the toner.

[0025] 2. Glycerol and sodium hexametaphosphate make starch and polybutylene terephthalate more compatible. Polybutylene terephthalate penetrates into the starch chain segments, sodium hexametaphosphate makes the starch cross-linked, and calcium carbonate is filled on the surface of polyethylene terephthalate, thereby improving the toughness and processing stability of polybutylene terephthalate, which is beneficial to improving the stability of the toner, reducing the influence of the high temperature and high humidity environment on the toner, and allowing the toner to be fixed in a lower temperature environment. DETAILED DESCRIPTION

[0026] The present application is further described in detail below with reference to examples and comparative examples. Example

[0027] Example 1 A method for preparing a toner for ultra-low temperature fixing comprises the following steps: 60g of modified polybutylene terephthalate, 40g of PETG, 2g of dispersant, 1g of antioxidant and 10g of carbon black were put into a high-speed mixer, mixed and stirred for 5 minutes at a temperature of 60°C and a speed of 800r / min, transferred to a mixer and melted at a temperature of 135°C, and then pulverized into particles after cooling to room temperature, and screened into 100 mesh to obtain a toner. PETG was purchased from SK of South Korea, with the item number of PETG K2012; polyethylene wax was selected as the dispersant, and Qihong D1016 was selected, and the antioxidant was antioxidant 1010.

[0028] The preparation method of the modified polybutylene terephthalate is as follows: 80g starch, 10g glycerol, 10g polybutylene terephthalate and 5g sodium hexametaphosphate are added to a magnetic stirrer, mixed and stirred for 0.5h at a temperature of 95°C, transferred to a drying oven, dried at a temperature of 50°C for 72h, crushed to 200 mesh, and then added with 50g calcium carbonate and 5g calcium stearate to a high-speed mixer for mixing and stirring for 10min, transferred to an internal mixer, and granulated at a temperature of 160°C and a speed of 75r / min to obtain the modified polybutylene terephthalate. Polybutylene terephthalate is purchased from DuPont S650FR NC010 of the United States.

[0029] Example 2 A method for preparing a toner for ultra-low temperature fixing comprises the following steps: 100g of modified polybutylene terephthalate, 80g of PETG, 8g of dispersant, 3g of antioxidant and 30g of carbon black were put into a high-speed mixer, mixed and stirred for 5 minutes at a temperature of 60°C and a speed of 800r / min, transferred to a mixer and melted at a temperature of 135°C, and then pulverized into particles after cooling to room temperature, and screened into 100 mesh to obtain a toner. PETG was purchased from SK of South Korea, with the item number of PETG K2012; zinc stearate was selected as the dispersant, and antioxidant was antioxidant 1010.

[0030] The preparation method of the modified polybutylene terephthalate is as follows: 80g starch, 10g glycerol, 10g polybutylene terephthalate and 5g sodium hexametaphosphate are added to a magnetic stirrer, mixed and stirred for 0.5h at a temperature of 95°C, transferred to a drying oven, dried at a temperature of 50°C for 72h, crushed to 200 mesh, and then added with 50g calcium carbonate and 5g calcium stearate to a high-speed mixer for mixing and stirring for 10min, transferred to an internal mixer, and granulated at a temperature of 160°C and a speed of 75r / min to obtain the modified polybutylene terephthalate. Polybutylene terephthalate is purchased from DuPont S650FR NC010 of the United States.

[0031] Example 3 A method for preparing a toner for ultra-low temperature fixing comprises the following steps: 80g of modified polybutylene terephthalate, 60g of PETG, 5g of dispersant, 2g of antioxidant and 20g of carbon black were put into a high-speed mixer, mixed and stirred for 5 minutes at a temperature of 60°C and a speed of 800r / min, transferred to a mixer and melted at a temperature of 135°C, and then pulverized into particles after cooling to room temperature, and screened into 100 mesh to obtain a toner. PETG was purchased from SK of South Korea, with the item number of PETG K2012; polyethylene wax was selected as the dispersant, and Qihong D1016 was selected, and the antioxidant was antioxidant 168.

[0032] The preparation method of the modified polybutylene terephthalate is as follows: 80g starch, 10g glycerol, 10g polybutylene terephthalate and 5g sodium hexametaphosphate are added to a magnetic stirrer, mixed and stirred for 0.5h at a temperature of 95°C, transferred to a drying oven, dried at a temperature of 50°C for 72h, crushed to 200 mesh, and then added with 50g calcium carbonate and 5g calcium stearate to a high-speed mixer for mixing and stirring for 10min, transferred to an internal mixer, and granulated at a temperature of 160°C and a speed of 75r / min to obtain the modified polybutylene terephthalate. Polybutylene terephthalate is purchased from DuPont S650FR NC010 of the United States.

[0033] Example 4 A method for preparing a toner for ultra-low temperature fixing, which is different from Example 3 in that: the preparation method of modified polybutylene terephthalate is as follows: 120g of starch, 30g of glycerol, 20g of polybutylene terephthalate and 15g of sodium hexametaphosphate are added to a magnetic stirrer, mixed and stirred for 0.5h at a temperature of 95°C, transferred to a drying oven, dried at a temperature of 50°C for 72h, and then crushed to 200 mesh, then added with 90g of calcium carbonate and 15g of calcium stearate in a high-speed mixer, mixed and stirred for 10min, transferred to an internal mixer, and granulated at a temperature of 160°C and a rotation speed of 75r / min to obtain modified polybutylene terephthalate.

[0034] Example 5 A method for preparing an ultra-low temperature fixing toner, which is different from Example 3 in that: the input amount of polybutylene terephthalate is 16g, the input amount of starch is 100g, the input amount of sodium hexametaphosphate is 11g, and the input amount of calcium stearate is 6g.

[0035] Example 6 A method for preparing an ultra-low temperature fixing toner, which is different from Example 3 in that: the input amount of polybutylene terephthalate is 18g, the input amount of starch is 100g, the input amount of sodium hexametaphosphate is 15g, and the input amount of calcium stearate is 8g.

[0036] Example 7 A method for preparing a toner for ultra-low temperature fixing, which is different from Example 6 in that an equal amount of carbon black is replaced with modified carbon black, and the preparation method of the modified carbon black is as follows: 10g of barium sulfate and 20g of carbon black are mixed, firstly ultrasonically dispersed with 200g of 0.1mol / L hydrochloric acid solution for 30min, then 5g of ethyl orthosilicate is added and mixed and stirred at a temperature of 60°C for 2h, washed with deionized water and dried at a temperature of 60°C, 2g of KH-570 and 9g of distilled water are added and heated to 80°C and mixed for 2h, dried at a temperature of 100°C for 6h, then 5g of epoxy resin and 1g of trimethylethylenediamine are added and mixed and stirred for 10min, and the modified carbon black is obtained after standing and curing at room temperature. The epoxy resin is purchased from Nantong Phoenix, with a brand of E-44.

[0037] Example 8 A method for preparing a toner for ultra-low temperature fixing, which is different from Example 6 in that an equal amount of carbon black is replaced with modified carbon black, and the preparation method of the modified carbon black is as follows: 20g of barium sulfate and 30g of carbon black are mixed, firstly 300g of 0.1mol / L hydrochloric acid solution is used for ultrasonic dispersion for 30min, then 15g of ethyl orthosilicate is added and mixed and stirred at a temperature of 60°C for 2h, washed with deionized water and dried at a temperature of 60°C, 8g of KH-570 and 20g of distilled water are added and heated to 80°C and mixed for 2h, dried at a temperature of 100°C for 6h, and then 15g of epoxy resin and 3g of trimethylethylenediamine are added and mixed and stirred for 10min, and the modified carbon black is obtained after standing and curing at room temperature. The epoxy resin is purchased from Nantong Phoenix, with a brand name of E-44.

[0038] Example 9 A method for preparing a toner for ultra-low temperature fixing is different from that of Example 8 in that: the input amount of barium sulfate is 12 g, the input amount of carbon black is 26 g, and the input amount of epoxy resin is 10 g.

[0039] Example 10 A method for preparing a toner for ultra-low temperature fixing is different from that of Example 8 in that: the input amount of barium sulfate is 15 g, the input amount of carbon black is 28 g, and the input amount of epoxy resin is 10 g.

[0040] Embodiment 11 A method for preparing an ultra-low temperature fixing toner, which is different from Example 10 in that the input amount of modified polybutylene terephthalate is 88g, the input amount of PETG is 50g, and the input amount of modified carbon black is 18g.

[0041] Example 12 A method for preparing an ultra-low temperature fixing toner, which is different from Example 10 in that the input amount of modified polybutylene terephthalate is 96g, the input amount of PETG is 50g, and the input amount of modified carbon black is 24g.

[0042] Comparative Example Comparative Example 1 A method for preparing a toner capable of ultra-low temperature fixing is different from that of Example 3 in that an equal amount of modified polybutylene terephthalate is replaced by polybutylene terephthalate.

[0043] Comparative Example 2 A method for preparing a toner capable of ultra-low temperature fixing is different from that of Example 3 in that an equal amount of modified polybutylene terephthalate is replaced by polyethylene terephthalate.

[0044] Comparative Example 3 A method for preparing an ultra-low temperature fixing toner, which is different from Example 3 in that an equal amount of PETG is replaced by PCTG.

[0045] Comparative Example 4 A method for preparing an ultra-low temperature fixing toner, which is different from that of Example 3 in that an equal amount of carbon black is replaced by silicon dioxide.

[0046] Comparative Example 5 A method for preparing a toner for ultra-low temperature fixing is different from that of Example 3 in that an equal amount of PETG is replaced with modified polybutylene terephthalate.

[0047] Performance testing: Evaluation of printing image effect: The toners prepared in Examples 1-12 and Comparative Examples 1-5 were added to the toner cartridge of the printer, and the temperature of the fixing roller was raised from 80° C. to 180° C. to perform a fixing test. During the fixing test, if the fixing effect was unsatisfactory, the temperature was raised and the fixing was performed again. If the fixing was qualified, the lowest temperature corresponding to the qualified fixing was recorded.

[0048] Heat stability: 10 g of the toners of Examples 1-12 and Comparative Examples 1-5 were weighed in an propylene cup and placed in an environment of 50°C and 50% humidity for 24 h. The toner agglomeration was visually determined and classified into three grades: A, B, C, and D from good to bad.

[0049] Print image stability: The toners prepared in Examples 1-12 and Comparative Examples 1-15 were added to the toner cartridge of the printer, and in an environment with a temperature of 25°C and a humidity of 75%, the temperature of the fixing roller was controlled to be 180°C, and 2,000 images with a printing rate of 5% were continuously printed. The color density value and the bottom gray value of the first and 10,000th images were compared, wherein the higher the color density value, the clearer the printed image and the richer the details; the lower the bottom gray value, the cleaner the background and the less unnecessary gray or dirt appeared. In this application, a color density value of 1.35 or more and a bottom gray value of less than 2 are considered qualified. Minimum fixing temperature / ℃ Heat stability Color Density Example 1 104℃ A 1.38 Example 2 106℃ A 1.37 Example 3 103℃ A 1.39 Example 4 103℃ A 1.39 Example 5 98℃ A 1.40 Example 6 97℃ A 1.41 Example 7 94℃ A 1.42 Example 8 95℃ A 1.43 Example 9 92℃ A 1.46 Example 10 91℃ A 1.47 Embodiment 11 87℃ A 1.49 Example 12 86℃ A 1.48 Comparative Example 1 130℃ B 1.19 Comparative Example 2 140℃ A 1.22 Comparative Example 3 145℃ B 1.33 Comparative Example 4 135℃ A 1.26 Comparative Example 5 140℃ B 1.18

[0050] According to the data comparison of Examples 1-4 and Comparative Examples 1-5, it can be obtained that PETG and modified polybutylene terephthalate are used as carriers, carbon black is added as a pigment, and the polybutylene terephthalate is modified to make the modified polybutylene terephthalate have good compatibility with PETG. The combination with carbon black with good stability is beneficial to uniform dispersion of each component and lowering the minimum fixing temperature of the toner; glycerol and sodium hexametaphosphate make starch and polybutylene terephthalate have good compatibility, polybutylene terephthalate is interspersed into the starch chain segment, sodium hexametaphosphate makes the starch cross-linked, and calcium carbonate is filled on the surface of polyethylene terephthalate, thereby improving the toughness and processing stability of polybutylene terephthalate, which is beneficial to improving the stability of the toner, reducing the influence of the high temperature and high humidity environment on the toner, and allowing the toner to be fixed in a relatively low temperature environment.

[0051] According to the data comparison of Examples 3-6, when polybutylene terephthalate, starch, sodium hexametaphosphate and calcium stearate are in a specific weight ratio, the four together can further reduce the minimum fixing temperature and adhesion of the toner, thereby improving the stability of the toner.

[0052] According to the data comparison of Examples 6-8, it can be obtained that mixing barium sulfate with carbon black can effectively prevent pigment agglomeration, the toner acts on the coating surface to improve the mechanical strength of the coating, tetraethyl orthosilicate improves the adhesion between carbon black and epoxy resin, thereby improving the adhesion of the toner, and trimethylethylenediamine is used as a curing agent to adjust the curing speed of the epoxy resin, so that the epoxy resin and carbon black are more closely connected, which is beneficial to reducing the fixing temperature of the toner and the adhesion to the fixing roller.

[0053] According to the data comparison of Examples 8-10, it can be obtained that when barium sulfate, carbon black and epoxy resin are in a specific weight ratio, the three are coordinated together, barium sulfate and carbon black are evenly dispersed in the epoxy resin, and the curing agent initiates the polymerization of the epoxy resin with the barium sulfate and carbon black surfaces, which is beneficial to reduce the fixing temperature of the toner.

[0054] According to the data comparison of Examples 10-12, when the modified polybutylene terephthalate, PETG and modified carbon black are in a specific weight ratio, the modified carbon black is evenly dispersed in the components, improving the dispersibility of the toner, which is beneficial to reducing the fixing temperature and heat resistance stability of the toner.

[0055] This specific implementation manner is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the specific implementation manner as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A toner for ultra-low temperature fixing, characterized in that: The modified polybutylene terephthalate is made of the following raw materials in parts by weight: 60-100 parts of modified polybutylene terephthalate; 40-80 parts of PETG; 2-8 parts of dispersant; 10-30 parts of carbon black; and 1-3 parts of antioxidant. The modified polybutylene terephthalate is made of the following raw materials: polybutylene terephthalate, starch, glycerol, sodium hexametaphosphate, calcium carbonate and calcium stearate.

2. The ultra-low temperature fixing toner according to claim 1, characterized in that: The preparation method of the modified polybutylene terephthalate is as follows: 80-120 parts by weight of starch, 10-30 parts by weight of glycerol, 10-20 parts by weight of polybutylene terephthalate and 5-15 parts by weight of sodium hexametaphosphate are mixed and stirred evenly, dried and crushed, then mixed and stirred with 50-90 parts by weight of calcium carbonate and 5-15 parts by weight of calcium stearate, and the modified polybutylene terephthalate is obtained after banburying and granulation.

3. The ultra-low temperature fixing toner according to claim 2, characterized in that: The weight ratio of the polybutylene terephthalate, starch, sodium hexametaphosphate and calcium stearate is (0.16-0.18):1:(0.11-0.15):(0.06-0.08).

4. The ultra-low temperature fixing toner according to claim 1, characterized in that: The carbon black is modified carbon black. The preparation method of the modified carbon black is as follows: 10-20 parts by weight of barium sulfate and 20-30 parts by weight of carbon black are mixed, firstly ultrasonically dispersed with 200-300 parts by weight of hydrochloric acid solution, then 5-15 parts by weight of tetraethyl orthosilicate are added, after washing and drying, 2-8 parts by weight of KH-570 are added, heated and mixed, after drying, 5-15 parts by weight of epoxy resin and 1-3 parts by weight of trimethylethylenediamine are added, mixed and stirred, and the modified carbon black is obtained after curing.

5. The ultra-low temperature fixing toner according to claim 4, characterized in that: The weight ratio of the barium sulfate, carbon black and epoxy resin is (1.2-1.5): (2.6-2.8):

1.

6. The ultra-low temperature fixing toner according to claim 4, characterized in that: The weight ratio of the modified polybutylene terephthalate, PETG and modified carbon black is (1.76-1.92):1:(0.36-0.48).

7. The ultra-low temperature fixing toner according to claim 1, characterized in that: The dispersant includes one of polyethylene wax and zinc stearate.

8. The ultra-low temperature fixing toner according to claim 1, characterized in that: The antioxidant includes one of antioxidant 168 and antioxidant 1010 .

9. A method for preparing a toner for ultra-low temperature fixing, characterized in that: The method for preparing the ultra-low temperature fixing toner according to any one of claims 1 to 8 comprises the following steps: mixing and stirring modified polybutylene terephthalate, PETG, a dispersant, an antioxidant and carbon black, and then melting and kneading and crushing to obtain the toner.

10. The ultra-low temperature fixing toner according to claim 9, characterized in that: The crushed particle size is 80-150 meshes.