A polyimide composite for a transfer film of a printing copier and a preparation method and applications thereof

Abstract

The present application relates to a kind of printing copier transfer film polyimide composite and its preparation method and application, including mass fraction as follows component: polyimide resin 80-100 parts, conductive agent 10-30 parts, auxiliary agent 1-10 parts;The conductive agent includes polyimide adhesive, modified conductive filler, dispersing agent;The polyimide adhesive is 2,2'-di [4- (4-aminophenoxy) phenyl] propane, 2,4,6-triamino pyrimidine and 3,3',4,4'-benzophenone tetracarboxylic dianhydride polymerization reaction product;The modified conductive filler is fatty acid modified conductive filler;The conductive filler is selected from one or more of metal, metal oxide, carbon nanotube, carbon black, carbon nanofiber, graphene, graphene oxide.The present application greatly improves the conductive performance of product while ensuring stability, overcomes the deficiencies existing in the prior art, has good application prospect.

Description

Technical Field

[0001] This invention belongs to the field of polyimide materials, specifically relating to a polyimide composite material for transfer films in printers and copiers, its preparation method, and its application. Background Technology

[0002] Printers and copiers generally use thermal fixing for printing. This method involves passing the printing material, already coated with a toner image, through a fixing belt containing a heat source. The heat melts the unfixed toner, fixing it onto the material to be printed, thus forming an image. The transfer belt is typically prepared by applying a coating solution to the inner surface of a mold, drying and heat-treating it to form a tubular film, and then demolding it into a transfer belt of suitable width.

[0003] However, existing transfer belt products still have many defects, including low surface gloss, poor cleanability, and unstable surface resistivity under various environments, which greatly affects image quality and makes it difficult to meet the ever-increasing demands for printing and copying effects.

[0004] In conclusion, there is an urgent need to develop a new technical solution to address the problems existing in the current technology and meet the development needs of the current market. Summary of the Invention

[0005] Therefore, adopting appropriate methods to improve the conductivity and stability of polyimide materials to ensure good printing results is of great significance. This invention prepares a polyimide composite material for transfer films in printers and copiers by combining a specific polyimide adhesive with a modified conductive filler to obtain a conductive agent. This material significantly improves the conductivity of the product while ensuring stability, overcoming the shortcomings of existing technologies and showing promising application prospects.

[0006] One object of the present invention is to provide a polyimide composite material for transfer films in printers and copiers, the polyimide composite material for transfer films in printers and copiers comprising the following components in parts by weight:

[0007] 80-100 parts of polyimide resin

[0008] 10-30 parts of conductive agent

[0009] 1-10 parts of auxiliary agent;

[0010] in,

[0011] The conductive agent includes polyimide adhesive, modified conductive filler, and dispersant;

[0012] The polyimide adhesive is a product of the polymerization reaction of 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,4,6-triaminopyrimidine and 3,3',4,4'-benzophenone tetracarboxylic dianhydride;

[0013] The modified conductive filler is a fatty acid modified conductive filler;

[0014] The conductive filler is selected from one or more of the following: metal, metal oxide, carbon nanotube, carbon black, carbon nanofiber, graphene, and graphene oxide.

[0015] Furthermore, the method for preparing the conductive agent includes the following steps:

[0016] S1. Add the conductive filler to a sodium hydroxide solution, sonicate it, add hydrogen peroxide, stir and react for 8-10 hours, and then wash and dry to obtain the hydroxylated conductive filler.

[0017] S2. The hydroxylated conductive filler is added to a fatty acid solution, and after ultrasonic heating and reaction, it is washed and dried to obtain the modified conductive filler.

[0018] S3. The modified conductive filler, polyimide adhesive, and dispersant are mixed and then heated and stirred to obtain the conductive agent.

[0019] Further, in step S1, the concentration of the sodium hydroxide solution is 5-10 mol / L.

[0020] Further, in step S2, the mass ratio of the hydroxylated conductive filler to the fatty acid is (50-150):1.

[0021] Furthermore, in step S2, the temperature of the ultrasonic heating reaction is 30-50℃.

[0022] Furthermore, the preparation method of the polyimide adhesive includes the following steps:

[0023] L1. 2,2'-bis[4-(4-aminophenoxy)phenyl]propane and 2,4,6-triaminopyrimidine were added to a solvent and stirred under an inert atmosphere. Then, 3,3',4,4'-benzophenone tetracarboxylic dianhydride was added and stirred to obtain an intermediate product.

[0024] L2. Add xylene to the intermediate product, react at 100-180℃ for 1-6 hours, cool, purify, and dissolve in a solvent to obtain the polyimide adhesive.

[0025] Furthermore, the molar ratio of 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,4,6-triaminopyrimidine, and 3,3',4,4'-benzophenone tetracarboxylic dianhydride is 1:1.5:3.

[0026] Furthermore, the general structural formula of the polyimide resin is as follows:

[0027]

[0028] The number n is selected from 4 to 1000.

[0029] Furthermore, the additive is selected from one or more of the following: wetting agents, leveling agents, defoamers, humectants, mildew inhibitors, thickeners, and viscosity reducers.

[0030] Another object of the present invention is to provide a method for preparing the polyimide composite material for the transfer film of the above-mentioned printer / copier, comprising the following steps:

[0031] After the polyimide resin, conductive agent, and additives are mixed evenly, a thermoforming process is performed to obtain the polyimide composite material for the transfer film of the printer / copier.

[0032] Another object of the present invention is to provide the application of the above-mentioned polyimide composite material for transfer film of printers and copiers in printers and copiers.

[0033] The beneficial effects of this invention are as follows:

[0034] 1. The polyimide composite material for the transfer film of the printer / copier of the present invention uses a specific material as a conductive agent. The conductive agent includes a modified conductive filler grafted with long-chain fatty acids, which effectively enhances the compatibility between the filler and the polyimide. When compounded with a dispersant, it can achieve a uniform dispersion effect and improve electrical performance. On the other hand, the conductive agent also contains a polyimide adhesive obtained by polymerization of specific diamine, triamine, and dianhydride monomers, which can form a denser and more stable network structure, thereby further improving the stability and mechanical properties of the material.

[0035] 2. The transfer film prepared using the polyimide composite material of the present invention can form a more uniform surface. The product that is demolded after film formation has the advantages of good gloss and easy cleaning, and has stable surface resistivity and good image quality. Detailed Implementation

[0036] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0037] The conductive filler in this embodiment of the invention is carbon nanofiber, purchased from Teijin Corporation's "PotenCia".

[0038] In this embodiment of the invention, the polyimide resin was purchased from DuPont's "Kapton" and its structural formula is as follows:

[0039]

[0040] Where n is 4.

[0041] The additives in this embodiment of the invention include a defoamer, a wetting agent, and a leveling agent in a mass ratio of 1:1:1. The defoamer is Dow Chemical Silicone Oil FZ-2110; the wetting agent is Saint-Gobain Silicone Oil SI-2047; and the leveling agent is DISPARLON L1980N.

[0042] The preparation method of the polyimide adhesive in this embodiment of the invention includes the following steps:

[0043] L1. 2,2'-bis[4-(4-aminophenoxy)phenyl]propane and 2,4,6-triaminopyrimidine were dissolved sequentially in N,N-dimethylacetamide and stirred for 10 min under a nitrogen atmosphere. Then, 3,3',4,4'-benzophenone tetracarboxylic dianhydride (2,2'-bis[4-(4-aminophenoxy)phenyl]propane:2,4,6-triaminopyrimidine:3,3',4,4'-benzophenone tetracarboxylic dianhydride = 1:1.5:3, n / n / n) was added and the reaction was stirred for 48 h to obtain the intermediate product.

[0044] L2. Add sufficient xylene to the intermediate product, then react at 160°C for 6 hours. After cooling, wash with ethanol, filter and dry. Add the obtained solid product to NMP solvent to obtain a 30% polyimide adhesive.

[0045] The preparation method of the conductive agent in this embodiment of the invention includes the following steps:

[0046] S1. Add 1g of carbon nanofibers to 400mL of 10mol / mL sodium hydroxide solution, disperse by ultrasonication for 40min, add catalyst (3mL 30% hydrogen peroxide), stir and react for 10h, centrifuge to remove the supernatant, wash with distilled water until neutral, and dry to obtain hydroxylated carbon nanofibers.

[0047] S2. The hydroxylated carbon nanofibers are added to palmitic acid solution (hydroxylated carbon nanofibers: palmitic acid = 100:1, m / m), and ultrasonically reacted at 30°C for 10 min. After filtration, washing and drying, the modified conductive filler is obtained.

[0048] S3. The modified conductive filler, polyimide adhesive and sodium dodecyl sulfate in a mass ratio of 20:80:1 are mixed and heated and stirred at 30°C for 10 min to obtain the conductive agent.

[0049] Example 1

[0050] A polyimide composite material for transfer films in printers and copiers, comprising the following components in parts by weight:

[0051] 80 parts of polyimide resin

[0052] 10 parts of conductive agent

[0053] One part of the auxiliary agent.

[0054] The preparation method of the polyimide composite material for the transfer film of the above-mentioned printer / copier includes the following steps:

[0055] According to the above-mentioned mass proportions, the polyimide resin, conductive agent, and additives are mixed and stirred evenly, then treated at 80°C for 1 hour, at 200°C for 1 hour, and then at 310°C for 1 hour. After cooling, the polyimide composite material for the transfer film of the printer / copier is obtained.

[0056] Example 2

[0057] A polyimide composite material for transfer films in printers and copiers, comprising the following components in parts by weight:

[0058] 100 parts of polyimide resin

[0059] 30 parts of conductive agent

[0060] 10 parts of auxiliary agent.

[0061] The preparation method of the polyimide composite material for the transfer film of the above-mentioned printer / copier includes the following steps:

[0062] According to the above-mentioned mass proportions, the polyimide resin, conductive agent, and additives are mixed and stirred evenly, then treated at 80°C for 1 hour, at 200°C for 1 hour, and then at 310°C for 1 hour. After cooling, the polyimide composite material for the transfer film of the printer / copier is obtained.

[0063] Example 3

[0064] A polyimide composite material for transfer films in printers and copiers, comprising the following components in parts by weight:

[0065] 90 parts of polyimide resin

[0066] 20 parts of conductive agent

[0067] Five parts of auxiliary agent.

[0068] The preparation method of the polyimide composite material for the transfer film of the above-mentioned printer / copier includes the following steps:

[0069] According to the above-mentioned mass proportions, the polyimide resin, conductive agent, and additives are mixed and stirred evenly, then treated at 80°C for 1 hour, at 200°C for 1 hour, and then at 310°C for 1 hour. After cooling, the polyimide composite material for the transfer film of the printer / copier is obtained.

[0070] Comparative Example 1

[0071] A polyimide composite material, the difference between this comparative example and Example 1 is that in the preparation method of the conductive agent, an equal amount of ordinary carbon nanofibers are used to replace the modified conductive filler, while other materials and preparation methods are the same as in Example 1.

[0072] Comparative Example 2

[0073] A polyimide composite material, the difference between this comparative example and Example 1 is that in the preparation method of the polyimide adhesive, an equal amount of diamine monomer (4,4'-diaminodiphenyl ether) is used to replace 2,4,6-triaminopyrimidine, while other materials and preparation methods are the same as in Example 1.

[0074] Test Example 1

[0075] The performance of the polyimide composites prepared in Example 1 and Comparative Examples 1-2 was tested.

[0076] Test method:

[0077] The volume resistivity of the polyimide composites prepared in Example 1 and Comparative Examples 1-2 was measured at different temperatures; then, different polyimide composites were used for printing tests to check whether the printed samples were uniform and clear.

[0078] The test results are shown in Table 1.

[0079] Table 1 Performance Test Results

[0080]

[0081] Table 1 shows that the polyimide composite material for transfer films in printers and copiers prepared in Example 1 of this invention exhibits good electrical conductivity, relatively stable surface resistivity at different temperatures, minimal susceptibility to external influences, and good image quality. In contrast, comparative examples 1-2, which replaced the modified conductive filler or polyimide adhesive, showed significantly reduced performance, higher volume resistivity, poor stability, and uneven printing, resulting in unsatisfactory performance improvement. In conclusion, the combination of modified conductive filler and polyimide adhesive effectively enhances the material's performance, and the polyimide composite material for transfer films in printers and copiers of this invention shows promising application prospects.

[0082] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0083] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A polyimide composite material for transfer films in printers and copiers, characterized in that, The polyimide composite material for the transfer film of the printer / copier comprises the following components in parts by weight: 80-100 parts of polyimide resin 10-30 parts of conductive agent 1-10 parts of auxiliary agent; in, The conductive agent includes polyimide adhesive, modified conductive filler, and dispersant; The polyimide adhesive is a product of the polymerization reaction of 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,4,6-triaminopyrimidine and 3,3',4,4'-benzophenone tetracarboxylic dianhydride; The modified conductive filler is a fatty acid modified conductive filler; The conductive filler is selected from one or more of the following: metals, metal oxides, carbon nanotubes, carbon black, carbon nanofibers, graphene, and graphene oxide. The fatty acid is palmitic acid.

2. The polyimide composite material for the transfer film of the printer / copier according to claim 1, characterized in that, The method for preparing the conductive agent includes the following steps: S1. The conductive filler is added to a sodium hydroxide solution, ultrasonically treated, hydrogen peroxide is added, and the reaction is stirred for 8-10 h. After washing and drying, the hydroxylated conductive filler is obtained. S2. The hydroxylated conductive filler is added to a fatty acid solution, and after ultrasonic heating and reaction, it is washed and dried to obtain the modified conductive filler. S3. The modified conductive filler, polyimide adhesive, and dispersant are mixed and then heated and stirred to obtain the conductive agent.

3. The polyimide composite material for the transfer film of the printer / copier according to claim 2, characterized in that, In step S1, the concentration of the sodium hydroxide solution is 5-10 mol / L.

4. The polyimide composite material for the transfer film of the printer / copier according to claim 2, characterized in that, In step S2, the mass ratio of the hydroxylated conductive filler to the fatty acid is (50-150):

1.

5. The polyimide composite material for the transfer film of a printer / copier according to claim 2, characterized in that, In step S2, the temperature of the ultrasonic heating reaction is 30-50℃.

6. The polyimide composite material for the transfer film of the printer / copier according to claim 2, characterized in that, The preparation method of the polyimide adhesive includes the following steps: L1. 2,2'-bis[4-(4-aminophenoxy)phenyl]propane and 2,4,6-triaminopyrimidine were added to a solvent and stirred under an inert atmosphere. Then 3,3',4,4'-benzophenone tetracarboxylic dianhydride was added and stirred to obtain an intermediate product. L2. Add xylene to the intermediate product, react at 100-180℃ for 1-6 h, cool, purify, and dissolve in a solvent to obtain the polyimide adhesive.

7. The polyimide composite material for the transfer film of the printer / copier according to claim 1, characterized in that, The general structural formula of the polyimide resin is shown below: ； The number n is selected from 4 to 1000.

8. The polyimide composite material for the transfer film of the printer / copier according to claim 1, characterized in that, The additives are selected from one or more of the following: wetting agents, leveling agents, defoamers, humectants, mildew inhibitors, thickeners, and viscosity reducers.

9. A method for preparing the polyimide composite material for the transfer film of the printer / copier according to any one of claims 1-8, characterized in that, Includes the following steps: After the polyimide resin, conductive agent, and additives are mixed evenly, a thermoforming process is performed to obtain the polyimide composite material for the transfer film of the printer / copier.

10. The application of the polyimide composite material for the transfer film of the printer / copier according to any one of claims 1-8 in printers and copiers.

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