A high-temperature and solvent-resistant antistatic primer, an antistatic layer, and a method for preparing the same.

Abstract

This invention relates to the field of polymer materials, specifically disclosing a high-temperature and solvent-resistant antistatic primer, an antistatic layer, and a method for preparing the same. The invention incorporates a carboxyl-containing polythiophene conductive polymer, along with an epoxy-containing silane coupling agent, a hydroxyl-containing waterborne polyurethane, and a modified isocyanate, into the antistatic primer. During thermosetting, the carboxyl, hydroxyl, epoxy, and isocyanate groups form a stable interpenetrating network structure through hydrogen bonding and chemical cross-linking reactions, increasing the cross-linking density of the antistatic layer and thus enhancing its high-temperature resistance, solvent resistance, and abrasion resistance. Through chemical cross-linking and hydrogen bonding between functional groups, the migration and precipitation of antistatic components under high-temperature and high-humidity conditions are effectively prevented, thus effectively solving the problems of whitening, fogging, and decreased antistatic performance of the antistatic layer under these conditions.

Description

Technical Field

[0001] This invention relates to the field of polymer materials, specifically to a high-temperature and solvent-resistant antistatic primer, an antistatic layer, and a method for preparing the same. Background Technology

[0002] OLED displays are rapidly evolving towards curved and flexible designs, and the polarizers used in OLEDs are also becoming thinner and more flexible. Currently, TAC film is the most widely used raw material in polarizer production. However, to achieve specific optical effects and considering overall cost factors, the market has begun using materials such as PET to replace some of the TAC material.

[0003] OLED displays are primarily used in the electronic display field. Since electrostatic discharge (ESD) can damage electronic products, and polarizers are a crucial component of OLED displays, their antistatic capabilities are subject to stringent requirements. Currently, an antistatic functional layer is typically formed by coating the PET material of the polarizer with an antistatic liquid. However, because the polarizer needs to be cleaned with organic solvents before assembly during OLED display manufacturing, the antistatic layer must possess excellent solvent resistance. Furthermore, the manufacturing process of OLED displays involves high-temperature and high-humidity environments, requiring the antistatic layer to also have good high-temperature resistance. Current antistatic layers often exhibit whitening or fogging after solvent wiping or exposure to high-temperature and high-humidity environments, severely impacting their antistatic performance. Summary of the Invention

[0004] The purpose of this invention is to provide a high-temperature and solvent-resistant antistatic primer, an antistatic layer, and a method for preparing the same, in order to solve the problems mentioned in the background art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0006] A high-temperature resistant, solvent-resistant, and antistatic primer comprises: Component A: PEDOT / PSS antistatic liquid with a solid content of 1.2-1.6%; Component B: waterborne polyurethane containing hydroxyl groups with a solid content of 25-35%; Component C: modified isocyanate with a solid content of 9-11%; Component D: a mixed solution of water and isopropanol; Component E: a polythiophene conductive polymer containing carboxyl groups, a conductivity enhancer, a silane coupling agent, a surfactant, and a pH adjuster.

[0007] Furthermore, the mass ratio of component A to component B is 4:1-3:1, the mass ratio of component A to component C is 40:1-40:2, the mass of component D is 10-12 times the total mass of components A and B, and the mass of the carboxyl-containing polythiophene conductive polymer, the conductivity enhancer, and the silane coupling agent in component E is 0.3-0.7%, 8-10%, and 0.2-0.5% of the mass of component A, respectively.

[0008] Furthermore, component C is a mixed solution of water and isopropanol in a mass ratio of 1:2.

[0009] Furthermore, the mass ratio of component A to component B is 4:1.

[0010] Furthermore, the carboxyl-containing polythiophene conductive polymer is one or more of poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), and poly(3-methyl-4-carboxybutylthiophene).

[0011] Furthermore, the conductivity enhancer is a compound having an amide group in its molecule, including but not limited to one or more of 2-pyrrolidone, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylformamide, formamide, acetamide, and N,N-dimethylformamide.

[0012] Furthermore, the silane coupling agent is a silane coupling agent containing an epoxy group, including but not limited to 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane.

[0013] Furthermore, the surfactant is a nonionic surfactant, specifically an ethoxylated acetylene diol surfactant.

[0014] Furthermore, the mass of the surfactant is 0.2-0.5% of the mass of component A.

[0015] Furthermore, the pH adjuster is an amine compound, including but not limited to one or more of N,N-dimethylethanolamine, diethanolamine, and triethanolamine.

[0016] Furthermore, the mass of the pH adjuster is 1-3% of the mass of component A.

[0017] The present invention also discloses a high-temperature resistant and solvent-resistant antistatic layer, which is prepared from the aforementioned antistatic liquid and has a thickness of 0.05 to 0.1 μm.

[0018] This invention also discloses a method for preparing a high-temperature and solvent-resistant antistatic layer, comprising the following steps:

[0019] S1. Mix components D and E except for the surfactant, stir until homogeneous to obtain a mixture, then add components A, B and C to the mixture in sequence, disperse and let stand for 20-30 minutes, finally add the surfactant and disperse until homogeneous to obtain an antistatic primer.

[0020] S2. Apply the antistatic primer prepared in step S1 onto a PET substrate, control the thickness of the dried coating to be 0.05-0.1 μm, and cure at 120℃ for 1 min to obtain a stable antistatic layer that is resistant to high temperature and solvents.

[0021] The present invention also discloses the application of a high-temperature resistant, solvent-resistant, and antistatic layer in polarizers.

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0023] This invention incorporates a carboxyl-containing polythiophene conductive polymer, along with an epoxy-containing silane coupling agent, a hydroxyl-containing waterborne polyurethane, and a modified isocyanate, into an antistatic primer. During thermosetting, the carboxyl, hydroxyl, epoxy, and isocyanate groups form a stable interpenetrating network structure through hydrogen bonding and chemical cross-linking reactions, increasing the cross-linking density of the antistatic layer and thus enhancing its high-temperature resistance, solvent resistance, and abrasion resistance. Through chemical cross-linking and hydrogen bonding between functional groups, the migration and precipitation of antistatic components under high-temperature and high-humidity conditions are effectively prevented, thus effectively solving the problems of whitening, fogging, and decreased antistatic performance of the antistatic layer under these conditions. By rationally adjusting the amounts of each component in the antistatic layer, an antistatic layer with excellent antistatic properties, high-temperature resistance, and solvent resistance is prepared. Detailed Implementation

[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] The antistatic liquid, hydroxyl-containing aqueous polyurethane, modified isocyanate, and surfactant used in the embodiments of this invention, along with their respective models and purchase channels, are as follows:

[0026] PEDOT / PSS antistatic liquid, CPD01, Zhiertai New Materials.

[0027] Hydroxyl-containing waterborne polyurethane, CX01, Zhiertai New Materials.

[0028] Modified isocyanate, CL600, Arakawa Chemical.

[0029] Surfactant, Dynol 604, Shanghai Sangjing Chemical Co., Ltd.

[0030] Example 1:

[0031] The formula for the antistatic liquid is as follows: Component A 1kg, Component B 250g, Component C 25g, Component D: Water 4.2kg, Isopropanol 8.4kg, Component E: Poly(3-carboxythiophene) 5g, Methylpyrrolidone 88g, 3-glycidyl etheroxypropyltrimethoxysilane 2g, Surfactant 2.8g, N,N-dimethylethanolamine 21g.

[0032] A method for preparing a high-temperature and solvent-resistant antistatic layer includes the following steps:

[0033] S1. Mix components D and E except for the surfactant, stir until homogeneous to obtain a mixture, then add components A, B and C to the mixture in sequence, disperse and let stand for 20 minutes, finally add the surfactant and disperse to obtain an antistatic primer.

[0034] S2. Apply the antistatic primer prepared in step S1 onto a PET substrate, control the thickness of the dried coating to be 0.08 μm, and cure at 120°C for 1 min to obtain a stable antistatic layer that is resistant to high temperature and solvents.

[0035] Example 2:

[0036] The formula for the antistatic liquid is as follows: Component A: 1 kg, Component B: 300 g, Component C: 50 g, Component D: 5.2 kg of water, 10.4 kg of isopropanol, Component E: 4 g of poly(3-carboxythiophene), 94 g of methylpyrrolidone, 3 glycidyl etheroxypropyltrimethoxysilane, 3.2 g of surfactant, and 26 g of N,N-dimethylethanolamine.

[0037] A method for preparing a high-temperature and solvent-resistant antistatic layer includes the following steps:

[0038] S1. Mix components D and E except for the surfactant, stir until homogeneous to obtain a mixture, then add components A, B and C to the mixture in sequence, disperse and let stand for 20 minutes, finally add the surfactant and disperse to obtain an antistatic primer.

[0039] S2. Apply the antistatic primer prepared in step S1 onto a PET substrate, control the thickness of the dried coating to be 0.05 μm, and cure at 120°C for 1 min to obtain a stable antistatic layer that is resistant to high temperature and solvents.

[0040] Example 3:

[0041] The formula for the antistatic liquid is as follows: Component A: 1 kg, Component B: 250 g, Component C: 38 g, Component D: 4.5 kg of water and 9 kg of isopropanol, Component E: 4 g of poly(3-carboxythiophene), 82 g of methylpyrrolidone, 2 g of 3-glycidyl etheroxypropyltrimethoxysilane, 2.8 g of surfactant, and 18 g of N,N-dimethylethanolamine.

[0042] A method for preparing a high-temperature and solvent-resistant antistatic layer includes the following steps:

[0043] S1. Mix components D and E except for the surfactant, stir until homogeneous to obtain a mixture, then add components A, B and C to the mixture in sequence, disperse and let stand for 20 minutes, finally add the surfactant and disperse to obtain an antistatic primer.

[0044] S2. Apply the antistatic primer prepared in step S1 onto a PET substrate, control the thickness of the dried coating to be 0.1 μm, and cure at 120°C for 1 min to obtain a stable antistatic layer that is resistant to high temperature and solvents.

[0045] Comparative Example 1:

[0046] The high-temperature and solvent-resistant antistatic layer was prepared using the same method as in Example 1, except that poly(3-methylthiophene) was used instead of poly(3-carboxythiophene).

[0047] Comparative Example 2:

[0048] The high-temperature and solvent-resistant antistatic layer was prepared using the same method as in Example 1, except that the amount of component C was 20g.

[0049] Comparative Example 3:

[0050] The high-temperature and solvent-resistant antistatic layer was prepared using the same method as in Example 1, except that the amount of component C was 85g.

[0051] Comparative Example 4:

[0052] The high-temperature and solvent-resistant antistatic layer was prepared using the same method as in Example 1, except that γ-methacryloyloxypropyltrimethoxysilane was used instead of 3-glycidoxypropyltrimethoxysilane as the silane coupling agent.

[0053] Comparative Example 5:

[0054] The high-temperature and solvent-resistant antistatic layer was prepared using the same method as in Example 1, except that the amount of methylpyrrolidone used was 40g.

[0055] Comparative Example 6:

[0056] The high-temperature and solvent-resistant antistatic layer was prepared using the same method as in Example 1, except that the amount of methylpyrrolidone used was 120g.

[0057] experiment

[0058] 1. Antistatic properties: After the sample coating is completed and removed from the machine, the surface resistance of the sample is tested using a resistance meter. The test value is within 10. 6 -10 9 Ω indicates that the result is acceptable.

[0059] 2. Aging Resistance: Samples were placed at 60℃ / 90%RH and 85℃ / 85%RH for 4 days respectively, and then left to stand at room temperature for 2 hours. The surface of the antistatic layer was then observed using a 1500L lamp for any white fog contamination. White fog contamination indicates the presence of antistatic components, which represents aging resistance. (Note:)

[0060] No dirt or grime (qualified);

[0061] Slightly soiled (acceptable);

[0062] Moderately dirty (unacceptable);

[0063] Severely soiled (unacceptable).

[0064] 3. Solvent Resistance: Fold a cleanroom cloth twice and lay it on the membrane surface. Drop 8ml of alcohol onto the cleanroom cloth, press a 2kg weight onto the area where the alcohol was dropped, and then drag the cleanroom cloth to scrape it. Finally, test the resistance value of the antistatic layer. (Note:)

[0065] ○: When the antistatic properties remain almost unchanged and there are no scratches.

[0066] △: When the antistatic properties decrease or there are scratches

[0067] ×: When the antistatic properties are lost, or when the coating surface is worn.

[0068]

[0069]

[0070] From the test results of Examples 1-3 and Comparative Examples 1-6 above, it can be seen that the antistatic properties, high-temperature aging resistance, and solvent resistance of Example 1 all meet the usage requirements; in Example 2, the amount of methylpyrrolidone and curing agent was increased, while the coating thickness was reduced to 0.05 μm, resulting in a slight decrease in surface resistivity and aging resistance, but still meeting the usage requirements; in Example 3, the amount of curing agent was increased while the amount of methylpyrrolidone was reduced, and the coating thickness was increased to 1 μm, resulting in a certain decrease in surface resistivity, while the aging resistance was slightly different.

[0071] Compared with Example 1, Comparative Example 1 used poly(3-methylthiophene) instead of poly(3-carboxythiophene), which improved the surface resistivity. However, the aging resistance and solvent resistance could not meet the requirements. The performance of poly(3-methylthiophene) was significantly different from that of poly(3-carboxythiophene).

[0072] Compared with Example 1, the amount of curing agent used in Comparative Example 2 was reduced to 20g, and there was no significant difference in surface resistivity and aging resistance, but the solvent resistance was significantly reduced.

[0073] Compared with Example 1, the amount of curing agent used in Comparative Example 3 was increased to 85g. There was no significant difference in surface resistivity and solvent resistance, but the aging resistance was significantly reduced. The increased amount of curing agent used led to precipitation.

[0074] Compared with Example 1, Comparative Example 4 used γ-methacryloyloxypropyltrimethoxysilane instead of 3-glycidoxypropyltrimethoxysilane as the curing agent. There was no significant difference in surface resistivity and aging resistance, but the solvent resistance was significantly reduced.

[0075] Compared with Example 1, the amount of 5-methylpyrrolidone used in Comparative Example was reduced to 40g. There was no significant difference in solvent resistance and aging resistance, but the surface resistivity was significantly increased.

[0076] Compared with Example 1, the amount of 6-methylpyrrolidone in Comparative Example was increased to 120g, and the surface resistivity value decreased significantly. At the same time, the solvent resistance was still satisfactory, but the aging resistance decreased significantly. The increase in the amount of 6-methylpyrrolidone led to precipitation.

[0077] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are exhaustively listed. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0078] For those skilled in the art, various modifications and improvements can be made without departing from the concept of the present invention, and these modifications and improvements are all within the scope of protection of the present invention. The scope of protection of the present invention is defined by the appended claims.

Claims

1. A high-temperature and solvent-resistant antistatic layer, characterized in that, The antistatic layer is obtained by coating a high-temperature and solvent-resistant antistatic primer onto a PET substrate, controlling the thickness of the dried coating to be 0.05-0.1 μm, and curing it at 120°C. The high-temperature and solvent-resistant antistatic primer comprises: Component A: PEDOT / PSS antistatic liquid with a solid content of 1.2-1.6%; Component B: waterborne polyurethane containing hydroxyl groups with a solid content of 25-35%; Component C: CL600 curing agent; Component D: a mixed solution of water and isopropanol; Component E: a polythiophene conductive polymer containing carboxyl groups, a conductivity enhancer, a silane coupling agent containing epoxy groups, a surfactant, and a pH adjuster. The mass ratio of component A to component B is 4:1-3:1, the mass ratio of component A to component C is 40:1-40:2, the mass of component D is 10-12 times the total mass of components A and B, and the mass of the carboxyl-containing polythiophene conductive polymer, the conductivity enhancer, and the epoxy-containing silane coupling agent in component E are 0.3-0.7%, 8-10%, and 0.2-0.5% of the mass of component A, respectively.

2. The high-temperature and solvent-resistant antistatic layer according to claim 1, characterized in that, The carboxyl-containing polythiophene conductive polymer is one or more of poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), and poly(3-methyl-4-carboxybutylthiophene).

3. The high-temperature and solvent-resistant antistatic layer according to claim 1, characterized in that, The conductivity enhancer is a compound with an amide group in its molecule, specifically one or more of 2-pyrrolidone, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylformamide, formamide, acetamide, and N,N-dimethylformamide.

4. The high-temperature and solvent-resistant antistatic layer according to claim 1, characterized in that, The epoxy-containing silane coupling agent is 3-glycidoxypropyltrimethoxysilane and / or 3-glycidoxypropyltriethoxysilane.

5. The high-temperature and solvent-resistant antistatic layer according to claim 1, characterized in that, The surfactant is a nonionic surfactant, and the mass of the surfactant is 0.2-0.5% of the mass of component A.

6. The high-temperature and solvent-resistant antistatic layer according to claim 1, characterized in that, The pH adjuster is an amine compound, and the mass of the pH adjuster is 1-3% of the mass of component A.

7. A method for preparing a high-temperature resistant and solvent-resistant antistatic layer according to any one of claims 1-6, characterized in that, Includes the following steps: S1. Mix components D and E except for the surfactant, stir until homogeneous to obtain a mixture, then add components A, B and C to the mixture in sequence, disperse and let stand for 20-30 minutes, finally add the surfactant and disperse until homogeneous to obtain an antistatic primer. S2. Apply the antistatic primer prepared in step S1 onto a PET substrate, control the thickness of the dried coating to be 0.05-0.1 μm, and cure at 120℃ for 1 min to obtain a stable antistatic layer that is resistant to high temperature and solvents.

8. The application of an antistatic layer in a polarizer, characterized in that, The antistatic layer is the high-temperature resistant and solvent-resistant antistatic layer as described in any one of claims 1-6.

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