Aluminum foil composite anti-self-breaking production process
By compounding carbon nanotube-modified polyurethane and high-molecular polyester film layers on the surface of aluminum foil, the problems of easy breakage of aluminum foil and insufficient interface bonding strength are solved, efficient and stable production of aluminum foil composite materials is achieved, and the anti-breakage performance and heat resistance of aluminum foil are improved.
Patent Information
- Application Number
- CN202510808069.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-17
- Publication Date
- 2025-10-10
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Traditional aluminum foil is prone to spontaneous fracture and insufficient interface bonding strength due to stress concentration during processing and use, resulting in unstable composite material structure. In addition, the existing curing process is inefficient and energy-intensive, and the adhesive layer has a single function.
Carbon nanotube-modified polyurethane is coated on the surface of aluminum foil, and a high-molecular polyester film layer is composited through corona treatment and roller pressing. Combined with the microwave sensitivity and high strength characteristics of carbon nanotubes, rapid and uniform curing and stress dispersion are achieved, thereby enhancing the toughness and adhesion of the aluminum foil.
The anti-breaking performance of aluminum foil is significantly improved, the tensile strength is increased by 20%-22%, the elongation at break is increased by nearly 1 times, and the curing time is shortened, and the heat resistance and bonding stability of the aluminum foil are enhanced.
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Figure SMS_1
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of aluminum foil production, and in particular to a production process for composite aluminum foil that prevents self-breaking. Background Art
[0002] Aluminum foil, a lightweight, highly conductive metal material with excellent barrier properties, is widely used in electronic device packaging, new energy battery current collectors, food packaging, and other fields. However, traditional aluminum foil faces significant challenges during processing and use. First, its thin thickness (typically 6-20μm) makes it susceptible to stress concentration during mechanical processing (such as stamping and slitting) or under long-term cyclic loading, causing microcracks to propagate and lead to spontaneous fracture. Second, the interface bonding strength between the aluminum foil surface and the polymer material is insufficient, making interlayer delamination prone to thermal stress or environmental corrosion, seriously affecting the structural stability of the composite material.
[0003] Existing aluminum foil composite materials still face the following technical bottlenecks: low curing process efficiency and high energy consumption; the adhesive layer has a single function, unable to simultaneously achieve rapid curing, stress dispersion, and long-term antioxidant properties. Therefore, it is necessary to develop an aluminum foil composite anti-self-fracture material that combines an efficient preparation process with excellent mechanical properties and long-term stability. Summary of the Invention
[0004] The object of the present invention is to provide a production process for composite aluminum foil to prevent self-breakage, so as to solve at least one of the above-mentioned problems of the prior art.
[0005] A production process for aluminum foil composite anti-self-breakage, comprising the following steps: Step 1: Use acetone or ethanol ultrasonic cleaning (frequency 40kHz, power 300W, time 3-5 minutes) to remove oil stains on the surface of the aluminum foil layer; then perform corona treatment on the aluminum foil layer; Step 2: coating the carbon nanotube-modified polyurethane on the surface of the aluminum foil to obtain a polyurethane adhesive layer; Step 3: Roll-pressing a composite high-molecular polyester on the surface of the polyurethane adhesive layer to obtain a high-molecular polyester film layer; Step 4: Curing the aluminum foil layer compounded with the high molecular polyester film layer and the polyurethane adhesive layer at a temperature of 60-70° C. to obtain a composite anti-self-breaking aluminum foil.
[0006] As a further technical solution of the present invention: parameters of the corona treatment are: power 80-120 W / m², treatment speed 10-20 m / min, and the surface tension of the aluminum foil is increased to ≥38 dyn / cm.
[0007] As a further technical solution of the present invention: the coating temperature is 50-70° C., and the pressure is 0.2-0.5 MPa.
[0008] As a further technical scheme of the present application: the roll compounding parameter is 0.4-0.8 MPa.
[0009] As a further technical scheme of the present application: the curing time is 6-9 hours.
[0010] As a further technical scheme of the present application: the preparation of carbon nanotube modified polyurethane comprises the following steps: Mixing amino silane coupling agent, hydroxylated carbon nanotube and benzene solvent to obtain amino silane coupling agent modified carbon nanotube solution; the silane coupling agent is octadecyltrichlorosilane; Ultrasonic dispersion of the polyurethane with amino acid structure in the main chain in dry N,N-dimethylformamide, adding N'N-carbonyldiimidazole, keeping dry inert gas, stirring and reacting at 40-80 DEG C for 3-6 hours; then adding the amino silane coupling agent modified carbon nanotube solution, stirring and reacting at 40-80 DEG C for 8-24 hours to obtain carbon nanotube modified polyurethane.
[0011] As a further technical scheme of the present application: the mass ratio of amino silane coupling agent, hydroxylated carbon nanotube and benzene is 23-50:1-2:1000.
[0012] As a further technical scheme of the present application: the amino silane coupling agent is one or more of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane and gamma-aminoethyl aminopropyl trimethoxysilane.
[0013] As a further technical scheme of the present application: the mass ratio of the polyurethane with amino acid structure in the main chain, N'N-carbonyldiimidazole and the amino silane coupling agent modified carbon nanotube is 1:0.1-0.5:5-20.
[0014] As a further technical scheme of the present application: it comprises a high molecular polyester film layer, a polyurethane adhesive layer and an aluminum foil layer.
[0015] The present application has the following advantages: The present application has the following advantages:
[0016] The carbon nanotube as microwave sensitive filler can absorb microwave energy and convert it into heat energy when the polyurethane adhesive is cured on the surface of the aluminum foil, realizing rapid and uniform heating inside the adhesive layer, which effectively shortens the time for curing the polyurethane adhesive on the aluminum foil, and the carbon nanotube realizes rapid and uniform curing of the polyurethane adhesive; The carbon nanotube has very high tensile strength and elastic modulus. The tensile strength of the carbon nanotube fiber can be as high as 4.2 GPa, and has very high fracture toughness, thereby effectively guaranteeing the anti-fracture performance of the carbon nanotube itself; The carbon nanotube has high strength, high modulus and excellent heat conduction performance. These characteristics enable the carbon nanotube to significantly improve the mechanical properties and heat conduction performance of the polyurethane material, thereby enhancing the heat resistance of the aluminum foil; The polyurethane containing the amino acid structure in the main chain introduces a monomer amino acid with specific functions into the polyurethane material, which can effectively improve the oxidation resistance and adhesion of the aluminum foil bonding layer. Therefore, by improving the oxidation resistance and adhesion of the bonding layer, the anti-self-breaking performance of the composite aluminum foil is further improved. DETAILED DESCRIPTION
[0017] In order for those skilled in the art to better understand the present application, the technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor should belong to the scope of protection of the present application. Embodiment 1
[0018] The present application provides a production process of aluminum foil composite anti-self-breaking, comprising the following steps: Step 1: ultrasonic cleaning (frequency 40 kHz, power 300 W, time 3-5 minutes) with acetone or ethanol to remove oil stains on the surface of the aluminum foil layer; then corona treatment is performed on the aluminum foil layer; the parameters of the corona treatment are: power 80 W / m², treatment speed 10 m / min, and the surface tension of the aluminum foil is increased to 38 dyn / cm; Step 2: carbon nanotube modified polyurethane is coated on the surface of the aluminum foil, the coating temperature is 50°C, and the pressure is 0.2 MPa, to obtain a polyurethane adhesive layer; Step 3: roll composite high molecular polyester on the surface of the polyurethane adhesive layer to obtain a high molecular polyester film layer; wherein the roll composite parameter is 0.4-MPa; Step 4: curing the aluminum foil layer with the composite high molecular polyester film layer and the polyurethane adhesive layer at a temperature of 60°C for 6 hours to obtain a composite anti-self-breaking aluminum foil; Preparation of carbon nanotube modified polyurethane, comprising the following steps: Mixing amino silane coupling agent, hydroxylated carbon nanotube and benzene solvent to obtain an amino silane coupling agent modified carbon nanotube solution; the silane coupling agent is octadecyltrichlorosilane; the mass ratio of the amino silane coupling agent, the hydroxylated carbon nanotube and benzene is 23:1:1000; the amino silane coupling agent is γ-aminopropyltriethoxysilane; The main chain amino acid structure containing polyurethane is ultrasonically dispersed in dry N,N-dimethylformamide, N'N-carbonyldiimidazole is added, dry inert gas is introduced, and stirring is carried out at 40℃ for 3h; then the amino silane coupling agent modified carbon nanotube solution is added, and stirring is carried out at 40℃ for 8-24h to obtain the carbon nanotube modified polyurethane; The mass ratio of the main chain amino acid structure containing polyurethane, N'N-carbonyldiimidazole and the amino silane coupling agent modified carbon nanotube is 1:0.1-0.5:5-20; The preparation process of the main chain amino acid structure containing polyurethane comprises the following steps: Step 1: the amino acid (10 mmol) is dissolved in excess methanol (50 mL), and concentrated sulfuric acid (0.5 mL) is added as a catalyst; refluxing is carried out (refluxing temperature 65℃, refluxing time 6h), methanol is removed by rotary evaporation, the product is washed with diethyl ether and dried to generate a methyl carboxylate; Step 2: the lysine (10 mmol) and PCL-diol (5 mmol) are dissolved in anhydrous DMF (50 mL); DCC (12 mmol) and DMAP (1 mmol) are added, and the reaction is carried out at room temperature under nitrogen protection for 24h; the generated dicyclohexyl urea (DCU) is removed by filtration, the solvent is removed by rotary evaporation, and the product is precipitated with ethanol and vacuum dried to obtain the amino acid modified polyol; Step 3: the amino acid modified polyol (10 g) is dissolved in anhydrous DMF with excess diisocyanate (such as HDI, molar ratio NCO:OH=2:1); the catalyst DBTDL (0.1 wt%) is added, the temperature is raised to 80℃, and the reaction is carried out for 2h to generate an isocyanate-terminated prepolymer; the chain extender (such as 1,4-butanediol (BDO), the molar ratio is matched with the remaining NCO groups) is added, and the reaction is continued for 1h. Pour the reaction liquid into a polytetrafluoroethylene mold, and vacuum dry at 80℃ for 24h to obtain the main chain amino acid structure containing polyurethane. Example 2
[0019] The present application provides an aluminum foil composite self-breaking prevention production process, comprising the following steps: Step 1: acetone or ethanol ultrasonic cleaning (frequency 40kHz, power 300W, time 4 minutes) is used to remove the oil stains on the surface of the aluminum foil layer; then the aluminum foil layer is subjected to corona treatment; the parameters of the corona treatment are: power 100W / m², treatment speed 15m / min, and the surface tension of the aluminum foil is increased to 40 dyn / cm; Step 2: the carbon nanotube modified polyurethane is coated on the surface of the aluminum foil, the coating temperature is 60℃, and the pressure is 0.4MPa to obtain a polyurethane adhesive layer; Step 3: Roll-compounding a high molecular weight polyester on the surface of the polyurethane adhesive layer to obtain a high molecular weight polyester film layer; wherein the rolling lamination parameter is 0.6 MPa; Step 4: curing the aluminum foil layer composited with the high molecular polyester film layer and the polyurethane adhesive layer at a temperature of 65° C. to obtain a composite anti-self-breaking aluminum foil, wherein the curing time is 7 hours; An aminosilane coupling agent, hydroxylated carbon nanotubes and benzene solvent are mixed to obtain an aminosilane coupling agent-modified carbon nanotube solution; the silane coupling agent is octadecyltrichlorosilane; the mass ratio of the aminosilane coupling agent, hydroxylated carbon nanotubes and benzene is 35:1.5:1000; the aminosilane coupling agent is γ-aminopropyltrimethoxysilane; The polyurethane containing an amino acid structure in the main chain is ultrasonically dispersed in dry N,N-dimethylformamide, N'N-carbonyldiimidazole is added, and a dry inert gas is kept flowing, and the reaction is stirred at 60°C for 3 to 6 hours; then, an aminosilane coupling agent is added to modify the carbon nanotube solution, and the reaction is stirred at 60°C for 8 to 24 hours to obtain a carbon nanotube-modified polyurethane; The mass ratio of polyurethane containing amino acid structure in the main chain, N'N-carbonyldiimidazole and aminosilane coupling agent modified carbon nanotubes is 1:0.3:13; The preparation process of polyurethane containing an amino acid structure in the main chain comprises the following steps: Step 1: Dissolve the amino acid (10 mmol) in excess methanol (50 mL) and add concentrated sulfuric acid (0.5 mL) as a catalyst. Reflux the reaction (65°C for 7 h). Remove the methanol by rotary evaporation. Wash the product with ether and dry it to produce the methyl carboxylate. Step 2: Lysine (10 mmol) and PCL-diol (5 mmol) were dissolved in anhydrous DMF (50 mL); DCC (12 mmol) and DMAP (1 mmol) were added and reacted at room temperature under nitrogen for 24 h. The generated dicyclohexylurea (DCU) was filtered out, the solvent was removed by rotary evaporation, the product was precipitated with ethanol and dried in vacuo to obtain the amino acid-modified polyol. Step 3: Dissolve the amino acid-modified polyol (10 g) and an excess diisocyanate (e.g., HDI, at a molar ratio of NCO:OH = 2:1) in anhydrous DMF. Add the catalyst, DBTDL (0.1 wt%), heat to 80°C, and react with stirring for 2 hours to produce an isocyanate-terminated prepolymer. Add a chain extender (e.g., 1,4-butanediol (BDO), at a molar ratio matching the remaining NCO groups) and continue the reaction for 1 hour. Pour the reaction solution into a polytetrafluoroethylene mold and dry it in a vacuum at 80°C for 24 hours to obtain a polyurethane containing an amino acid structure in the backbone. Example 3
[0020] The embodiment of the present invention provides a production process for aluminum foil composite anti-self-breakage, comprising the following steps: Step 1: Use acetone or ethanol ultrasonic cleaning (frequency 40kHz, power 300W, time 5 minutes) to remove oil stains on the aluminum foil layer. Then, perform corona treatment on the aluminum foil layer. The corona treatment parameters are: power 120W / m², processing speed 20m / min, and the surface tension of the aluminum foil is increased to 45 dyn / cm. Step 2: coating the carbon nanotube-modified polyurethane on the surface of the aluminum foil at a coating temperature of 70°C and a pressure of 0.5 MPa to obtain a polyurethane adhesive layer; Step 3: Roll-pressing the high molecular weight polyester on the surface of the polyurethane adhesive layer to obtain a high molecular weight polyester film layer; wherein the rolling lamination parameter is 0.8 MPa; Step 4: curing the aluminum foil layer composited with the high molecular polyester film layer and the polyurethane adhesive layer at a temperature of 70° C. to obtain a composite anti-self-breaking aluminum foil, wherein the curing time is 9 hours; An aminosilane coupling agent, hydroxylated carbon nanotubes and benzene solvent are mixed to obtain an aminosilane coupling agent-modified carbon nanotube solution; the silane coupling agent is octadecyltrichlorosilane; the mass ratio of the aminosilane coupling agent, hydroxylated carbon nanotubes and benzene is 50:2:1000; the aminosilane coupling agent is γ-aminoethylaminopropyltrimethoxysilane; A polyurethane containing an amino acid structure in the main chain was ultrasonically dispersed in dry N,N-dimethylformamide, N'N-carbonyldiimidazole was added, and a dry inert gas was kept flowing. The mixture was stirred and reacted at 80°C for 6 hours. Then, an aminosilane coupling agent-modified carbon nanotube solution was added and the mixture was stirred and reacted at 80°C for 24 hours to obtain a carbon nanotube-modified polyurethane. The mass ratio of polyurethane containing amino acid structure in the main chain, N'N-carbonyldiimidazole and aminosilane coupling agent modified carbon nanotubes is 1:0.5:20; The preparation process of polyurethane containing an amino acid structure in the main chain comprises the following steps: Step 1: Dissolve the amino acid (10 mmol) in excess methanol (50 mL) and add concentrated sulfuric acid (0.5 mL) as a catalyst. Reflux the reaction (65°C for 6-8 h). Remove the methanol by rotary evaporation. Wash the product with ether and dry it to produce the methyl carboxylate. Step 2: Lysine (10 mmol) and PCL-diol (5 mmol) were dissolved in anhydrous DMF (50 mL); DCC (12 mmol) and DMAP (1 mmol) were added and reacted at room temperature under nitrogen for 24 h. The generated dicyclohexylurea (DCU) was filtered out, the solvent was removed by rotary evaporation, the product was precipitated with ethanol and dried in vacuo to obtain the amino acid-modified polyol. Step 3: Dissolve the amino acid-modified polyol (10 g) and an excess diisocyanate (e.g., HDI, at a molar ratio of NCO:OH = 2:1) in anhydrous DMF. Add the catalyst, DBTDL (0.1 wt%), heat to 80°C, and react with stirring for 2 hours to produce an isocyanate-terminated prepolymer. Add a chain extender (e.g., 1,4-butanediol (BDO), at a molar ratio matching the remaining NCO groups) and continue the reaction for 1 hour. Pour the reaction solution into a polytetrafluoroethylene mold and dry it in a vacuum at 80°C for 24 hours to obtain a polyurethane containing an amino acid structure in the backbone.
[0021] Comparative Example 1 Comparative Example 1 differs from Example 1 in that polyurethane is directly used instead of carbon nanotube-modified polyurethane. The aluminum foil composite anti-self-breaking production process comprises the following steps: Step 1: Use acetone or ethanol ultrasonic cleaning (frequency 40kHz, power 300W, time 3 minutes) to remove oil stains on the aluminum foil surface. Then, perform corona treatment on the aluminum foil. The corona treatment parameters are: power 80W / m², processing speed 10m / min, and the surface tension of the aluminum foil is increased to 38 dyn / cm. Step 2: coating polyurethane on the surface of the aluminum foil at a coating temperature of 50°C and a pressure of 0.2 MPa to obtain a polyurethane adhesive layer; Step 3: Roll-compounding a high molecular weight polyester on the surface of the polyurethane adhesive layer to obtain a high molecular weight polyester film layer; wherein the rolling lamination parameter is 0.4 MPa; Step 4: Curing the aluminum foil layer compounded with the high molecular polyester film layer and the polyurethane adhesive layer at a temperature of 60° C. to obtain a composite anti-self-breaking aluminum foil, wherein the curing time is 6 hours.
[0022] The performance anti-fracture test was carried out on Examples 1-3 and Comparative Example 1. The test results are shown in the following table:
[0023] As can be seen from the above table, the composite aluminum foil prepared from carbon nanotube-modified polyurethane in the present invention has a tensile strength increased by about 20%-22%, and an elongation at break increased by nearly 100%, indicating that carbon nanotube-modified polyurethane can effectively improve the anti-breaking performance of aluminum foil.
[0024] The above is a detailed description of an embodiment of the present invention. However, the content described is only a preferred embodiment of the present invention and should not be considered to limit the scope of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.
Claims
1. A production process for aluminum foil composite anti-self-breaking, characterized in that: The following steps are involved: Step 1: Use acetone or ethanol to ultrasonically clean the aluminum foil to remove oil stains on the surface; then perform corona treatment on the aluminum foil; Step 2: coating the carbon nanotube-modified polyurethane on the surface of the aluminum foil to obtain a polyurethane adhesive layer; Step 3: Roll-pressing a composite high-molecular polyester on the surface of the polyurethane adhesive layer to obtain a high-molecular polyester film layer; Step 4: Curing the aluminum foil layer compounded with the high molecular polyester film layer and the polyurethane adhesive layer at a temperature of 60-70° C. to obtain a composite anti-self-breaking aluminum foil.
2. The aluminum foil composite anti-self-breaking production process according to claim 1 is characterized in that: Corona treatment parameters: power 80-120W / m², treatment speed 10-20m / min, aluminum foil surface tension increased to ≥38 dyn / cm.
3. The aluminum foil composite anti-self-breaking production process according to claim 1 is characterized in that: Coating temperature is 50-70℃, pressure is 0.2-0.5MPa.
4. The aluminum foil composite anti-self-breaking production process according to claim 1 is characterized in that: Roller pressing parameters are 0.4-0.8MPa.
5. The aluminum foil composite anti-self-breaking production process according to claim 1 is characterized in that: Curing time 6-9 hours.
6. The aluminum foil composite anti-self-breaking production process according to claim 1 is characterized in that: The preparation of carbon nanotube-modified polyurethane comprises the following steps: Mixing an aminosilane coupling agent, hydroxylated carbon nanotubes and a benzene solvent to obtain an aminosilane coupling agent-modified carbon nanotube solution; the silane coupling agent is octadecyltrichlorosilane; A polyurethane containing an amino acid structure in the main chain is ultrasonically dispersed in dry N,N-dimethylformamide, N'N-carbonyldiimidazole is added, and a dry inert gas is kept flowing. The mixture is stirred and reacted at 40°C to 80°C for 3 to 6 hours; then, an aminosilane coupling agent is added to modify the carbon nanotube solution, and the mixture is stirred and reacted at 40°C to 80°C for 8 to 24 hours to obtain a carbon nanotube-modified polyurethane.
7. The aluminum foil composite anti-self-breaking production process according to claim 6 is characterized in that: The mass ratio of the aminosilane coupling agent, the hydroxylated carbon nanotubes and benzene is 23-50:1-2:1000.
8. The aluminum foil composite anti-self-breaking production process according to claim 7 is characterized in that: The aminosilane coupling agent is one or more of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminoethylaminopropyltrimethoxysilane.
9. The aluminum foil composite anti-self-breaking production process according to claim 8 is characterized in that: The mass ratio of polyurethane with amino acid structure in the main chain, N'N-carbonyldiimidazole and aminosilane coupling agent modified carbon nanotube is 1:0.1-0.5:5-20.
10. The aluminum foil composite anti-self-breaking production process according to claim 1 is characterized in that: include: High molecular polyester film layer, polyurethane adhesive layer and aluminum foil layer.