Low-residual copper rolling liquid and application thereof

Abstract

This invention belongs to the field of lubricating materials technology, specifically relating to a low-residue copper rolling fluid and its application. This low-residue copper rolling fluid, by mass percentage, consists of 90.0%–94.6% base oil, 0.2%–0.5% copper corrosion inhibitor, 0.2%–0.5% 2-alkyl-1-alkanol, 0.5%–2.0% isopropyl phosphate, 0.5%–1.0% triphenyl phosphate, 0.5%–2.0% butyl stearate, 0.5%–1.5% composite antioxidant, and 3.0%–10.0% diisooctyl sebacate. The base oil in this low-residue copper rolling fluid formulation does not contain harmful components such as aromatic hydrocarbons, chlorides, and heavy metals. The addition of flame retardants increases the flash point, reduces oil mist generated during rolling, and minimizes pollution, resulting in excellent health, safety, and environmental characteristics. By maintaining high lubricity while reducing residue, it can be applied in the copper rolling field, especially suitable for thin copper rolling.

Description

Technical Field

[0001] This invention belongs to the field of lubricating materials technology, specifically relating to a low-residue copper rolling fluid and its application. Background Technology

[0002] In copper and copper alloy processing, lubrication control during cold rolling is a crucial factor. Proper lubrication reduces rolling forces and wear, improves product surface quality and finish, and extends the service life of the rolling mill. The primary lubricant used in copper rolling is rolling oil. Different copper alloys have different lubrication requirements, thus demanding increasingly higher performance from the rolling media used in the processing. In particular, emerging high-tech fields are driving increased downstream demand, such as PCB copper foil for 5G base station construction and electronic copper sheets and foils for shipbuilding and marine engineering.

[0003] Currently, blended oil is the most widely used oil in copper strip rolling. Blended oil is made by blending refined mineral oil with various functional additives, thus possessing characteristics such as high oil film strength, resistance to breakage, strong oxidation resistance, good surface finish of rolled material, low roughness, and high cleanliness after annealing. However, due to the relatively low heat capacity and poor cooling effect of mineral oil, it limits the increase in rolling speed to some extent.

[0004] Copper rolling fluids are typically formulated with solvent refining, paraffin-based mineral oil, and high-performance lubricating additives. Based on the requirements of the on-site process, parameters such as viscosity, lubrication capacity, anti-wear properties, and detergency of the rolling fluid are designed to effectively ensure good lubrication and cooling capabilities. This results in a high-smoothness surface finish and minimal residue after rolling, meeting the lubrication requirements of copper cold rolling.

[0005] Currently, most commercially available cold rolling media for copper and copper alloys are made of pure oil-based media mixed with additives, suitable only for general production processes, such as cold rolling and foil rolling of 1-5mm. However, they are not suitable for cold rolling and foil rolling of less than 1mm. Cold rolling and foil rolling of less than 1mm requires higher requirements for lubrication and residue, especially for cold rolling and foil rolling of less than 0.1mm, which requires even higher precision lubrication and low residue. There is an urgent need to develop copper rolling fluids that simultaneously meet the requirements of high lubricity and low residue. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a low-residue copper rolling fluid and its application. In solving the lubrication and residue issues, this invention, based on the screening of base oils, rigorously screens each additive, conducts formulation research, and finally develops a copper rolling fluid that simultaneously satisfies high lubricity and low residue, and can be used for rolling thin and ultra-thin copper foils.

[0007] On one hand, the present invention provides a low-residual copper rolling solution, which is composed of 90.0% to 94.6% base oil, 0.2% to 0.5% copper corrosion inhibitor, 0.2% to 0.5% 2-alkyl-1-alkanol, 0.5% to 2.0% isopropyl phosphate, 0.5% to 1.0% triphenyl phosphate, 0.5% to 2.0% butyl stearate, 0.5% to 1.5% composite antioxidant and 3.0% to 10.0% diisooctyl sebacate by weight percentage.

[0008] Furthermore, in the low residual copper rolling solution, the base oil is composed of paraffin-based low viscosity solvent oil.

[0009] Furthermore, in the low residual copper rolling solution, the paraffin-based low viscosity solvent oil is a C12-20 isoparaffin and a 60N base oil.

[0010] Furthermore, in the low residual copper rolling solution, the composite antioxidant is composed of propylene glycol and butylated hydroxyanisole.

[0011] Furthermore, in the low residual copper rolling solution, the composite antioxidant consists of 50% propylene glycol and 50% butylated hydroxyanisole by mass percentage.

[0012] Furthermore, in the low residual copper rolling solution, the butyl hydroxyanisole is a mixture of 2-tert-butyl-4-hydroxyanisole and 3-tert-butyl-4-hydroxyanisole.

[0013] Furthermore, in the low residual copper rolling solution, the mass percentage of 2-tert-butyl-4-hydroxyanisole to 3-tert-butyl-4-hydroxyanisole is 1:1.5-2.

[0014] On the other hand, the present invention also provides the application of the low residual copper rolling solution in the rolling of copper or copper alloys.

[0015] Furthermore, the low-residual copper rolling solution is applied to the rolling of copper or copper alloys with a thickness ranging from 0.06 to 1.5 mm.

[0016] Furthermore, the low-residual copper rolling solution is applied to the rolling of copper or copper alloys with a thickness in the range of 0.06-0.001 mm.

[0017] Compared with the prior art, the present invention has at least the following advantages or beneficial effects:

[0018] This invention, through extensive screening of formulation components and formulation research, has developed a low-residual copper rolling fluid. This low-residual copper rolling fluid, by mass percentage, comprises 90.0%–94.6% base oil, 0.2%–0.5% copper corrosion inhibitor, 0.2%–0.5% 2-alkyl-1-anol, 0.5%–2.0% isopropyl phosphate, 0.5%–1.0% triphenyl phosphate, 0.5%–2.0% butyl stearate, 0.5%–1.5% composite antioxidant, and 3.0%–10.0% diisooctyl sebacate.

[0019] The antioxidant in the copper rolling solution provided by this invention is a composite antioxidant with excellent antioxidant properties. In addition, the butylated hydroxyanisole in the composite antioxidant is a mixture of 2-tert-butyl-4-hydroxyanisole and 3-tert-butyl-4-hydroxyanisole. The mixture of 3-tert-butyl-4-hydroxyanisole and 2-tert-butyl-4-hydroxyanisole has a synergistic effect.

[0020] The copper rolling fluid of this invention has undergone component screening and formulation research to improve lubrication and reduce residue, meeting the high-end manufacturing process requirements for extremely high-precision surface quality of copper and copper alloys; it can provide good lubrication performance and maximize the extension of roll life, enabling the rolls to maintain excellent rolling performance under high-speed rolling; it maintains the best surface quality of the strip and reduces the scrap rate in high-end manufacturing, thus reducing the production cost of copper strip and foil.

[0021] The copper rolling fluid provided by this invention contains no harmful components such as aromatic hydrocarbons, chlorides, and heavy metals in its base oil formulation. The addition of flame retardants increases the ignition point, reduces oil mist generated during rolling, and minimizes pollution, resulting in excellent health, safety, and environmental protection properties. Detailed Implementation

[0022] The technical solution of the present invention will be described below with reference to the embodiments. However, the present invention is not limited to the following embodiments.

[0023] Unless otherwise specified, the experimental and testing methods in the following embodiments are conventional methods; the raw materials and materials are commercially available unless otherwise specified; and the index data are conventional measurement methods unless otherwise specified.

[0024] "Copper rolling fluid" is a special liquid used for copper processing. It can not only protect and lubricate the surface of copper and cool the heat generated during processing, but also promote the plastic deformation of copper and improve processing efficiency.

[0025] "Copper strip" refers to rolled copper products with a thickness between 0.06 and 1.5 mm.

[0026] "Copper foil" refers to the copper rolling process with a thickness between 0.06 and 0.001 mm.

[0027] The following are some exemplary components and their properties in this invention:

[0028] Base oil: Mineral oil, a non-polar substance, can only form a non-polar physical adsorption film on the surface of copper materials. Its lubricating performance is poor, and it is rarely used directly in process lubrication, usually serving as a base oil for formulating process lubricants. However, since it accounts for about 90% of rolling oil, its selection directly affects the application environment of the product. Safety and surface cleanliness are also important factors that cannot be ignored. Therefore, it is required to have advantages such as strong cleaning power, good compatibility with additive materials, non-toxicity, and no environmental pollution. Therefore, base oil (solvent oil) needs to be precisely controlled in terms of viscosity, flash point, distillation range, sulfur content, aromatic content, annealing detergency, and acid value. For high-end manufacturing of copper plates, strips, and foils, C12-20 isoparaffinic hydrocarbons are used as the main base oil, with 60N base oil as a secondary base oil.

[0029] Isopropyl phosphate: a mixture of monoesters and diesters. Molecular structural formula:

[0030]

[0031] It has the following characteristics: 1) It provides extreme pressure lubricant with a very small amount of usage; 2) Due to its relatively small molecular weight and isomers, it has relatively high volatility, which can reduce residue in the copper cold foil rolling process; 3) It simultaneously satisfies the dual contradiction of providing extreme pressure lubrication while reducing residue.

[0032] 2-alkyl-1-alkanols are a class of saturated primary alcohols. Due to their unique structure with two 100% linear alkyl chains, they possess the following characteristics: 1) low volatility; 2) low irritation; 3) low freezing point; 4) excellent lubricity; 5) excellent oxidative stability; 6) good solubility and dissolving power; 7) low viscosity; 8) good biodegradability; and 9) good wettability, adsorption, and cleaning properties.

[0033] Butyl stearate: an oil-soluble ester with the following characteristics: 1) Good thermal stability, allowing use at higher temperatures without easily decomposing or deteriorating; 2) Good low-temperature performance, with a low freezing point, allowing use at low temperatures without easily solidifying. Because copper cold and foil rolling oils are used in unheated environments, with only frictional heat under low-temperature conditions, their properties ensure the uniformity of the rolling oil.

[0034] Triphenyl phosphate: a flame retardant and lubricant. In traditional copper rolling oil products, it plays a role in raising the ignition point and flash point, effectively increasing the ignition point of the solvent oil by 30°C.

[0035] Antioxidant Complex Additive: The antioxidant is a complex agent, avoiding the need for heating and melting during product manufacturing. The antioxidant complex additive, by mass percentage, consists of propylene glycol and butylated hydroxyanisole (BHA) in a 50:50 ratio. The BHA is composed of two isomers: 3-tert-butyl-4-hydroxyanisole and 2-tert-butyl-4-hydroxyanisole. Compared to BHA, the antioxidant effect of 3-tert-butyl-4-hydroxyanisole is 1.5 to 2 times stronger. The combination of the two exhibits a synergistic effect. Furthermore, it has good ester compatibility with other components.

[0036] Copper corrosion inhibitor: Lanxess brand lubricant additives are selected. RC8239 is an effective inhibitor of corrosion prevention for copper and its alloys. It forms a stable film on the metal surface through chemisorption, providing protection without leaving any residue. The free copper ions have virtually no adverse effect on the oxidative stability of the lubricating oil. Compared to solid benzotriazole derivatives, RC8239 exhibits good solubility and excellent corrosion inhibition, isolation, and rust prevention properties, even in PAO and Group 2 base oils. Experiments have verified that RC8239's anti-corrosion effect in copper rolling oils is superior to benzotriazole and methylbenzotriazole.

[0037] Diisooctyl sebacate: It is a relatively small molecule ester that can reduce residue while providing dynamic and boundary lubrication, and has good solubility.

[0038] Example 1

[0039] This example demonstrates the preparation of a low-residual-copper rolling solution.

[0040] Weigh out 90.0%–94.6% base oil, 0.2%–0.5% copper corrosion inhibitor, 0.2%–0.5% 2-alkyl-1-alkanol, 0.5%–2.0% isopropyl phosphate, 0.5%–1.0% triphenyl phosphate, 0.5%–2.0% butyl stearate, 0.5%–1.5% compound antioxidant, and 3.0%–10.0% diisooctyl sebacate by weight percentage.

[0041] The base oil is mainly composed of paraffinic low-viscosity solvent oil C12-20 isoparaffinic hydrocarbons, with 60N base oil as a secondary base oil.

[0042] The compound antioxidant consists of 50% propylene glycol and 50% butylated hydroxyanisole by weight percentage. Butylated hydroxyanisole is a mixture of 2-tert-butyl-4-hydroxyanisole and 3-tert-butyl-4-hydroxyanisole.

[0043] Table 1

[0044]

[0045] The above components were added to a 250ml beaker according to the mass percentage of the formula, and stirred and mixed at 25-30℃ for 3 hours to obtain a colorless and transparent oil, which is the low residual copper rolling solution of Example 1, and marked as No. 1 low residual copper rolling solution for later use.

[0046] Example 2

[0047] This example demonstrates the preparation of a low-residual-copper rolling solution.

[0048] Weigh each component according to the mass percentage of each component in Table 2, and set aside for later use.

[0049] Table 2

[0050]

[0051] Add the above components to a 250ml beaker according to the mass percentage of the formula, stir and mix at 25-30℃ for 3 hours to obtain a colorless and transparent oil, which is the low residual copper rolling solution of Example 2, and marked as No. 2 low residual copper rolling solution for later use.

[0052] Example 3

[0053] This example demonstrates the preparation of a low-residual-copper rolling solution.

[0054] Weigh each component according to the mass percentage of each component in Table 3, and set aside for later use.

[0055] Table 3

[0056]

[0057]

[0058] Add the above components to a 250ml beaker according to the mass percentage of the formula, stir and mix at 25-30℃ for 3 hours to obtain a colorless and transparent oil, which is the low residual copper rolling solution of Example 3, and marked as No. 3 low residual copper rolling solution for later use.

[0059] Example 4

[0060] This example demonstrates the preparation of a low-residual-copper rolling solution.

[0061] Weigh each component according to the mass percentage of each component in Table 4, and set aside for later use.

[0062] Table 4

[0063]

[0064]

[0065] Add the above components to a 250ml beaker according to the mass percentage of the formula, stir and mix at 25-30℃ for 3 hours to obtain a colorless and transparent oil, which is the low residual copper rolling solution of Example 4, and is marked as No. 4 low residual copper rolling solution for later use.

[0066] The formulations in the above examples follow a pattern of decreasing base oil proportions and increasing proportions of other components.

[0067] Example 5

[0068] This example demonstrates the testing of different physicochemical parameters of copper rolling solutions.

[0069] Two commercially available imported copper rolling solutions, type A and type B, were compared with the low-residue copper rolling solutions (1#-4#) prepared in Examples 1-4 of the invention for physicochemical parameter testing. The equipment and experimental environment used in the comparative experiments were kept consistent; the only variable was the type of copper rolling solution.

[0070] Table 5. Test results of physicochemical parameters of different copper rolling solutions

[0071]

[0072] Comparison results: The physicochemical properties of the copper rolling solutions #1-#4 prepared in Examples 1-4 of this patent are very close to those of copper rolling solutions of types A and B. Specifically:

[0073] 1. The saponification values ​​of the copper rolling solutions #1-#4 prepared in Examples 1-4 of this patent are 15.48 mgKOH / g, 15.66 mgKOH / g, 16.23 mgKOH / g, and 16.86 mgKOH / g, respectively, which are higher than those of copper rolling solutions of types A and B (13.43 mgKOH / g and 11.80 mgKOH / g, respectively). These solutions offer significant advantages in protecting the copper strip against scratches and extending roll life.

[0074] 2. The flash point of copper molten metal #1 and #2 prepared in Examples 1 and 2 of this patent is 156℃, the same as that of copper molten metal A, and higher than that of copper molten metal B (154℃). The flash point of copper molten metal #3 and #4 prepared in Examples 3 and 4 is 158℃, higher than that of copper molten metals A and B. Therefore, the copper molten metal of this patent is superior to copper molten metals A and B in terms of oxidation resistance, safety, and environmental friendliness.

[0075] 3. The sulfur content of the copper rolling melts prepared in Examples 1-4 of this patent is 7.54 ppm, 7.66 ppm, 6.71 ppm, and 6.51 ppm, respectively, which is lower than that of type A copper rolling melt (8.12 ppm) and type B copper rolling melt (7.77 ppm). Therefore, the copper rolling melt of this patent is superior to type A and type B copper rolling melts in terms of corrosion resistance.

[0076] 4. The total evaporation temperatures of the copper plating solutions #1-#4 prepared in Examples 1-4 of this patent, as determined by TGA analysis, were 212.3℃, 216.3℃, 216.9℃, and 218.3℃, respectively, which are higher than those of type A copper plating solution (210.2℃) and type B copper plating solution (205.8℃). Therefore, the copper plating solution of this patent exhibits superior antioxidant properties compared to types A and B copper plating solutions.

[0077] Example 6

[0078] This embodiment is a comparative test and analysis of residual oil and impurities per unit area after the use of different copper rolling solutions. The test method refers to the industry standard HG / T2387-2007.

[0079] Two commonly available imported copper rolling solutions, type A and type B, were compared with the low-residue copper rolling solutions (1#-4#) prepared in Examples 1-4 of the invention for testing. The equipment and experimental environment used in the comparative tests were kept consistent; the only variable was the type of copper rolling solution.

[0080] Table 6. Residual oil and impurities per unit area after use of different copper rolling solutions.

[0081] Copper rolling fluid type <![CDATA[Residual oil (g / m 2 )]]> <![CDATA[Impurity (g / m 2 )]]> 1# 0.453 0.108 2# 0.489 0.111 3# 0.501 0.126 4# 0.553 0.201 Type A Copper Rolling Fluid 0.852 0.312 Type B Copper Rolling Fluid 0.634 0.220

[0082] Comparative results: The residual oil per unit area of ​​the copper rolling solution prepared in Examples 1-4 of this patent is 0.454 g / m². 2 0.489g / m 2 0.501g / m 2 0.553g / m 2 It is lower than the 0.852 g / m of Type A copper rolling solution. 2 And 0.634 g / m of type B copper rolling melt 2 The residual impurities per unit area of ​​the copper rolling melts prepared in Examples 1-4 were 0.108 g / m². 2 0.111g / m 2 0.126g / m 2 0.201g / m 2 It is lower than the 0.312 g / m of Type A copper rolling solution. 2 And 0.220 g / m of type B copper rolling melt 2 Therefore, the annealing cleaning properties of the copper rolling solution in this patent are superior to those of copper rolling solutions of types A and B.

[0083] Example 7

[0084] This example demonstrates the wear resistance test of four balls using different copper rolling solutions.

[0085] Two commercially available imported copper rolling solutions, type A and type B, were compared with the low-residue copper rolling solutions (types 1-4) prepared in Examples 1-4 of the invention for performance testing. The equipment and experimental environment used in the comparative tests were kept consistent; the only variable was the type of copper rolling solution.

[0086] Table 7. Test of wear resistance of four balls with different copper rolling solutions.

[0087]

[0088] Comparison Results: Under the same environment and testing methods, the four-ball wear resistance test of copper rolling solution showed that the maximum non-seize load P of copper rolling solutions #1 and #2 prepared in Examples 1 and 2 of this patent was the highest. B The anti-wear performance of 510N is comparable to that of 510N in type A copper rolling fluid, and slightly better than that of 471N in type B copper rolling fluid. The maximum non-seize load P of copper rolling fluids #3 and #4 prepared in Examples 3 and 4 of this patent is shown. B It has a strength of 549N, which is superior to copper rolling solution of types A and B.

[0089] Example 8

[0090] This embodiment is a test experiment on the corrosiveness of copper sheets by different copper rolling solutions.

[0091] Two commonly available imported copper rolling solutions, type A and type B, were compared with the low-residue copper rolling solutions (1#-4#) prepared in Examples 1-4 of the invention for testing. The equipment and experimental environment used in the comparative tests were kept consistent; the only variable was the type of copper rolling solution.

[0092] Different rolling solutions were placed in a constant temperature oil bath at 100℃ for 3 hours to test the corrosion of each product on copper sheets.

[0093] Table 8. Test results of corrosion of copper sheets by different copper rolling solutions.

[0094] Copper rolling fluid type 1# 2# 3# 4# Model A Model B Copper corrosiveness 1a level 1a level 1a level 1a level 1a level Level 1b

[0095] Note: Grade 1a is the best in terms of protection performance, indicating that the copper sheet is light orange in color before and after immersion, almost the same as a newly polished copper sheet; Grade 4c is the worst, indicating that the copper sheet turns into a glossy black or jet black after immersion.

[0096] As shown in Example 8, the copper sheet corrosion of the No. 1-4# low residual copper rolling solution prepared in Examples 1-4 of this patent is grade 1a, which is the same as that of the copper rolling solution of type A, and slightly better than that of the copper rolling solution of type B, grade 1b.

[0097] As described above, the present invention can be well implemented. The above embodiments are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, all changes and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the present invention.

Claims

1. A low-residual copper rolling solution, characterized in that, The low-residual copper rolling solution comprises, by weight percentage, 90.0%–94.6% base oil, 0.2%–0.5% copper corrosion inhibitor, 0.2%–0.5% 2-alkyl-1-alkanol, 0.5%–2.0% isopropyl phosphate, 0.5%–1.0% triphenyl phosphate, 0.5%–2.0% butyl stearate, 0.5%–1.5% composite antioxidant, and 3.0%–10.0% diisooctyl sebacate; the base oil is C12-20. The compound antioxidant is composed of propylene glycol and butylated hydroxyanisole; the butylated hydroxyanisole is a mixture of 2-tert-butyl-4-hydroxyanisole and 3-tert-butyl-4-hydroxyanisole; the mass percentage of 2-tert-butyl-4-hydroxyanisole and 3-tert-butyl-4-hydroxyanisole is 1:1.5~2.

2. The low-residual copper rolling solution according to claim 1, characterized in that, The composite antioxidant is composed of 50% propylene glycol and 50% butylated hydroxyanisole by weight percentage.

3. The low-residual copper rolling solution according to any one of claims 1-2 is applied to the rolling of copper or copper alloys.

4. The application according to claim 3, characterized in that, The thickness of the copper or copper alloy is 0.06 to 1.5 mm.

5. The application according to claim 3, characterized in that, The thickness of the copper or copper alloy is 0.06-0.001 mm.

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