Low-residual copper rolling liquid and application thereof

Abstract

The invention belongs to the technical field of lubricating materials, and particularly relates to low-residual copper rolling liquid and application thereof. The low-residual copper rolling liquid is prepared from the following components in percentage by mass: 90.0%-94.6% of base oil, 0.2%-0.5% of a copper corrosion inhibitor, 0.2%-0.5% of 2-alkyl-1-alkanol, 0.5%-2.0% of isopropyl phosphate, 0.5%-1.0% of triphenyl phosphate, 0.5%-2.0% of butyl stearate, 0.5%-1.5% of a composite antioxidant and 3.0%-10.0% of diisooctyl sebacate. The base oil in the formula of the low-residual copper rolling liquid does not contain aromatic hydrocarbon, chloride, heavy metal and other harmful components, the fire retardant is added, the ignition point is increased, oil mist generated in the rolling process is reduced, pollution is reduced, and the low-residual copper rolling liquid has excellent healthy, safe and environment-friendly characteristics. High lubricity is maintained while residues are reduced, and the copper alloy can be applied to the field of copper rolling, in particular to the field of thin copper rolling.

Description

Technical Field

[0001] The invention belongs to the technical field of lubricating materials, and in particular relates to a low-residue copper rolling liquid and an application thereof. Background Art

[0002] In the processing of copper and copper alloys, lubrication control in the cold rolling process is a key factor. Proper lubrication can reduce rolling force and wear, improve the surface quality and surface finish of the product, and extend the service life of the rolling mill. The medium used for process lubrication in the copper rolling process is mainly rolling oil. Different copper alloy products have different requirements for lubrication, so the performance requirements for the rolling medium used in the processing process are getting higher and higher. In particular, some emerging high-tech fields are driving the increase in downstream demand, such as PCB copper foil required for 5G base station construction, electronic copper sheets and foils required for shipbuilding and marine engineering, etc.

[0003] At present, the most commonly used oil in copper strip rolling is blended oil. Blended oil is made by adding a variety of functional additives to refined mineral oil, so it has the characteristics of high oil film strength, not easy to break, strong antioxidant ability, good surface precision of rolled materials, low roughness, and high cleanliness after annealing. Since mineral oil has a small heat capacity and poor cooling effect, it limits the increase of rolling speed of the rolling mill to a certain extent.

[0004] Copper rolling fluid is usually made of solvent refining, paraffin-based mineral oil and high-performance lubricating additives. According to the requirements of the on-site process, the viscosity, lubrication ability, wear resistance, cleanliness and other parameters of the rolling fluid are designed to effectively ensure good lubrication and cooling capabilities. The surface finish of the rolled plate is high and the residue is small, which can meet the process lubrication requirements of copper cold rolling.

[0005] At present, most of the cold rolling medium for copper and copper alloys on the market is made of pure oily medium mixed with additives, which is only suitable for general production and processing, such as 1-5mm cold rolling and foil rolling, but not for cold rolling and foil rolling less than 1mm. Cold rolling and foil rolling less than 1mm have higher requirements for lubrication and residue, especially for cold rolling and foil rolling less than 0.1mm and below, which requires more refined lubricity and low residue. It is urgent to develop copper rolling fluid that meets both high lubricity and low residue. Summary of the invention

[0006] In order to solve the above technical problems, the present invention provides a low-residue copper rolling liquid and its application. In solving the problems of lubrication and residue, the present invention strictly screens each additive on the basis of screening the base oil, conducts formula research, and finally develops a copper rolling liquid that meets both high lubricity and low residue and can be used for rolling thin and ultra-thin copper foil.

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

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

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

[0010] Furthermore, in the low-residue copper rolling liquid, the composite antioxidant consists of propylene glycol and butylated hydroxyanisole.

[0011] Furthermore, in the low-residue copper rolling liquid, the composite antioxidant is composed of 50% propylene glycol and 50% butylated hydroxyanisole by mass percentage.

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

[0013] Furthermore, in the low-residue copper rolling liquid, 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 application of the low-residue copper rolling liquid in copper or copper alloy rolling.

[0015] Furthermore, the low-residue copper rolling liquid is used in the rolling of copper or copper alloy with a thickness ranging from 0.06 to 1.5 mm.

[0016] Furthermore, the low-residue copper rolling liquid is used for rolling copper or copper alloy 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] The invention develops a low-residue copper rolling liquid by screening a large number of formula components and studying the formula. The low-residue copper rolling liquid consists of 90.0% to 94.6% of base oil, 0.2% to 0.5% of copper corrosion inhibitor, 0.2% to 0.5% of 2-alkyl-1-alkanol, 0.5% to 2.0% of isopropyl phosphate, 0.5% to 1.0% of triphenyl phosphate, 0.5% to 2.0% of butyl stearate, 0.5% to 1.5% of composite antioxidant and 3.0% to 10.0% of diisooctyl sebacate in terms of mass percentage.

[0019] The antioxidant in the copper rolling liquid provided by the present invention adopts a composite antioxidant with excellent antioxidant performance. In addition, the butylated hydroxyanisole in the composite antioxidant is prepared by mixing 2-tert-butyl-4-hydroxyanisole and 3-tert-butyl-4-hydroxyanisole, and the mixture of 3-tert-butyl-4-hydroxyanisole and 2-tert-butyl-4-hydroxyanisole has a synergistic effect.

[0020] The copper rolling fluid of the present invention has been screened for components and studied for formula from the aspects of improving lubrication and reducing residue, thus 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 extend the life of the roller to a large extent, so that the roller can still exert excellent rolling performance under high-speed rolling; it maintains the best surface quality state of the plate and strip, reduces the scrap rate of high-end manufacturing, and thus can reduce the production cost of copper plate, strip and foil.

[0021] The formulated base oil in the copper rolling fluid provided by the present invention does not contain harmful components such as aromatic hydrocarbons, chlorides and heavy metals, and the addition of flame retardants increases the ignition point, reduces the oil mist generated during the rolling process, reduces pollution, and has excellent health, safety and environmental protection characteristics. DETAILED DESCRIPTION

[0022] The technical solution of the present invention is described below in conjunction with embodiments; however, the present invention is not limited to the following embodiments.

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

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

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

[0026] "Copper foil" refers to the copper rolling process between 0.06-0.001mm.

[0027] Exemplary components and their properties of the present invention are as follows:

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

[0029] Isopropyl phosphate: (a mixture of monoester and diester) molecular structure:

[0030]

[0031] Because it has the following characteristics: 1) It provides extreme pressure lubricant with its extremely small usage; 2) Due to its relatively small molecular weight and isomers, it has relative volatility, which can reduce residue in the copper cold foil rolling process; 3) It can provide extreme pressure lubrication while reducing residue, solving two contradictory aspects at the same time.

[0032] 2-Alkyl-1-alkanol: It is a kind of saturated primary alcohol. Due to its special structure of two 100% linear alkyl chains, it has the following characteristics: 1) low volatility; 2) low irritation; 3) low freezing point; 4) excellent lubricity; 5) excellent oxidation stability; 6) good solubility and dissolving power; 7) low viscosity; 8) good biodegradability; 9) board surface wettability, adsorption and cleaning properties.

[0033] Butyl stearate: oil-soluble ester, with the following characteristics: 1) good thermal stability, can be used at higher temperatures, not easy to decompose and deteriorate; 2) good low temperature performance, with a lower freezing point, can be used at low temperatures, not easy to solidify. Because the copper cold and foil rolling oil is not heated in the use environment, only friction heat is generated under low environmental conditions, and its properties ensure the uniformity of the rolling oil.

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

[0035] Antioxidant composite additive: The antioxidant adopts composite agent to avoid heating and dissolving powder during product production. The antioxidant composite additive is composed of propylene glycol: butylated hydroxyanisole = 50:50 by mass percentage, wherein butylated hydroxyanisole is composed of two isomers, 3-tert-butyl-4-hydroxyanisole and 2-tert-butyl-4-hydroxyanisole. Compared with 3-tert-butyl-4-hydroxyanisole and 2-tert-butyl-4-hydroxyanisole, the antioxidant effect of 3-tert-butyl-4-hydroxyanisole is 1.5 to 2 times stronger than that of 2-tert-butyl-4-hydroxyanisole, and the mixture of the two has a synergistic effect. And the compatibility with the esters of other components is good.

[0036] Copper corrosion inhibitors: Choose LANXESS brand lubricant additives RC8239. RC8239 is an effective inhibitor to prevent corrosion of copper and its alloys. It protects the metal surface by forming a stable film through chemical adsorption, and does not leave any residue on the metal surface. The free copper ions basically have no adverse effect on the oxidation stability of the lubricant. Compared with solid benzotriazole derivatives, RC 8239 has good solubility even in PAO and Class 2 base oils and can inhibit corrosion, isolate or prevent rust. Experimental verification shows that the anti-corrosion effect of RC8239 in copper rolling oil is better than that of benzotriazole and methylbenzotriazole.

[0037] Di(2-ethylhexyl)sebacate: It is an ester with a relatively small molecule. It can provide dynamic lubrication and boundary lubrication while reducing residue and has good solubility.

[0038] Example 1

[0039] This embodiment is for preparing a low-residue copper rolling liquid.

[0040] According to mass percentage, 90.0% to 94.6% of base oil, 0.2% to 0.5% of copper corrosion inhibitor, 0.2% to 0.5% of 2-alkyl-1-alkanol, 0.5% to 2.0% of isopropyl phosphate, 0.5% to 1.0% of triphenyl phosphate, 0.5% to 2.0% of butyl stearate, 0.5% to 1.5% of composite antioxidant and 3.0% to 10.0% of diisooctyl sebacate are weighed.

[0041] The base oil is composed of paraffin-based low-viscosity solvent oil C12-20 isoparaffin as the main base oil and 60N base oil as the auxiliary base oil.

[0042] The composite antioxidant is composed of 50% propylene glycol and 50% butylated hydroxyanisole by mass percentage. The 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 into a 250 ml beaker according to the mass percentage of the formula, and stirred and mixed at 25-30° C. for 3 h to obtain a colorless transparent oil, namely the low-residue copper rolling liquid of Example 1, which was marked as 1# low-residue copper rolling liquid for later use.

[0046] Example 2

[0047] This embodiment is for preparing a low-residue copper rolling liquid.

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

[0049] Table 2

[0050]

[0051] The above components were added into a 250 ml beaker according to the mass percentage of the formula, and stirred and mixed at 25-30° C. for 3 h to obtain a colorless transparent oil, namely the low-residue copper rolling liquid of Example 2, which was marked as 2# low-residue copper rolling liquid for later use.

[0052] Example 3

[0053] This embodiment is for preparing a low-residue copper rolling liquid.

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

[0055] Table 3

[0056]

[0057]

[0058] The above components were added into a 250 ml beaker according to the mass percentage of the formula, and stirred and mixed at 25-30° C. for 3 h to obtain a colorless transparent oil, namely the low-residue copper rolling liquid of Example 3, which was marked as 3# low-residue copper rolling liquid for later use.

[0059] Example 4

[0060] This embodiment is for preparing a low-residue copper rolling liquid.

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

[0062] Table 4

[0063]

[0064]

[0065] The above components were added into a 250 ml beaker according to the mass percentage of the formula, and stirred and mixed at 25-30° C. for 3 h to obtain a colorless transparent oil, namely the low-residue copper rolling liquid of Example 4, which was marked as 4# low-residue copper rolling liquid for later use.

[0066] The formulas in the above cases are based on a decreasing proportion of base oil and increasing proportions of other components.

[0067] Example 5

[0068] This embodiment is a test experiment for testing the physical and chemical parameters of different copper rolling fluids.

[0069] Two common imported copper rolling liquids, Model A and Model B, were tested for physical and chemical parameters with the 1#-4# low-residue copper rolling liquids prepared in Inventive Examples 1 to 4. The equipment, experimental environment and other factors used in the comparative test were kept consistent, and the only variable was the different copper rolling liquid models.

[0070] Table 5 Test results of physical and chemical parameters of different copper rolling liquids

[0071]

[0072] Comparison results: The physical and chemical indicators of the 1#-4# copper rolling liquids prepared in Examples 1-4 of this patent are close to those of the copper rolling liquids of Models A and B. Among them:

[0073] 1. The saponification values ​​of 1#-4# copper rolling solutions prepared in Examples 1-4 of this patent are 15.48mgKOH / g, 15.66mgKOH / g, 16.23mgKOH / g, and 16.86mgKOH / g, respectively, which are higher than 13.43mgKOH / g and 11.80mgKOH / g of A and B type copper rolling solutions. They are more advantageous than 1#-4# copper rolling solutions in protecting the anti-scratch property of copper plates and strips and extending the life of the rollers.

[0074] 2. The flash point of the copper rolling liquids 1# and 2# prepared in Examples 1 and 2 of this patent is 156°C, which is the same as 156°C of the copper rolling liquid of type A, and higher than 154°C of the copper rolling liquid of type B; the flash point of the copper rolling liquids 3# and 4# prepared in Examples 3 and 4 is 158°C, which is higher than the copper rolling liquids of types A and B. Therefore, the copper rolling liquid of this patent is superior to the copper rolling liquids of types A and B in terms of oxidation resistance, safety and environmental protection.

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

[0076] 4. The total volatilization temperatures of the 1#-4# copper rolling solutions prepared in Examples 1 to 4 of this patent are 212.3°C, 216.3°C, 216.9°C, and 218.3°C, respectively, which are higher than 210.2°C of the A-type copper rolling solution and 205.8°C of the B-type copper rolling solution. Therefore, the copper rolling solution of this patent is superior to the A-type and B-type copper rolling solutions in terms of antioxidant performance.

[0077] Example 6

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

[0079] Two common imported copper rolling liquids, Model A and Model B, were tested with the 1#-4# low-residue copper rolling liquids prepared in Inventive Examples 1 to 4. The equipment, experimental environment and other factors used in the comparative test were kept consistent, and the only variable was the different copper rolling liquid models.

[0080] Table 6 Residual oil and impurities per unit area after using different copper rolling liquids

[0081] Copper rolling fluid model <![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 A type copper rolling liquid 0.852 0.312 B type copper rolling liquid 0.634 0.220

[0082] Comparison results: The residual oil per unit area of ​​1#-4# copper rolling liquid prepared in Examples 1-4 of this invention is 0.454 g / m 2 , 0.489g / m 2 , 0.501g / m 2 , 0.553g / m 2 , lower than 0.852g / m of A-type copper rolling liquid 2 and 0.634g / m of B-type copper rolling liquid 2 The residual impurities per unit area of ​​1#-4# copper rolling liquid prepared in Example 1-Example 4 were 0.108 g / m 2 , 0.111g / m 2 , 0.126g / m 2 , 0.201g / m 2 , lower than 0.312g / m of A-type copper rolling liquid 2 and 0.220g / m 2 Therefore, the annealing cleanliness of the copper rolling solution of this patent is better than that of the copper rolling solution of types A and B.

[0083] Example 7

[0084] This embodiment is a test of the wear resistance of four balls of different copper rolling fluids.

[0085] The performance of two common imported copper rolling liquids A and B on the market and the 1#-4# low-residue copper rolling liquids prepared in Inventive Examples 1 to 4 were tested. The equipment, experimental environment and other factors used in the comparative test were kept consistent, and the only variable was the different copper rolling liquid models.

[0086] Table 7 Wear resistance test of four balls with different copper rolling fluids

[0087]

[0088] Comparison results: In the same environment and with the same test method, the four-ball wear resistance test of copper rolling liquid shows that the maximum no-seizure load P of 1# and 2# copper rolling liquids prepared in Examples 1 and 2 of this patent is B The maximum no-seizure load P of the 3# and 4# copper rolling liquids prepared in Examples 3 and 4 of this patent is 510N, which is equivalent to the 510N anti-wear performance of the A-type copper rolling liquid and slightly better than the 471N of the B-type copper rolling liquid. B It is 549N, which is better than A and B types of copper rolling liquid.

[0089] Example 8

[0090] This embodiment is a test of the corrosion of different copper rolling liquids on copper sheets.

[0091] Two common imported copper rolling liquids, Model A and Model B, were tested with the 1#-4# low-residue copper rolling liquids prepared in Inventive Examples 1 to 4. The equipment, experimental environment and other factors used in the comparative test were kept consistent, and the only variable was the different copper rolling liquid models.

[0092] Different rolling liquids were placed in a constant temperature oil bath test tank at 100°C 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 liquids

[0094] Copper rolling fluid model 1# 2# 3# 4# Model A B Model Copper Corrosion Level 1a Level 1a Level 1a Level 1a Level 1a Level 1b

[0095] Note: The protection performance level 1a is the best, which means that the color of the copper sheet before and after immersion is light orange, almost the same as a newly polished copper sheet; level 4c is the worst, which means that the copper sheet becomes shiny black or shiny black after immersion.

[0096] The results are shown in Example 8. The copper sheet corrosion of the 1#-4# low-residue copper rolling liquid prepared in Examples 1 to 4 of this patent is level 1a, which is the same as the copper rolling liquid of type A, and slightly better than the copper rolling liquid of type B, which is level 1b.

[0097] As described above, the present invention can be well implemented. The above embodiments only describe the preferred implementation methods of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various changes and improvements made to the technical scheme of the present invention by ordinary technicians in this field should fall within the protection scope determined by the present invention.

Claims

1. A low-residue copper rolling liquid, characterized in that: The low-residue copper rolling liquid consists of 90.0% to 94.6% of base oil, 0.2% to 0.5% of copper corrosion inhibitor, 0.2% to 0.5% of 2-alkyl-1-alkanol, 0.5% to 2.0% of isopropyl phosphate, 0.5% to 1.0% of triphenyl phosphate, 0.5% to 2.0% of butyl stearate, 0.5% to 1.5% of composite antioxidant and 3.0% to 10.0% of diisooctyl sebacate, in terms of mass percentage.

2. The low-residue copper rolling liquid according to claim 1, characterized in that: The base oil is composed of paraffin-based low-viscosity solvent oil.

3. The low-residue copper rolling liquid according to claim 2, characterized in that: The paraffin-based low-viscosity solvent oil is C12-20 isoparaffin and 60N base oil.

4. The low-residue copper rolling liquid according to claim 1, characterized in that: The composite antioxidant consists of propylene glycol and butylated hydroxyanisole.

5. The low-residue copper rolling liquid according to claim 4, characterized in that: The composite antioxidant consists of 50% of propylene glycol and 50% of butylated hydroxyanisole in terms of mass percentage.

6. The low-residue copper rolling liquid according to claim 5, characterized in that: The butylated hydroxyanisole is prepared by mixing 2-tert-butyl-4-hydroxyanisole and 3-tert-butyl-4-hydroxyanisole.

7. The low-residue copper rolling liquid according to claim 6, characterized in that: The mass percentage of the 2-tert-butyl-4-hydroxyanisole to the 3-tert-butyl-4-hydroxyanisole is 1:1.5-2.

8. The low-residue copper rolling liquid according to any one of claims 1 to 7 is used for copper or copper alloy rolling.

9. The use according to claim 8, characterized in that: The thickness of the copper or copper alloy is 0.06-1.5 mm.

10. The use according to claim 8, characterized in that: The thickness of the copper or copper alloy is 0.06-0.001 mm.

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