A pre-coating oil for 3104 can body material and a method for preparing the same

Abstract

The present application relates to the technical field of pre-coating oil, in particular to IPC C10M169, more particularly to an easy-to-clean pre-coating oil specially used for 3104 can body material and a preparation method thereof.The raw materials for preparation in the present application include mineral oil, synthetic ester, lubrication enhancer, high-molecular emulsifier, penetrant, small-molecule cleaning agent, coupling agent, antioxidant and antirust agent.The use of the pre-coating oil in the present application solves the blackening problem of 3104 can body material, improves the product quality of aluminum pop can, reduces the waste rate, effectively reduces the amount of cleaning agent, reduces the discharge of waste chemicals and waste water, and avoids water eutrophication pollution.

Description

Technical Field

[0001] This invention relates to the field of pre-coating technology, particularly to IPC C10M169, and more specifically to an easy-to-clean pre-coating oil specifically for 3104 tank body material and its preparation method. Background Technology

[0002] Aluminum beverage cans are widely used for packaging beverages, oils, and other liquids due to their low density, high plasticity, and ease of processing. Currently, the domestic annual demand is 60-70 billion units, with a maximum annual capacity of up to 100 billion units. The can body material is typically 3104 series aluminum coil. During the manufacturing process, a special process oil, commonly known as pre-coating oil, is applied, primarily serving the following functions: protecting the aluminum material during transportation and storage; effectively combining with cup-washing oil to provide a lubricating base for the stretching and leveling of the aluminum sheet; acting as a safety net when the metal surface is not coated with cup-washing oil; dispersing debris generated during cold rolling of the aluminum sheet; and ensuring the aluminum sheet surface does not oxidize.

[0003] However, during the use of pre-coated oil, it was found that cleaning was difficult, and some pre-coated oils caused the 3104 can material to turn black after cleaning. Existing patent CN201911369763 discloses a rapid method for judging the blackening of 3104 can material after pasteurization, explaining that when the amount of oil applied is too high or the pre-coated oil is substandard, residual oil remains on the surface of the finished can after cleaning, resulting in a blackening defect at the bottom of the can after pasteurization. Summary of the Invention

[0004] To address the problems in the prior art, the first aspect of this invention provides an easy-to-clean pre-coating oil specifically for 3104 tank body material, the raw materials for which include mineral oil, synthetic ester, lubricant enhancer, polymeric emulsifier, penetrant, small molecule cleaning agent, coupling agent, antioxidant, and rust inhibitor.

[0005] Preferably, the easy-to-clean pre-coating oil specifically for the 3104 tank body material is prepared by means of the following raw materials, by mass percentage: 40-90% mineral oil, 5-15% synthetic ester, 5-10% lubricant enhancer, 1-5% polymeric emulsifier, 1-5% penetrant, 0.1-2% small molecule cleaning agent, 1-5% coupling agent, 1-5% antioxidant, and 1-5% rust inhibitor.

[0006] Preferably, the mineral oil includes GTL base oil and white oil.

[0007] Preferably, the mass ratio of the GTL base oil to the white oil is (2-6):(2-3); more preferably, it is 5:2 to 5:2.45.

[0008] Preferably, the kinematic viscosity of the GTL base oil is 40-50 mm. 2 / s, 40℃; more preferably, 44.13mm. 2 / s, 40℃.

[0009] Preferably, the GTL base oil is Shell's GTL430.

[0010] Preferably, the kinematic viscosity of the white oil is 8-12 mm. 2 / s, 40℃; more preferably, 9.5~10.7mm. 2 / s, 40℃.

[0011] Preferably, the white oil is purchased from Hangzhou Petrochemical's No. 10 white oil.

[0012] Preferably, the synthetic ester includes one or more of polyethylene glycol monooleate, polyethylene glycol dioleate, polyethylene glycol stearate, and polyethylene glycol laurate.

[0013] Preferably, the polyethylene glycol monooleate includes one or more of polyethylene glycol 200 monooleate, polyethylene glycol 400 monooleate, and polyethylene glycol 600 monooleate.

[0014] Preferably, the polyethylene glycol 200 monooleate is purchased from Sanda Chemical (Nantong) Co., Ltd.

[0015] Preferably, the lubricant enhancer comprises a long-chain fatty alcohol; the long-chain fatty alcohol has 12-18 carbon atoms on its carbon chain; more preferably, it is dodecyltetradecyl alcohol.

[0016] Preferably, the dodecyltetradecyl alcohol is purchased from Sasol Yihai (Lianyungang) Alcohol Industry Co., Ltd.

[0017] Preferably, the polymeric emulsifier comprises an ethylene oxide (EO) / propylene oxide (PO) block copolymer, wherein the ethylene oxide group content is 10-20%; more preferably, it is 20%.

[0018] Preferably, the ethylene oxide (EO) / propylene oxide (PO) block copolymer has an HLB value of 3 to 5 and a cloud point of 27 to 33; more preferably, it has an HLB value of 4 and a cloud point of 29.

[0019] Preferably, the ethylene oxide (EO) / propylene oxide (PO) block copolymer is purchased from BASF's Pluronic® 25R2.

[0020] In this invention, by adding an emulsifier of ethylene oxide (EO) / propylene oxide (PO) block copolymer with an HLB value of 3-5, the cleaning performance of the pre-coated oil is improved while maintaining the lubrication effect. The inventors have creatively discovered that by using ethylene oxide (EO) / propylene oxide (PO) block copolymer, where ethylene oxide is highly hydrophilic and propylene oxide is highly lipophilic, when the ethylene oxide content is 10-20%, the EO and PO molecules are arranged more neatly in this system, resulting in stronger intermolecular forces and enhanced permeability. Under the washing of a large amount of water, oils and esters are removed, reducing the washing time and improving the cleaning performance.

[0021] Preferably, the penetrant includes one or more of acetylenic glycol, propylene glycol, and isooctyl alcohol.

[0022] Preferably, the acetylenol is purchased from Air Products' Surfynol 104E.

[0023] Preferably, the small molecule cleaning agent includes one or more of cyclodextrin, methanol, and isopropanol.

[0024] Preferably, the cyclodextrin is purchased from Sinopharm's β-cyclodextrin.

[0025] In this invention, the emulsification effect of cyclodextrin and polymeric emulsifier is further improved by adding the small-molecule cleaning agent cyclodextrin and the penetrant acetylenol, thereby enhancing cleaning performance and reducing cleaning time. The inventors discovered that if only polymeric emulsifier is added, some small molecules are not completely cleaned, leading to blackening of the can material and a prolonged cleaning time. Adding acetylenol increases the kinetic rates of cyclodextrin and polymeric emulsifier in the system, thus improving the emulsification effect and consequently the cleaning performance. Furthermore, in the dextrin molecule structure, hydroxyl groups are mainly distributed outside the cavity, while glycosidic bonds and oxygen atoms are located inside the cavity. This results in a hydrophobic interior and a hydrophilic exterior. When cyclodextrin is added to the system, it can encapsulate small molecules in the 3104 can material during the cleaning process, further improving cleaning performance and reducing blackening of the 3104 can material.

[0026] Preferably, the coupling agent includes at least one of hexanediol, isohexanediol, and diethylene glycol monobutyl ether.

[0027] Preferably, the hexanediol is purchased from ARKEMA.

[0028] In this invention, the addition of hexanediol improves the compatibility of mineral oil, synthetic esters, lubricant enhancers, polymeric emulsifiers, penetrants, and small-molecule cleaning agents. During the research and development process, the inventors discovered that mineral oil and polymeric emulsifiers did not blend well, resulting in suboptimal cleaning performance. When using ethylene glycol, the coupling effect was poor, the system was unstable, and stratification was common. Unexpectedly, the addition of hexanediol improved the stability of the pre-coated oil and simultaneously enhanced the cleaning effect. This is likely because the longer carbon chain of hexanediol allows for tighter binding with the long carbon chains of ethylene oxide (EO) / propylene oxide (PO) block copolymers and non-polar compounds in the system. Furthermore, the hydroxyl groups on hexanediol form hydrogen bonds with water molecules, thereby improving the overall compatibility and stability of the system.

[0029] Preferably, the antioxidant includes one or more of BHT, 1076, 1330, and 1010.

[0030] Preferably, the BHT is purchased from Sinopharm's 501.

[0031] Preferably, the rust inhibitor is one or more of methylbenzotriazole, imidazoline, and tetrasodium ethylenediaminetetraacetate.

[0032] Preferably, the easy-to-clean pre-coating oil specifically for the 3104 tank body is prepared from raw materials, by mass percentage, comprising 70-74.5% mineral oil, 10% synthetic ester, 10% lubricant enhancer, 1-3% polymeric emulsifier, 1-2% penetrant, 0.5-2% small molecule cleaning agent, 1% coupling agent, 1% antioxidant, and 1% rust inhibitor.

[0033] The second aspect of the present invention provides a method for preparing an easy-to-clean pre-coating oil specifically for 3104 can body material, comprising the following steps: mixing mineral oil, synthetic ester, lubricant enhancer, polymeric emulsifier, penetrant, small molecule cleaning agent, coupling agent, antioxidant and rust inhibitor according to the mass percentage of the easy-to-clean pre-coating oil specifically for 3104 can body material.

[0034] Beneficial effects

[0035] 1. In this invention, by adding an emulsifier of ethylene oxide (EO) / propylene oxide (PO) block copolymer with an HLB value of 3 to 5, the cleaning performance of the pre-coated oil is improved while maintaining the lubrication effect.

[0036] 2. In this invention, by adding the small molecule cleaning agent cyclodextrin and the penetrant acetylacetonate, the emulsification effect of cyclodextrin and the high molecular weight emulsifier is further improved, and the cleaning performance is also improved, while the cleaning time is reduced.

[0037] 3. In this invention, the addition of hexanediol improves the compatibility of mineral oil, synthetic esters, lubricant enhancers, polymeric emulsifiers, penetrants, and small molecule cleaning agents.

[0038] 4. In this invention, by compounding GTL base oil, white oil, polyethylene glycol monooleate, and long-chain fatty alcohol with specific parameters, it has excellent lubrication performance and good cleaning effect. When it is combined with other substances in the system, it emulsifies well when cleaning with cleaning agent and is carried away by water molecules, which effectively reduces the amount of cleaning agent used, reduces costs, and reduces cleaning time.

[0039] 5. This invention uses phosphorus-free raw materials, avoiding the generation of phosphorus in wastewater and preventing eutrophication pollution, making it more environmentally friendly. The pre-coating oil in this invention solves the problem of blackening after boiling due to insufficient pre-coating oil cleaning, improves the product quality of aluminum cans, reduces scrap rate, effectively reduces the amount of cleaning agent used, and reduces the discharge of waste chemicals and wastewater. Detailed Implementation

[0040] Example 1

[0041] The first aspect of this embodiment provides an easy-to-clean pre-coating oil specifically for 3104 tank body material, the raw materials for which are prepared by mass percentage as follows: 70% mineral oil, 10% synthetic ester, 10% lubricant enhancer, 3% polymeric emulsifier, 2% penetrant, 2% small molecule cleaning agent, 1% coupling agent, 1% antioxidant and 1% rust inhibitor.

[0042] The mineral oil is GTL base oil and white oil.

[0043] The mass ratio of the GTL base oil to the white oil is 5:2.

[0044] The kinematic viscosity of the GTL base oil is 44.13 mm. 2 / s, 40℃.

[0045] The GTL base oil is Shell's GTL430.

[0046] The kinematic viscosity of the white oil is 9.5–10.7 mm. 2 / s, 40℃.

[0047] The white oil was purchased from Hangzhou Petrochemical's No. 10 white oil.

[0048] The synthetic ester is polyethylene glycol monooleate.

[0049] The polyethylene glycol monooleate is polyethylene glycol 200 monooleate.

[0050] The polyethylene glycol 200 monooleate was purchased from Sanda Chemical (Nantong) Co., Ltd.

[0051] The lubricant enhancer is a long-chain fatty alcohol; the long-chain fatty alcohol is dodecyltetradecyl alcohol.

[0052] The dodecyltetradecyl alcohol was purchased from Sasol Yihai (Lianyungang) Alcohol Industry Co., Ltd.

[0053] The polymeric emulsifier is an ethylene oxide (EO) / propylene oxide (PO) block copolymer, wherein the ethylene oxide group content is 20%.

[0054] The ethylene oxide (EO) / propylene oxide (PO) block copolymer has an HLB value of 4 and a cloud point of 29.

[0055] The ethylene oxide (EO) / propylene oxide (PO) block copolymer was purchased from BASF's Pluronic® 25R2.

[0056] The penetrant is acetylenic diol.

[0057] The acetylenol was purchased from Air Products' Surfynol 104E.

[0058] The small molecule cleaning agent is cyclodextrin.

[0059] The cyclodextrin was purchased from Sinopharm's β-cyclodextrin.

[0060] The coupling agent is hexanediol.

[0061] The hexanediol was purchased from ARKEMA.

[0062] The antioxidant is BHT.

[0063] The BHT was purchased from Sinopharm's 501.

[0064] The rust inhibitor is methylbenzotriazole.

[0065] The second aspect of this embodiment provides a method for preparing an easy-to-clean pre-coating oil specifically for 3104 can body material, comprising the following steps: mixing mineral oil, synthetic ester, lubricant enhancer, polymeric emulsifier, penetrant, small molecule cleaning agent, coupling agent, antioxidant and rust inhibitor according to the mass percentage of the easy-to-clean pre-coating oil specifically for 3104 can body material.

[0066] Example 2

[0067] The specific implementation method of Example 2 is the same as that of Example 1, except that the mass percentage of the white oil is 24.5%; the mass percentage of the polymeric emulsifier is 1%; the mass percentage of the acetylacetic diol is 1%; and the mass percentage of the cyclodextrin is 0.5%.

[0068] The kinematic viscosity of the white oil is 9.5–10.7 mm. 2 / s, 40℃.

[0069] The white oil was purchased from Hangzhou Petrochemical's No. 10 white oil.

[0070] The polymeric emulsifier includes an ethylene oxide (EO) / propylene oxide (PO) block copolymer, wherein the ethylene oxide group content is 20%.

[0071] The ethylene oxide (EO) / propylene oxide (PO) block copolymer has an HLB value of 4 and a cloud point of 29.

[0072] The ethylene oxide (EO) / propylene oxide (PO) block copolymer was purchased from BASF's Pluronic® 25R2.

[0073] The penetrant is acetylenic diol.

[0074] The acetylenol was purchased from Air Products' Surfynol 104E.

[0075] The small molecule cleaning agent is cyclodextrin.

[0076] The cyclodextrin was purchased from Sinopharm's β-cyclodextrin.

[0077] Comparative Example 1

[0078] The specific implementation method of Comparative Example 1 is the same as that of Example 1, except that the mass percentage of the GTL base oil is 45%; the mass percentage of the polymeric emulsifier is 6%; the mass percentage of the acetylacetic diol is 5%; and the mass percentage of the cyclodextrin is 5%.

[0079] The kinematic viscosity of the GTL base oil is 40–50 mm. 2 / s, 40℃; more preferably, 44.13mm. 2 / s, 40℃.

[0080] The GTL base oil is Shell's GTL430.

[0081] The polymeric emulsifier includes an ethylene oxide (EO) / propylene oxide (PO) block copolymer, wherein the ethylene oxide group content is 20%.

[0082] The ethylene oxide (EO) / propylene oxide (PO) block copolymer has an HLB value of 4 and a cloud point of 29.

[0083] The ethylene oxide (EO) / propylene oxide (PO) block copolymer was purchased from BASF's Pluronic® 25R2.

[0084] The penetrant is acetylenic diol.

[0085] The acetylenol was purchased from Air Products' Surfynol 104E.

[0086] The small molecule cleaning agent is cyclodextrin.

[0087] The cyclodextrin was purchased from Sinopharm's β-cyclodextrin.

[0088] Comparative Example 2

[0089] The specific implementation method of Comparative Example 2 is the same as that of Example 1, except that the polymeric emulsifier is sodium petroleum sulfonate, which was purchased from Calume's Petrosul M-50 Sodium Sulfonate.

[0090] Comparative Example 3

[0091] The specific implementation method of Comparative Example 3 is the same as that of Example 1, except that the coupling agent is ethylene glycol, which is commercially available.

[0092] Comparative Example 4

[0093] The specific implementation method of Comparative Example 4 is the same as that of Example 1, except that the raw materials for preparing the easy-to-clean pre-coating oil specifically for 3104 can body material do not contain small molecule cleaning agents.

[0094] Performance testing

[0095] Test 1: Phosphorus Content Test

[0096] Test method: ICP test (inductively coupled plasma)

[0097] The phosphorus content of Examples 1, Comparative Examples 1-4, and Commercial Reference Example A (UNICHEM UNICOAT PL 9611 product) was measured.

[0098] As can be seen from the ICP test results of phosphorus content (see Table 1), compared with commercially available products, the product described in this invention does not contain phosphorus, is more environmentally friendly, and does not pose a potential hazard of eutrophication of water bodies.

[0099] Table 1

[0100]

[0101] Test 2: Oil Film Strength Test

[0102] Test method: Four-ball milling machine, conducted according to national standard GB / T 3142. PB value represents oil film strength; the higher the PB value, the stronger the oil film.

[0103] The oil film strength of Examples 1 and 2, Comparative Examples 1 to 4, and Commercial Reference Example A under different conditions was tested according to the test method. The results are shown in Table 2.

[0104] The results are shown in Table 2. The test results show that Examples 1 and 2 had sufficient lubrication, but Comparative Example 1 had insufficient lubrication. Comparative Examples 2 and 3, as well as commercially available products, all exhibited good lubrication performance. However, Comparative Example 3 failed to form a stable system, resulting in stratification, making testing impossible.

[0105] Table 2

[0106]

[0107] Test 3: Cleaning Performance Test

[0108] Test method: A certain thickness of oil film (250 mg / m²) is uniformly coated on an aluminum plate (specification: 3104H19, 0.5 mm) the size of an A4 sheet of paper. 2 Then, cut out small samples of 4 cm x 4 cm. Stack the samples together and clamp them with stainless steel clamps. Place them in a 50°C oven for one week to simulate the storage process of aluminum. Afterward, use tweezers to place the samples in a cleaning solution (cleaning agent brand: UNICLEAN 576, concentration: 2% aqueous solution, temperature: 60°C). Remove the samples every minute and observe whether the water film on the surface is continuous. If the water film is discontinuous, it indicates that the oil film on the sample has not been completely cleaned. If the water film is continuous, it indicates that the oil film on the sample has been completely cleaned. Record the time required for complete cleaning. The shorter the time, the easier the oil is to clean, that is, the better the cleaning performance of the oil, and vice versa.

[0109] The cleaning performance of Examples 1-2 and Comparative Examples 1-4 (comparative examples A) was tested according to the test method, and the results are shown in Table 3. The conclusions show that Examples 1 and 2, with sufficient lubrication, effectively improved cleaning performance, increasing by 50% and 25% respectively. Comparative Example 1, although improving cleaning performance by approximately 70%, suffered from insufficient lubrication. Comparative Examples 2 and 4, along with the commercially available product, all exhibited excellent lubrication, but their cleaning performance was poor, resulting in longer cleaning times. The product in Comparative Example 3 could not form a stable system and therefore could not be tested.

[0110] Table 3

[0111]

Claims

1. An easy-to-clean pre-coating oil specifically for the body material of tank 3104, characterized in that, The raw materials for its preparation, by mass percentage, include 40-90% mineral oil, 5-15% synthetic ester, 5-10% lubricant enhancer, 1-5% polymer emulsifier, 1-5% penetrant, 0.1-2% small molecule cleaning agent, 1-5% coupling agent, 1-5% antioxidant and 1-5% rust inhibitor; The polymeric emulsifier includes an ethylene oxide / propylene oxide block copolymer, wherein the ethylene oxide content is 10-20%; the ethylene oxide (EO) / propylene oxide (PO) block copolymer has an HLB value of 3-5 and a cloud point of 27-33. The penetrant is acetylenic diol; The small molecule cleaning agent is cyclodextrin; the coupling agent is hexanediol; The mineral oil is GTL base oil and white oil, and the mass ratio of the GTL base oil to the white oil is (2-6):(2-3). The lubricant enhancer includes a long-chain fatty alcohol; the long-chain fatty alcohol has 12-18 carbon atoms on its carbon chain.

2. The easy-to-clean pre-coating oil specifically for the body material of tank 3104 according to claim 1, characterized in that, The synthetic esters include one or more of polyethylene glycol monooleate, polyethylene glycol dioleate, polyethylene glycol stearate, and polyethylene glycol laurate.

3. A method for preparing an easy-to-clean pre-coating oil specifically for 3104 tank body material according to any one of claims 1 to 2, characterized in that, Mineral oil, synthetic ester, lubricant enhancer, polymeric emulsifier, penetrant, small molecule cleaner, coupling agent, antioxidant and rust inhibitor are mixed according to the mass percentage of the easy-to-clean pre-coating oil specifically for 3104 tank body material.

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