7-series aluminum alloy surface cleaning agent, application of 7-series aluminum alloy surface cleaning agent and 7-series aluminum alloy surface cleaning method

Abstract

The invention relates to a 7-series aluminum alloy surface cleaning agent, application of the 7-series aluminum alloy surface cleaning agent and a 7-series aluminum alloy surface cleaning method, and adopts the technical scheme that the 7-series aluminum alloy surface cleaning agent comprises 10 parts of hydroxyl substituted carboxylic acid; 2 to 15 parts of a surfactant; 2-10 parts of a metal complexing agent; and 1-10 parts of a corrosion inhibitor. The cleaning agent has the characteristics of high cleaning capacity and low corrosion to the surface of the 7-series aluminum alloy on silicon dioxide left on the surface of the 7-series aluminum alloy due to polishing of a silicon dioxide polishing solution.

Description

Technical Field

[0001] The invention relates to a 7-series aluminum alloy surface cleaning agent, application thereof and a 7-series aluminum alloy surface cleaning method. Background Art

[0002] 3C products are updated rapidly, and the requirements for the metal shell materials and processes of new smart watches, mobile phones, tablet computers and other electronic products are getting higher and higher. Due to its beautiful appearance, light weight, high strength, excellent performance, and no sensitivity to human skin, 7 series aluminum alloy has gradually replaced 5 series and 6 series aluminum alloys and become the most popular metal shell material. In order to obtain a high-gloss mirror effect, at least two processes are required. First, use aluminum oxide polishing liquid or diamond grinding liquid for roughing, and then use silica polishing liquid with smaller particle size for fine polishing to achieve a mirror effect.

[0003] At present, the surface polishing of 7 series aluminum materials adopts silica polishing liquid. The silica sol particles in the polishing liquid have strong adsorption due to the rich silicon hydroxyl groups on the surface, which makes the residual silica on the surface of the aluminum material after fine polishing and difficult to clean. If strong acids such as sulfuric acid or hydrochloric acid are used as pickling components, the corrosion to the substrate is strong, especially the 7 series aluminum alloy due to its high zinc content, which makes the 7 series aluminum alloy have poor corrosion resistance. Zinc is an active metal that is easily oxidized in air and water, resulting in a decrease in gloss after washing the surface. In addition, there is a potential difference between zinc and aluminum, and electron transfer will occur in a humid environment or in the presence of electrolytes, which can accelerate metal corrosion and cause serious corrosion spots on the surface after washing. These situations have a great impact on the subsequent aluminum alloy surface treatment processes such as anodizing, so it is necessary to select appropriate cleaning agents to thoroughly solve the above cleaning and corrosion problems. Summary of the invention

[0004] The first object of the present invention is to provide a 7-series aluminum alloy surface cleaning agent, which has the characteristics of high cleaning power for silicon dioxide remaining on the surface of the 7-series aluminum alloy due to polishing with silicon dioxide polishing liquid and low corrosion to the aluminum alloy surface.

[0005] To achieve the first purpose, the technical solution of the present invention is as follows:

[0006] 7 series aluminum alloy surface cleaning agent, including:

[0007] Hydroxyl-substituted carboxylic acid, 10 parts;

[0008] Surfactant, 2-15 parts;

[0009] Metal complexing agent, 2 to 10 parts;

[0010] Corrosion inhibitor, 1 to 10 parts.

[0011] The hydroxy-substituted carboxylic acid used in the present invention overcomes the disadvantages of sulfuric acid or hydrochloric acid and reduces the corrosion of the cleaning agent on the surface of the aluminum material.

[0012] In the above technical solution, it is preferred that the 7 series aluminum alloy surface cleaning agent includes a polymer dispersant, and the amount used is greater than 0 parts and less than 6 parts;

[0013] In the above technical solution, as a non-limiting example, the surfactant is 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts and the like.

[0014] In the above technical solution, as a non-limiting example, the metal complexing agent is 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, etc.

[0015] In the above technical solution, as a non-limiting example, the polymer dispersant is 0.5 parts, 1 parts, 2 parts, 3 parts, 4 parts, 5 parts, etc.

[0016] In the above technical solution, as a non-limiting example, the corrosion inhibitor is 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, etc.

[0017] In the above technical scheme, the carbon number of the hydroxycarboxylic acid molecule is preferably 2 to 7, for example but not limited to 3, 4, 5, 6, etc.; more preferably, the molar ratio of hydroxyl to carboxyl in the hydroxycarboxylic acid molecule is 0.3 to 3, for example but not limited to 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, etc.

[0018] In the above technical solution, the hydroxycarboxylic acid can be an aliphatic hydroxycarboxylic acid, such as but not limited to tartaric acid, glycolic acid, citric acid, malic acid, etc. The hydroxycarboxylic acid can also be an aromatic hydroxycarboxylic acid, such as dihydroxybenzoic acid or trihydroxybenzoic acid. The aromatic hydroxycarboxylic acid conforms to the following formula 1:

[0019]

[0020] Wherein, R1 to R5 are independently H or hydroxyl, and it is further preferred that any two groups or any three groups of R1 to R5 are hydroxyl. When the aromatic hydroxycarboxylic acid shown in Formula 1 is dihydroxybenzoic acid, any two groups of the five groups of R1 to R5 are hydroxyl, and the rest are H; when the aromatic hydroxycarboxylic acid shown in Formula 1 is trihydroxybenzoic acid, any three groups of the five groups of R1 to R5 are hydroxyl, and the rest are H.

[0021] As non-limiting examples of aromatic hydroxycarboxylic acids, dihydroxybenzoic acid can be 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4,5-dihydroxybenzoic acid, and trihydroxybenzoic acid can be 2,3,4-dihydroxybenzoic acid, 2,3,5-dihydroxybenzoic acid, 2,3,6-dihydroxybenzoic acid, 2,4,5-dihydroxybenzoic acid, 2,4,6-dihydroxybenzoic acid, 3,4,5-dihydroxybenzoic acid. For comparison only, the aromatic hydroxycarboxylic acid used in the specific embodiment of the present invention uses 3,4,5-trihydroxybenzoic acid.

[0022] We found that the combination of aromatic hydroxycarboxylic acid and aliphatic hydroxycarboxylic acid improves the cleaning power of the cleaning agent of the present invention on the surface of 7 series aluminum, reflecting that aromatic hydroxycarboxylic acid and aliphatic hydroxycarboxylic acid have a mutually reinforcing effect. There is no particular restriction on the ratio of aromatic hydroxycarboxylic acid to aliphatic hydroxycarboxylic acid, but preferably, the mass ratio of aromatic hydroxycarboxylic acid to aliphatic hydroxycarboxylic acid is 0.1 to 10, for example but not limited to 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.5, 2, 2.5, 3, 3.5, 4, 5, 6, 7, etc., more preferably 0.3 to 5, and further preferably 0.5 to 3.

[0023] In the above technical solution, preferably, the surfactant includes at least one selected from the group consisting of nonionic surfactants and anionic surfactants.

[0024] In the above technical solution, preferably, the nonionic surfactant includes at least one selected from the group consisting of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and alkyl glycoside.

[0025] In the above technical scheme, the fatty alcohol in the fatty alcohol polyoxyethylene ether is preferably a C8-C20 fatty alcohol. For example, but not limited to, C9 fatty alcohol, C10 fatty alcohol, C11 fatty alcohol, C12 fatty alcohol, C13 fatty alcohol, C14 fatty alcohol, C15 fatty alcohol, C16 fatty alcohol, C17 fatty alcohol, C18 fatty alcohol, C19 fatty alcohol, or a mixture thereof. The carbon chain in the fatty alcohol can be a straight chain or a branched chain, and the alcohol hydroxyl group can be a primary hydroxyl group or a secondary hydroxyl group.

[0026] In the above technical scheme, it is preferred that the addition number of ethylene oxide in the fatty alcohol polyoxyethylene ether is 4 to 15, for example but not limited to 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and the like.

[0027] For comparison only, the fatty alcohol polyoxyethylene ether used in the embodiment of the present invention is isomeric alcohol polyoxyethylene ether, the isomeric alcohol is isomeric tridecanol, and the ethylene oxide addition number is 9. It is supplied by BASF, with a brand number of 1309 and an effective matter content of 99%.

[0028] In the above technical solution, the alkylphenol in the alkylphenol polyoxyethylene ether preferably has an alkyl group of C5 to C10, such as an alkyl group of C6, an alkyl group of C7, an alkyl group of C8 or an alkyl group of C9. Among the commercially available varieties, there are mainly octylphenol polyoxyethylene ether or nonylphenol polyoxyethylene ether.

[0029] In the above technical solution, the number of ethylene oxide addition in the alkylphenol polyoxyethylene ether is preferably 4-15.

[0030] In the above technical solution, the carbon number of the alkyl group in the alkyl glycoside is preferably 8 to 16, for example but not limited to 9, 10, 11, 12, 13, 14, 15, or a mixture of the above alkyl groups with different carbon numbers.

[0031] In the above technical solution, the degree of polymerization of the alkyl glycoside or the number of sugar residues n is 1.1-3, for example but not limited to n is 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.2, 2.5, 2.7, 2.9 and the like.

[0032] For comparison only, the alkyl glycoside used in the embodiments of the present invention and the comparative examples is specifically: C8-C10 alkyl glycoside, the product is supplied by Shanghai Fakai Chemical Co., Ltd., the brand is Green APG 0810, the appearance is light yellow liquid, the effective matter content is 50%, and the polymerization degree is 1.4.

[0033] In the above technical solution, preferably, the anionic surfactant includes at least one selected from the group consisting of α-olefin sulfonates or salts thereof, alkylbenzene sulfonic acid or salts thereof, and alkanoyl amino acids or salts thereof; and the salts are each independently preferably alkali metal salts or triethanolamine salts. In the present invention, the anionic surfactant, whether in acid or salt form, is measured in the form of sodium salt.

[0034] In the above technical scheme, the α-olefin sulfonate or its salt is preferably a C14-C18 olefin, such as but not limited to C14 olefin, C15 olefin, C16 olefin, C17 olefin, C18 olefin, or a mixture thereof.

[0035] For comparison only, the sodium salt of α-olefin sulfonate, i.e. sodium α-olefin sulfonate, used in the embodiments of the present invention is supplied by Hunan Lichen Industrial Co., Ltd., with the brand name RSAW AOS35 / ZA, and is a colorless or light yellow liquid with a carbon number of C14-16 and an effective matter content of 35%.

[0036] In the above technical solution, it is preferred that the alkyl group described in the alkylbenzene sulfonic acid or its salt is a C11-C18 alkyl group, for example but not limited to a C11 alkyl group, a C12 alkyl group, a C13 alkyl group, a C14 alkyl group, a C15 alkyl group, a C16 alkyl group, a C17 alkyl group, a C18 alkyl group, or a mixture of the above alkyl groups with different carbon numbers.

[0037] In the above technical solution, preferably, in the alkanoyl amino acid or salt, the alkanoyl group is represented by RCO-, R is an alkyl group, and the alkyl group is a C11-C17 alkyl group, such as but not limited to a C11 alkyl group, a C12 alkyl group, a C13 alkyl group, a C14 alkyl group, a C15 alkyl group, a C16 alkyl group, a C17 alkyl group, or a mixture of the above alkyl groups with different carbon numbers. And / or preferably, the amino acid is, for example but not limited to, sarcosine, glutamic acid, alanine, glycine, taurine, methyltaurine, etc.

[0038] For example only, the commonly used surfactants in the embodiments of the present invention include α-olefin sulfonates (or their salts), fatty alcohol polyoxyethylene ethers and alkyl glycosides. In particular, by mass, preferably, the ratio of alkyl glycoside: fatty alcohol polyoxyethylene ether: α-olefin sulfonates (or their salts) is 1: a: b, a is 0.2 to 5 (for example, but not limited to, a is 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 3, 4, etc.), more preferably a is 0.5 to 2; b is 0.5 to 10 (for example, but not limited to, b is 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, etc.), more preferably b is 1 to 5.

[0039] In the above technical scheme, the metal complexing agent is not particularly limited and can be selected from those commonly used in the art. The most commonly used in industry is aminocarboxyl complexing agent, and therefore, the metal complexing agent described in the present invention includes selected from aminocarboxyl complexing agent. As the name suggests, aminocarboxyl complexing agent is a complexing agent containing amino (primary amino group, secondary amino group or tertiary amino group) and carboxyl group in its structure. A non-limiting example is that the aminocarboxyl complexing agent includes at least one selected from the group consisting of nitrilotriacetic acid or its salt, ethylenediaminetetraacetic acid or its salt, diethylenetriaminepentaacetic acid or its salt, glutamic acid diacetic acid or its salt, and methylglycine diacetic acid or its salt; the salts described herein are each independently preferably alkali metal salts or triethanolamine salts. In the present invention, amino acid complexing agents can use acid type, acid salt type, or normal salt type. The measurement of aminocarboxyl complexing agents in the present invention is converted into normal salt and measured in the form of sodium salt. For comparison only, the metal complexing agent in the embodiment of the present invention is tetrasodium glutamate diacetate (abbreviated as GLDA.Na4), which is supplied by Shandong Yuanlian Chemical Co., Ltd. and has an effective matter content of 47%.

[0040] There is no particular restriction on polymer dispersants, and those skilled in the art can choose them without creative effort. The function of the dispersant is to disperse the stains or particulate matter evenly in the liquid medium, prevent the particulate matter with extremely strong adhesion from re-precipitating or re-agglomerating in the liquid medium or on the surface of the workpiece, and effectively improve the decontamination ability of the cleaning agent. Preferred water-soluble polymer dispersants include, for example but not limited to, at least one selected from the group consisting of polystyrene sulfonic acid or its salt, polyacrylic acid or its salt, maleic acid-acrylic acid copolymer or its salt, polyoxysuccinic acid or its salt, polyacrylamide, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone and polyethyleneimine ethoxylate; the salts described herein are each independently preferably alkali metal salts or triethanolamine salts.

[0041] However, we have found that dispersants such as polyacrylic acid or its salts (referred to as the first dispersant) and polyethyleneimine ethoxylate (referred to as the second dispersant) have a mutually reinforcing effect in improving the cleaning power.

[0042] In the above technical solution, the mass ratio of the first type of dispersant to the second type of dispersant is preferably 0.5-5, for example but not limited to 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, etc., more preferably 1-4.

[0043] Only for comparison, the first type of dispersant commonly used in the embodiments of the present invention is sodium polyacrylate, which is supplied by Shenyang Xinqi Daily Chemical Co., Ltd. with the brand name PAA-45. The weight average molecular weight of sodium polyacrylate is 4000-5000, and it is in the form of aqueous solution with an effective matter content of 45%.

[0044] For comparison purposes only, the second type of dispersant commonly used in the embodiments of the present invention is polyethyleneimine ethoxylate. In the art, the chemical formula of polyethyleneimine ethoxylate is defined as conforming to Formula 2:

[0045] (PEI)x(EO)y, formula 2;

[0046] Wherein PEI represents the "polyethyleneimine core" in the compound described in Formula 2. The weight of this core is compared with the raw material polyethyleneimine used to synthesize the compound shown in Formula 2. The only difference is that this core lacks the H connected to the N atom that can be replaced by ethoxylation reaction (called replaceable hydrogen, represented as NH). The difference between the mass of this core and the raw material is only whether it contains replaceable hydrogen atoms, but this difference can be ignored in the industry and is within the error range. Wherein, x represents the weight average molecular weight of PEI, that is, the weight average molecular weight of the raw material polyethyleneimine regarded as the compound shown in Formula 2 within the allowable error range; the replaceable hydrogen in the polyethyleneimine is replaced by a polyoxyethylene chain "-(EO)yH"), and y is the average number of ethylene oxide units in the polyoxyethylene chain to which each replaceable hydrogen is connected, also known as the average number of ethylene oxide additions to NH.

[0047] For the dispersant, preferably x is 500-6000 (for example but not limited to x is 550, 600, 650, 700, 750, 800, 850, 900, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, etc.), more preferably x is 600-3000. And / or for the dispersant, preferably y is 5-40 (for example but not limited to y is 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, etc.), more preferably y is 10-30. For comparison only, polyethyleneimine ethoxylate is supplied by BASF with the brand name HP20, appearance is light yellow to yellowish brown transparent liquid, effective matter content is 80%, the weight average molecular weight of raw material polyethyleneimine is 800, y is 20.

[0048] The main purpose of the present invention is to improve the cleaning power. As for the corrosion inhibitor, those skilled in the art can reasonably select those already available in the prior art without having to make creative efforts. For example, but not limited to, the corrosion inhibitor includes at least one selected from the group consisting of alkyl phosphates or salts thereof, polyol phosphates or salts thereof, imidazoline phosphates or salts thereof, and fatty acid alkanolamide phosphates or salts thereof; here, the salts are each independently preferably selected from alkali metal salts or triethanolamine salts.

[0049] Only for comparison, the inositol hexaphosphate commonly used in the present invention belongs to the above-mentioned polyol phosphate. Inositol hexaphosphate has a unique molecular structure and excellent physical and chemical properties. It forms a very thin organic phosphating film on the metal surface, making the electrode potential of the metal surface close to that of inert metals such as platinum and gold; in addition, the dense monomolecular protective film can effectively prevent O2 and the like from entering the metal surface, effectively slowing down the corrosion problem of the acid cleaning agent system on the aluminum alloy surface, and achieving a satisfactory corrosion inhibition effect. In the embodiments of the present invention, inositol hexaphosphate is commonly used, which is supplied by Guangzhou Fufei Chemical Technology Co., Ltd. It has the appearance of a light yellow or light brown viscous liquid, and the effective matter content is 50%.

[0050] Liquid detergents, whether in the production process or in the field, are prone to foaming due to the use of surfactants in the detergent formula, which brings inconvenience to the operation. From this aspect, a defoamer can be added to the detergent of the present invention in advance. In the present invention, there is no special restriction on the defoamer, and those commonly used in the prior art can be used without creative labor. Only for comparison, the embodiments of the present invention generally use a polyether defoamer, which is supplied by Xuantong (Shanghai) Chemical Technology Co., Ltd., with a brand name of WESTAR XF-EP 101, and an effective matter content of ≥99%.

[0051] As for the amount of defoamer, the technicians in this field can reasonably choose the amount according to the specific use conditions and the degree of foaming without creative work. For example, the cleaning agent includes 0.1 to 1.0 parts of defoamer, such as but not limited to 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, etc.

[0052] Those skilled in the art will readily understand that, in order to reduce storage and transportation costs, the cleaning agent of the present invention may not use a solvent, but may add a solvent to the desired concentration at the cleaning site. However, in order to facilitate cleaning, the cleaning agent of the present invention may use a solvent to prepare a reserve liquid product with a concentration higher than the actual cleaning concentration, so that the solvent may be added on site to dilute the product to the concentration actually used in the cleaning operation. Furthermore, in order to make cleaning more convenient, the cleaning agent of the present invention may be directly prepared to the concentration required for the cleaning operation.

[0053] In the above technical solution, it is preferred that the solvent is mainly water. Mainly water means that the weight concentration of water in the solvent is greater than 50% and less than 100% (for example, but not limited to the weight concentration of water in the solvent is 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, etc.). In addition to mainly containing water, the solvent can also be used as an auxiliary solvent known in the art (for example, to increase the solubility of a specific component, such as to increase the spreadability of the cleaning agent on the cleaning surface, etc.) Those organic solvents that are easily soluble in water, such as ethanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether of C2-C4 alcohols, etc. For comparison only, the solvents in the specific embodiments of the present invention are all water.

[0054] In the above technical scheme, the preferred amount of solvent is such that the total weight of the cleaning agent reaches 100 to 1000 parts. For example, but not limited to, the amount of solvent is such that the total weight of the cleaning agent reaches 150 parts, 200 parts, 250 parts, 300 parts, 350 parts, 400 parts, 450 parts, 500 parts, 550 parts, 600 parts, 650 parts, 700 parts, 750 parts, 800 parts, 900 parts, etc.

[0055] The technical key of the present invention is the selection of cleaning agent components, and there is no special limitation on the preparation method. Those skilled in the art only need to simply mix the required components evenly without any creative work, and comparable technical effects can be achieved.

[0056] In the present invention, except for the total weight of the solvent and the cleaning agent, the amount of each component is calculated on the basis of the effective substance. Those skilled in the art can easily understand the meaning of the amount of each component being calculated on the basis of the effective substance, for example but not limited to, if a certain component is used in the form of containing crystal water, it is calculated on the basis of the anhydrous substance, if a certain component is in the form of a liquid in which the effective substance is dissolved or dispersed in a solvent, it is calculated on the basis of the effective substance actually contained therein, and if a certain component contains inevitable impurities in addition to the effective substance, it is measured on the basis of the effective substance therein.

[0057] The second object of the present invention is to provide the application of the above-mentioned cleaning agent.

[0058] To achieve the second purpose, the technical solution of the present invention is: the use of the cleaning agent in the cleaning of 7 series aluminum materials; preferably, the use of the cleaning agent in the cleaning of silicon dioxide polishing liquid residues on the surface of 7 series aluminum materials.

[0059] The technical key of the present invention is the selection of the required components of the cleaning agent, and the specific process conditions used in the cleaning of 7 series aluminum materials. Those skilled in the art can reasonably select them without having to make creative efforts.

[0060] This is only for example, and is also the third purpose to be achieved by the present invention:

[0061] A method for cleaning 7 series aluminum material comprises contacting the surface of the 7 series aluminum material to be cleaned with a cleaning agent solution.

[0062] In the above technical scheme, the preferred weight concentration of the cleaning agent solution (calculated as hydroxy-substituted carboxylic acid) is 0.5-10%, for example but not limited to 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%.

[0063] In the above technical solution, the contact temperature is preferably 30-60°C, for example but not limited to 35°C, 40°C, 45°C, 50°C, 55°C.

[0064] In the above technical solution, the preferred contact method is immersion, spraying, brushing, swing washing, bubbling cleaning, ultrasonic cleaning, or a combination thereof.

[0065] Evaluation method of the cleaning agent of the present invention

[0066] The cleaning power and corrosion tests are carried out according to the test methods specified in GB / T 35759-2017 for metal cleaning agents, except for the following differences:

[0067] Different from the material and specification of the test piece in 5.1.1 of the standard, the present invention is: 7 series aluminum alloy test piece (model 7050, specification 90mm×40mm×2.5mm), such as Figure 1 shown.

[0068] The difference between the grinding and cleaning of the test piece in 5.1.2 of the standard and the present invention is:

[0069] Use 3000# emery cloth for grinding.

[0070] Different from the preparation of the test solution in 5.2 of the standard, the present invention is:

[0071] The test solutions used for the evaluation of cleaning power and corrosiveness were all diluted with deionized water to a weight concentration (calculated as hydroxy-substituted carboxylic acid) of 2%.

[0072] Different from 5.7.2 Reagents and Materials in the standard, the present invention is:

[0073] Commercially available silica polishing liquid (provided by Shenzhen Chuanyan Technology Co., Ltd., brand CY-3803, silica sol particle size of 98.8nm, concentration of 40%, pH value of 9.76, specific gravity: 1.293) was used to replace the artificial oil in the standard. During the test, the silica polishing liquid was diluted to 15% with deionized water.

[0074] Different from the coating of artificial oil pollution in 5.7.4.2 of the standard, the present invention is:

[0075] Use tweezers to pick up the uncoated part of the upper surface (such as Figure 2 As shown), immerse the lower 80 mm of the test piece in the silica polishing liquid, take it out after 30 seconds, hang it on the test piece rack and place it in a (40±2)℃ constant temperature drying oven for drying for 30 minutes, then take it out, repeat the above immersion and drying operations until the dryer is cooled and weighed (accurate to ±0.0001g) and the amount of dirt coating is between 0.1000g and 0.2500g.

[0076] Different from the swing washing in 5.7.4.3 of the standard, the present invention is:

[0077] As mentioned above, in addition to the test solution being different from the standard, the immersion and swing washing temperatures used are controlled at (45±2)°C, and therefore are also different from those in the standard.

[0078] Different from the test procedure in 5.9.4 of the standard, the present invention:

[0079] The following four conditions were tested to replace the (80±2)℃ and 2-hour immersion test in the standard:

[0080] (1) Immersion test at (45±2)℃ for 4 hours;

[0081] (2) Immersion test at (45±2)℃ for 8 hours;

[0082] (3) Immersion test at (60±2)℃ for 4 hours;

[0083] (4) Immerse in water at (60±2)℃ for 8 hours.

[0084] The rating of corrosion appearance shall be carried out in accordance with the provisions of section b) of 5.9.5.2 of the standard. BRIEF DESCRIPTION OF THE DRAWINGS

[0085] Figure 1 It is a schematic diagram of the specifications of the 7 series aluminum alloy test piece used in the evaluation of the present invention.

[0086] The specifications are 90mm×40mm×2.5mm.

[0087] Figure 2 It is a schematic diagram of the coating of artificial oil pollution.

[0088] The present invention is illustrated below by means of specific embodiments. DETAILED DESCRIPTION

[0089] [Example 1]

[0090] (I) Preparation of 7 series aluminum alloy surface cleaning agent

[0091] First, add 30 parts by weight of primer water to the preparation container and heat it to 50-60°C, then add 5.0 parts by weight of sodium α-olefin sulfonate, 2.0 parts by weight of isomeric alcohol polyoxyethylene ether, 2.0 parts by weight of alkyl glucoside, 5.5 parts by weight of tetrasodium glutamate diacetate, 3.0 parts by weight of polyethyleneimine ethoxylate, and 0.5 parts by weight of defoamer, stir evenly, then add 10.0 parts by weight of citric acid and 3.5 parts by weight of corrosion inhibitor, and finally add water to the actual total weight of the cleaning agent to 100 parts, stir evenly, and cool to room temperature.

[0092] (II) Evaluation of cleaning agents

[0093] The cleaning agent in the above section "(i)" was diluted with deionized water to a weight concentration (calculated as hydroxy-substituted carboxylic acid) of 2% to serve as a test solution for evaluation.

[0094] The evaluation results are:

[0095] The cleaning power is 86.8%;

[0096] The appearance is level 0 after immersion at 45℃ for 4 hours and level 0 after 8 hours;

[0097] The appearance after immersion at 60℃ for 4 hours is Grade 0, and the appearance after 8 hours is Grade 1.

[0098] [Example 2]

[0099] (I) Preparation of 7 series aluminum alloy surface cleaning agent

[0100] First, add 30 parts by weight of primer water to the preparation container and heat it to 50-60°C, then add 5.0 parts by weight of sodium α-olefin sulfonate, 2.0 parts by weight of isomeric alcohol polyoxyethylene ether, 2.0 parts by weight of alkyl glucoside, 5.5 parts by weight of tetrasodium glutamate diacetate, 3.0 parts by weight of sodium polyacrylate, 0.5 parts by weight of defoamer, stir evenly, then add 10.0 parts by weight of citric acid and 3.5 parts by weight of corrosion inhibitor, finally add water to the actual total weight of the cleaning agent to 100 parts, stir evenly, and cool to room temperature.

[0101] (II) Evaluation of cleaning agents

[0102] The cleaning agent in the above section "(i)" was diluted with deionized water to a weight concentration (calculated as hydroxy-substituted carboxylic acid) of 2% to serve as a test solution for evaluation.

[0103] The evaluation results are:

[0104] The cleaning power is 88.5%;

[0105] The appearance is level 0 after immersion at 45℃ for 4 hours and level 0 after 8 hours;

[0106] The appearance after immersion at 60℃ for 4 hours is Grade 0, and the appearance after 8 hours is Grade 1.

[0107] [Example 3]

[0108] (I) Preparation of 7 series aluminum alloy surface cleaning agent

[0109] First, add 30 parts by weight of primer water to the preparation container and heat it to 50-60°C, then add 5.0 parts by weight of sodium α-olefin sulfonate, 2.0 parts by weight of isomeric alcohol polyoxyethylene ether, 2.0 parts by weight of alkyl glucoside, 5.5 parts by weight of tetrasodium glutamate diacetate, 2.0 parts by weight of sodium polyacrylate, 1.0 parts by weight of polyethyleneimine ethoxylate, 0.5 parts by weight of defoamer, stir evenly, then add 10.0 parts by weight of citric acid and 3.5 parts by weight of corrosion inhibitor, and finally add water to the actual total weight of the cleaning agent to 100 parts, stir evenly, and cool to room temperature.

[0110] (II) Evaluation of cleaning agents

[0111] The cleaning agent in the above section "(i)" was diluted with deionized water to a weight concentration (calculated as hydroxy-substituted carboxylic acid) of 2% to serve as a test solution for evaluation.

[0112] The evaluation results are:

[0113] The cleaning power is 92.4%;

[0114] Immersed at 45℃ for 4 hours, the appearance is level 0, and 8 hours, the appearance is level 1;

[0115] The appearance after immersion at 60℃ for 4 hours is Grade 0, and the appearance after 8 hours is Grade 1.

[0116] [Example 4]

[0117] (I) Preparation of 7 series aluminum alloy surface cleaning agent

[0118] First, add 30 parts by weight of primer water to the preparation container and heat it to 50-60°C, then add 5.0 parts by weight of sodium α-olefin sulfonate, 2.0 parts by weight of isomeric alcohol polyoxyethylene ether, 2.0 parts by weight of alkyl glucoside, 5.5 parts by weight of tetrasodium glutamate diacetate, 3.0 parts by weight of polyethyleneimine ethoxylate, and 0.5 parts by weight of defoamer, stir evenly, then add 10.0 parts by weight of 3,4,5-trihydroxybenzoic acid and 3.5 parts by weight of corrosion inhibitor, finally add water to the actual total weight of the cleaning agent to 100 parts, stir evenly, and cool to room temperature.

[0119] (II) Evaluation of cleaning agents

[0120] The cleaning agent in the above section "(i)" was diluted with deionized water to a weight concentration (calculated as hydroxy-substituted carboxylic acid) of 2% to serve as a test solution for evaluation.

[0121] The evaluation results are:

[0122] The cleaning power is 89.4%;

[0123] The appearance is level 0 after immersion at 45℃ for 4 hours and level 1 after 8 hours;

[0124] The appearance after immersion at 60℃ for 4 hours is Grade 0, and the appearance after 8 hours is Grade 1.

[0125] [Example 5]

[0126] (I) Preparation of 7 series aluminum alloy surface cleaning agent

[0127] First, add 30 parts by weight of primer water to the preparation container and heat it to 50-60°C, then add 5.0 parts by weight of sodium α-olefin sulfonate, 2.0 parts by weight of isomeric alcohol polyoxyethylene ether, 2.0 parts by weight of alkyl glucoside, 5.5 parts by weight of tetrasodium glutamate diacetate, 3.0 parts by weight of sodium polyacrylate, 0.5 parts by weight of defoamer, stir evenly, then add 10.0 parts by weight of 3,4,5-trihydroxybenzoic acid and 3.5 parts by weight of corrosion inhibitor, finally add water to the actual total weight of the cleaning agent to 100 parts, stir evenly, and cool to room temperature.

[0128] (II) Evaluation of cleaning agents

[0129] The cleaning agent in the above section "(i)" was diluted with deionized water to a weight concentration (calculated as hydroxy-substituted carboxylic acid) of 2% to serve as a test solution for evaluation.

[0130] The evaluation results are:

[0131] The cleaning power is 91.3%;

[0132] The appearance is level 0 after immersion at 45℃ for 4 hours and level 1 after 8 hours;

[0133] The appearance after immersion at 60℃ for 4 hours is Grade 0, and the appearance after 8 hours is Grade 1.

[0134] [Example 6]

[0135] (I) Preparation of 7 series aluminum alloy surface cleaning agent

[0136] First, add 30 parts by weight of primer water to the preparation container and heat it to 50-60°C, then add 5.0 parts by weight of sodium α-olefin sulfonate, 2.0 parts by weight of isomeric alcohol polyoxyethylene ether, 2.0 parts by weight of alkyl glucoside, 5.5 parts by weight of tetrasodium glutamate diacetate, 2.0 parts by weight of sodium polyacrylate, 1.0 parts by weight of polyethyleneimine ethoxylate, 0.5 parts by weight of defoamer, stir evenly, then add 10.0 parts by weight of 3,4,5-trihydroxybenzoic acid and 3.5 parts by weight of corrosion inhibitor, finally add water to the actual total weight of the cleaning agent to 100 parts, stir evenly, and cool to room temperature.

[0137] (II) Evaluation of cleaning agents

[0138] The cleaning agent in the above section "(i)" was diluted with deionized water to a weight concentration (calculated as hydroxy-substituted carboxylic acid) of 2% to serve as a test solution for evaluation.

[0139] The evaluation results are:

[0140] The cleaning power is 95.2%;

[0141] The appearance is level 0 after immersion at 45℃ for 4 hours and level 0 after 8 hours;

[0142] The appearance after immersion at 60℃ for 4 hours is Grade 0, and the appearance after 8 hours is Grade 1.

[0143] [Example 7]

[0144] (I) Preparation of 7 series aluminum alloy surface cleaning agent

[0145] First, add 30 parts by weight of primer water to the preparation container and heat it to 50-60°C, then add 5.0 parts by weight of sodium α-olefin sulfonate, 2.0 parts by weight of isomeric alcohol polyoxyethylene ether, 2.0 parts by weight of alkyl glucoside, 5.5 parts by weight of tetrasodium glutamate diacetate, 2.0 parts by weight of sodium polyacrylate, 1.0 parts by weight of polyethyleneimine ethoxylate, 0.5 parts by weight of defoamer, stir evenly, then add 6.0 parts by weight of 3,4,5-trihydroxybenzoic acid, 4.0 parts by weight of citric acid and 3.5 parts by weight of corrosion inhibitor, finally add water to the actual total weight of the cleaning agent to 100 parts, stir evenly, and cool to room temperature.

[0146] (II) Evaluation of cleaning agents

[0147] The cleaning agent in the above section "(i)" was diluted with deionized water to a weight concentration (calculated as hydroxy-substituted carboxylic acid) of 2% to serve as a test solution for evaluation.

[0148] The evaluation results are:

[0149] The cleaning power is 99.9%;

[0150] The appearance is level 0 after immersion at 45℃ for 4 hours and level 0 after 8 hours;

[0151] The appearance is level 0 after immersion at 60℃ for 4 hours and level 0 after 8 hours.

[0152] [Example 8]

[0153] (I) Preparation of 7 series aluminum alloy surface cleaning agent

[0154] First, add 30 parts by weight of primer water to the preparation container and heat it to 50-60°C, then add 5.0 parts by weight of sodium α-olefin sulfonate, 2.0 parts by weight of isomeric alcohol polyoxyethylene ether, 2.0 parts by weight of alkyl glucoside, 5.5 parts by weight of tetrasodium glutamate diacetate, 3.0 parts by weight of polyethyleneimine ethoxylate, 0.5 parts by weight of defoamer, stir evenly, then add 6.0 parts by weight of 3,4,5-trihydroxybenzoic acid, 4.0 parts by weight of citric acid and 3.5 parts by weight of corrosion inhibitor, finally add water to the actual total weight of the cleaning agent to 100 parts, stir evenly, and cool to room temperature.

[0155] (II) Evaluation of cleaning agents

[0156] The cleaning agent in the above section "(i)" was diluted with deionized water to a weight concentration (calculated as hydroxy-substituted carboxylic acid) of 2% to serve as a test solution for evaluation.

[0157] The evaluation results are:

[0158] The cleaning power is 92.6%;

[0159] The appearance is level 0 after immersion at 45℃ for 4 hours and level 0 after 8 hours;

[0160] The appearance is level 0 after immersion at 60℃ for 4 hours and level 0 after 8 hours.

[0161] [Example 9]

[0162] (I) Preparation of 7 series aluminum alloy surface cleaning agent

[0163] First, add 30 parts by weight of primer water to the preparation container and heat it to 50-60°C, then add 5.0 parts by weight of sodium α-olefin sulfonate, 2.0 parts by weight of isomeric alcohol polyoxyethylene ether, 2.0 parts by weight of alkyl glucoside, 5.5 parts by weight of tetrasodium glutamate diacetate, 3.0 parts by weight of sodium polyacrylate, 0.5 parts by weight of defoamer, stir evenly, then add 6.0 parts by weight of 3,4,5-trihydroxybenzoic acid, 4.0 parts by weight of citric acid and 3.5 parts by weight of corrosion inhibitor, finally add water to the actual total weight of the cleaning agent to 100 parts, stir evenly, and cool to room temperature.

[0164] (II) Evaluation of cleaning agents

[0165] The cleaning agent in the above section "(i)" was diluted with deionized water to a weight concentration (calculated as hydroxy-substituted carboxylic acid) of 2% to serve as a test solution for evaluation.

[0166] The evaluation results are:

[0167] The cleaning power is 93.5%;

[0168] The appearance is level 0 after immersion at 45℃ for 4 hours and level 0 after 8 hours;

[0169] The appearance is level 0 after immersion at 60℃ for 4 hours and level 0 after 8 hours.

[0170] Comparison of Examples 1 to 6 shows that the compounding of polyethyleneimine ethoxylate and sodium polyacrylate significantly improves the cleaning power, but long-term immersion at high temperature still causes slight corrosion to the metal; Comparison of Examples 8 to 9 with Examples 1 to 2 and 4 to 5 shows that the compounding of citric acid and 3,4,5-trihydroxybenzoic acid can improve the cleaning ability and is also of great help to the protection of the metal surface; The results of Example 7 show that the use of citric acid and 3,4,5-trihydroxybenzoic acid, polyethyleneimine ethoxylate and sodium polyacrylate in the formula at the same time has the best cleaning effect. Therefore, it can be concluded that the multifunctional cleaning agent for silica polishing liquid on the surface of 7 series aluminum alloy provided by the present invention has excellent cleaning ability for silica sol, can be used at medium and low temperatures, and has high practical application value.

[0171] The above description is only a specific embodiment of the present invention, and the scope of protection of the present invention cannot be limited by this. Any non-substantial changes made by using the present invention, changes in certain process technologies derived from the concept and specific embodiments of the present invention, or non-substantial changes such as replacement of related technologies, or direct or indirect application in other related technical fields, all fall within the scope of protection required by the present invention.

Claims

1. 7 series aluminum alloy surface cleaning agent, including: Hydroxyl-substituted carboxylic acid, 10 parts; Surfactant, 2-15 parts; Metal complexing agent, 2 to 10 parts; Corrosion inhibitor, 1 to 10 parts.

2. The cleaning agent according to claim 1, characterized in that The carbon number of the hydroxycarboxylic acid molecule is 2 to 7; preferably, the molar ratio of the hydroxyl group to the carboxyl group in the hydroxycarboxylic acid molecule is 0.3 to 3.

3. The cleaning agent according to claim 1, characterized in that The surfactant comprises at least one selected from the group consisting of nonionic surfactants and anionic surfactants; preferably, the nonionic surfactant comprises at least one selected from the group consisting of fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers or alkyl glycosides; and / or preferably The anionic surfactant comprises at least one selected from the group consisting of α-olefin sulfonates or salts thereof, alkylbenzene sulfonic acid or salts thereof, and alkanoyl amino acids or salts thereof; the salts are each independently preferably alkali metal salts or triethanolamine salts; More preferably, the surfactant includes α-olefin sulfonate, fatty alcohol polyoxyethylene ether and alkyl glycoside; more preferably, by mass, the ratio of alkyl glycoside: fatty alcohol polyoxyethylene ether: α-olefin sulfonate is 1:a:b, a is 0.2-5, and b is 0.5-10.

4. The cleaning agent according to claim 1, characterized in that The metal complexing agent includes an aminocarboxylic acid complexing agent. For example, the aminocarboxylic acid complexing agent includes at least one selected from the group consisting of nitrilotriacetic acid or its salt, ethylenediaminetetraacetic acid or its salt, diethylenetriaminepentaacetic acid or its salt, glutamic acid diacetic acid or its salt, and methylglycine diacetic acid or its salt.

5. The cleaning agent according to claim 1, characterized in that The corrosion inhibitor includes at least one selected from the group consisting of alkyl phosphates or salts thereof, polyol phosphates or salts thereof, imidazoline phosphates or salts thereof, and fatty acid alkanolamide phosphates or salts thereof.

6. The cleaning agent according to claim 1, characterized in that The cleaning agent includes 0.1 to 1 part of a defoaming agent.

7. The cleaning agent according to claim 3, characterized in that The cleaning agent includes a solvent, preferably the solvent is mainly water. It is further preferred that the amount of solvent used is such that the total weight of the cleaning agent reaches 100 to 1000 parts.

8. Use of the cleaning agent according to any one of claims 1 to 7 in cleaning 7 series aluminum materials.

9. A method for cleaning a 7 series aluminum material, comprising contacting the surface of the 7 series aluminum material to be cleaned with a solution of a cleaning agent as claimed in any one of claims 1 to 8. Preferably, the weight concentration of the cleaning agent solution is 0.5 to 10% in terms of hydroxy-substituted carboxylic acid; and / or the preferred contact temperature is 30 to 60° C.; and / or the preferred contact method is immersion, spraying, brushing, swing washing, bubbling cleaning, ultrasonic cleaning, or a combination thereof.

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