CN103451666A - Metal cleaning agent - Google Patents
Metal cleaning agent Download PDFInfo
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- CN103451666A CN103451666A CN2013104242768A CN201310424276A CN103451666A CN 103451666 A CN103451666 A CN 103451666A CN 2013104242768 A CN2013104242768 A CN 2013104242768A CN 201310424276 A CN201310424276 A CN 201310424276A CN 103451666 A CN103451666 A CN 103451666A
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Abstract
The invention relates to a metal cleaning agent and particularly relates to a cleaning agent for cleaning surface contaminants of mechanical metal. The metal cleaning agent disclosed by the invention is used for overcoming the defects of the existing cleaning agents that the cleaning efficiency of relatively heavy oil stains is low, the cleaning time is long and the environment is polluted. The metal cleaning agent is prepared from a mercapto-containing compound, alcohol ether, a strong chelating agent and water.
Description
Technical field
The present invention relates to a kind of metal cleaner, specifically, is the clean-out system of a kind of wash machine metallic surface pollutent.
Background technology
In the course of processing of metal parts product; usually can use oil, gel, ionogen etc., the metal product after processing, these materials have part and are attached to metallic surface and pollute; so will carry out cleaning to the metal parts after processing, clean and remove these residues.
Specifically, contain the graininess dirt that comes as the fatty oil of lubricating oil and mineral oil, dyestuff, flue dust and other upstream process, metal oxide etc. in greasy dirt, dirt related in the cleaning metal surface process is very extensive, the greasy dirt formed by these materials-unctuousness dirt, after the variation of experience long period, through chemical reactions such as heating, dryings, form the obstinate dirt of removing that is difficult to that the common washing composition of use very obstinate, that color is darker is difficult to reach good washing effect in metallic surface.When a metallic surface detergent formulation of design, its main purpose is not only except degreasing, and will keep metallic surface as excellent as before.
Often to use in the process of Metal Production and processing and clean the oil removing operation.The various degreasing agent for metals that often use at present, mainly contain strong acid, highly basic and tensio-active agent etc.They are all generally that the greasy dirt lighter for metal surface processed, low to heavier greasy dirt cleaning efficiency, show that scavenging period is long, and effect is also very poor; Foam is a lot, cleans after affecting the effect of oil removing and oil removing; Containing various hazardous and noxious substances, as Sodium Nitrite etc., contaminate environment, damage operator's health; Easily more active metal is caused to corrosion as aluminium etc., affect following process.
In view of the above problems, in the urgent need to a kind of environmental protection, close environment wetting ability excellence, also there is the efficient water-soluble metal cleaner of wipe oil fast when thering is good cleaning performance.
Summary of the invention
The present application provides following metal cleaner, and this metal cleaner, for for removing the clean-out system of metal surface greasy dirt, is compared with product in the past, and this clean-out system can be brought into play cleaning performance in the short period of time.
The inventor, through research repeatedly, found that, by using specific sequestrant, cleans thoroughly and can also accelerate the cleaning speed of metal cleaner in assurance, thereby completed the present invention simultaneously.
A kind of metal cleaner of the present invention, the component that comprises following weight part:
Compounds containing thiol groups 20-30
Alcohol ether 5-25
Water 100
Or
Compounds containing thiol groups 20-30
Strong chelating agent 20-30
Water 100
Embodiment
Below, the embodiment the present invention relates to is described.In addition, the present invention, the embodiment do not the following describes, the restriction of embodiment.
As mentioned above, a kind of metal cleaner according to the present invention is to comprise sequestrant, alcohol ether, tensio-active agent.
The present invention mainly selects water, sequestrant, alcohol ether auxiliary agent, tensio-active agent as the material comprised in embodiment.
water
Metal cleaner of the present invention can be solvent-laden liquid metal clean-out system, can be also that sequestrant and surfactivity combine and be prepared into the solid metal clean-out system.
Described solid metal clean-out system is used after needing in use to utilize solvent cut.
The preferred liquid metal clean-out system of metal cleaner of the present invention.
The available solvent of metal cleaner has hydro carbons (petroleum-type), hydrochloric ether, hydrofluoric ether, hydrobromic ether, alcohols, organosilicon, terpenes, alcohols, glycol ester, organic hydrocarbon, N-Methyl pyrrolidone, water etc.
According to the requirement to environment protection, solvent preferably water of the present invention.
Water take in embodiments of the invention as solvent.
compounds containing thiol groups
Compounds containing thiol groups of the present invention can be selected the compound containing following structural formula:
Be selected from-COOH of the preferred X of above-mentioned compounds containing thiol groups ,-a kind of in OH.N is not more than 5 positive integer.
Above-mentioned compounds containing thiol groups is preferably from mercaptoethanol, Thiovanic acid, 3-mercaprol, one or several in the 3-thiohydracrylic acid.
Above-mentioned compounds containing thiol groups molecular weight is little, contains sulfydryl simultaneously, and metal ion is had to very strong adsorptive power.
Above-mentioned compounds containing thiol groups has very strong cleansing power to the heavy dirt of metallic surface.Because heavy dirt is adsorbed on metallic surface, be mainly to adsorb by electrostatic attraction, this absorption is stronger than common Intermolecular Forces and hydrogen bond action.Heavy dirt produces oxidation and forms negatively charged ion in long-term precipitation process, with metallic cation, interpenetrates, and forms strong electrostatic attraction.Compounds containing thiol groups is the adsorbing metal positively charged ion effectively, and fast reducing weighs the cohesive force of dirt to metallic surface, reaches the purpose of cleaning.
Above-mentioned compounds containing thiol groups also can replace with its an alkali metal salt, alkaline earth salt, ammonium salt.
Compounds containing thiol groups content of the present invention the 10-25 weight part (take water as 100 weight parts be with reference to).
strong chelating agent
After the matting scale removal, the equipment surface activation, very easily be corroded, and therefore, requires to carry out Passivation Treatment after scale removal.In order to realize a step cleaning inhibition, most of metal cleaner all can add inhibiter, and adsorption corrosion inhibitor is the most frequently used selection.Yet oxidizing reaction, in metallic surface, especially easily occurs in nickeliferous metallic surface in compounds containing thiol groups.
Compounds containing thiol groups after oxidized, form disulfide linkage, and disulfide linkage has good hydrophobic interaction, can be used as adsorption corrosion inhibitor.Yet use separately the clean-out system of compounds containing thiol groups, corrosion mitigating effect is poor.
Clean-out system of the present invention can also contain strong chelating agent, and described strong chelating agent can be selected one or several in nitrilotriacetic acid(NTA) sodium (NTA), edetate (EDTA), diethylenetriamine pentacarboxylic acid salt (DTPA), ethylenediamine tetraacetic methene sodium phosphate (EDTMPS), diethylene triamine pentamethylene phosphonic salt (DETPMPS), nitrilotriacetic acid(NTA).
Above-mentioned sequestrant has larger molecular weight and space structure, there are a plurality of complexing groups, as strong chelating agent, with there is very high stability after metal ion-chelant, can capture the chelated metal ions containing disulfide linkage compound or compounds containing thiol groups, be conducive to the absorption in metallic surface of disulfide linkage compound and compounds containing thiol groups.Disulfide linkage has good hydrophobicity.Reaching the cleaning inhibition synchronously carries out.
The 0.1%-20%(that the usage quantity of strong chelating agent of the present invention is compounds containing thiol groups divides in quality).
alcohol ether
Alcohol ether is mainly the low-carbon alcohol ether of ethylene glycol and propylene glycol.Existing ehter bond in composition, have again hydroxyl.Ehter bond has lipophilicity, the solubilized hydrophobic compound, and hydroxyl has wetting ability, the solubilized water-soluble cpds.
Alcohol ether of the present invention, structural formula is as follows:
RO-（CH
2CH
2O）
nH
Wherein R is hydrogen atom, and carbon atom is in the individual straight chained alkyl of 1-5, and n is the integer of 1-5.
One or more in the optional spent glycol single-butyl ether of described alcohol ether, diethylene glycol monomethyl ether, TC, Diethylene Glycol single-butyl ether, DPGME, propylene glycol monomethyl ether, glycol ether, diethylene glycol monomethyl ether, glycol ether list ether, glycol ether list propyl ether, diethylene glycol monobutyl ether.
Alcohol ether preferred molecular weight of the present invention is lower than 200 straight chain alcohol ether, and the alcohol ether that the straight-chain molecule amount is low can promote sequestrant, the tensio-active agent rapid dispersion in aqueous solvent in metal cleaner, improves the cleaning speed of metal cleaner.
More specifically, alcohol ether RO-(CH
2cH
2o)
nin H, R is hydrogen atom, and carbon atom is in the individual straight chained alkyl of 1-4, and n is the integer of 1-3.
One or more in the present embodiment in the preferred ethylene glycol monobutyl ether of alcohol ether, diethylene glycol monomethyl ether, TC, Diethylene Glycol single-butyl ether, DPGME and propylene glycol monomethyl ether.
The present invention uses alcohol ether can reduce the surface tension of clean-out system, and the erosional competency of enhancing counterweight dirt, increase the wetting properties of metallic surface, thereby strengthen cleaning force.
The content of alcohol ether of the present invention the 5-25 weight part (take water as 100 weight parts be with reference to).
antioxidant
As everyone knows, sulfhydryl compound, especially micromolecular sulfhydryl compound, although have very strong complex ability with metal ion, sulfhydryl compound is very easily oxidized, especially under the katalysis of the metals such as nickel, copper, iron.In addition, sulfhydryl compound can also be by metal oxide, halogen-containing oxidation operation.In the use procedure of clean-out system, most of mode of spraying that adopts, this Cleaning Process agent meeting incorporates a large amount of air, and this can further strengthen the oxidation of sulfhydryl compound, simultaneously in dirt, also can there be some materials, make the oxidized or catalyzed oxidation of sulfhydryl compound.
The compound that the oxidized rear formation of sulfhydryl compound contains disulfide linkage, the sequestering power of the compound that contains disulfide linkage is lower.This defines the utilization of sulfhydryl compound as clean-out system.
Adopting antioxidant is a kind of available selection:
Optimization citric acid of the present invention, tartrate, gluconic acid, Sodium.alpha.-hydroxypropionate, Sunmorl N 60S, sodium polyacrylate are as antioxidant.
Above-claimed cpd, owing to having certain antioxygenation, can be used for clean-out system of the present invention in preparation, storage process.
The 1%-20% that the usage quantity of above-mentioned antioxidant is sulfhydryl compound.(in quality, dividing).
tensio-active agent
Tensio-active agent is as the main ingredient of metal cleaner, and the molecular structure of tensio-active agent is comprised of hydrophilic radical and hydrophobic group two portions.This structure, just make tensio-active agent have some special essential property just, as interfacial adsorption, aligns micella etc.These reduce the surface tension of water, greasy dirt is produced wetting, infiltration, emulsification, solubilising, disperse, and the multiple comprehensive action such as cleans.Whole cleaning process can be divided into two steps: the first step, and tensio-active agent is wetting to greasy dirt, and infiltration, make greasy dirt separate from metallic surface; Second step, utilize its emulsification, solubilising dispersive ability, further stable being dispersed in water the greasy dirt separated.
Tensio-active agent of the present invention is selected the tensio-active agent that tensio-active agent is non-ionic type.
The tensio-active agent of described non-ionic type can be selected one or more in the 8 carbon isooctyl alcohol Soxylat A 25-7s of 8 carbon octanol Soxylat A 25-7s, straight chain of 10 carbon polyoxyethylenated alcohol, the straight chain of Soxylat A 25-7, ethoxylated dodecyl alcohol, 12-14 carbon primary alconol Soxylat A 25-7,12-14 carbon secondary alcohol Soxylat A 25-7, collateralization 13 carbon Guerbet polyoxyethylenated alcohol, collateralization 10 carbon Guerbet polyoxyethylenated alcohol, the straight chain of alkylphenol.
The preferred isomery fatty alcohol-polyoxyethylene ether of the present invention.
The present invention selects the purpose of the isomery fatty alcohol-polyoxyethylene ether tensio-active agent contained to be, isomery fatty alcohol-polyoxyethylene ether tensio-active agent can reduce the surface tension of clean-out system, can the quick humidification metallic surface, peel off surface contaminant.
More specifically, the general molecular formula of described isomery fatty alcohol-polyoxyethylene ether tensio-active agent is C
nh
2n+1o(C
2h
4o)
xh, n=9～18, x=5～20, preferably n is 10-13, one or more of the isomery fatty alcohol-polyoxyethylene ether that x is 7-13.
In the present embodiment, preferred isomerous tridecanol polyoxyethylene ether is as alcohol ether.
The content of isomery fatty alcohol-polyoxyethylene ether tensio-active agent of the present invention the 10-20 weight part (take water as 100 weight parts be with reference to).
alcohol acid
Alcohol acid is to contain the compound of hydroxyl-OH and carboxyl-COOH in molecule simultaneously.Can be divided into aliphatic hydroxyl acid and aromatic hydroxyl acid two classes according to its structure.
Alcohol acid structural formula of the present invention is as follows:
OH-(CH2)n-COOH
Wherein, n is not more than 4 positive integer.
Sulfhydryl compound, go back facile hydrolysis under katalysis except metals such as the external nickel of oxidation, copper, iron very easily, hydroxide ion when hydrolysis reaction occurs in water can cement out sulfydryl and generate sulphur hydrogen radical ion, hydrogen ion in sulphur hydrogen radical ion and the water generation hydrogen sulfide that reacts, ion after sulfydryl is displaced is combined with hydroxide ion and is become glycol or alcohol acid, now, the content of sulfhydryl compound reduces, and affects the adsorption of sulfydryl to metal ion in metal surface greasy dirt.But well-known, hydrolysis reaction is reversible reaction, adds alcohol acid in metal cleaner, make hydroxyl and carboxyl-content increase, cause hydrolysis reaction to carry out to contrary direction, reach the effect that suppresses hydrolysis.
The content of alcohol acid of the present invention the 0.1-2 mass parts (take water as 100 weight parts be with reference to).
specific embodiment
The preparation of artificial greasy dirt and coating
By industrial vaseline, 30# machine oil, 20# machine oil miscellany, being heated to 120 ℃ of left and right is uniformly dissolved, pour lanolin, calcium grease, barium mahogany sulfonate and lanolin into, stirring and dissolving, control temperature and be no more than 130 ℃, after all dissolving, stop heating, add alumina powder, stir, be cooled to room temperature and get final product.
By polishing, cleaned steel test piece (50 * 25 * 3 ~ 5mm), with hanging up properly, after being placed in 40 ℃ of dry 30min of baking oven, cooling weighing, accurately to 0.2mg.Test piece by after claiming, lie on clean filter paper, with the artificial greasy dirt of little scraper tweezer, is coated in equably test piece and simultaneously goes up 2/3rds position, and the surface that its excess-three is divided does not apply, and the unnecessary greasy dirt in test piece both sides and base is wiped with filter paper.Greasy dirt applies and should be controlled between 0.08 ~ 0.19g.Then by the test piece that coats with hanging up properly, put into thermostatic drying chamber, temperature is controlled at 40 ℃, after dry 30min, takes out, and wipes the greasy dirt on base with filter paper, cooling weighing.
Remove the testing method of the ability of organic pollutant
Drip the ultrapure water of 0.5 microlitre in the steel test piece that applies good artificial greasy dirt, measure the contact angle before cleaning, then clean with metal cleaner of the present invention the steel test piece that applies artificial greasy dirt, will rinse with ultrapure water through the steel test piece of cleaning thereafter, then use the nitrogen drying.Then the ultrapure water of 0.5 microlitre is dropped in the steel test piece, and measure the contact angle after cleaning.
◎: good (contact angle reduces 40 ° or larger),
Zero: good (contact angle reduce 30 °～be less than 40 °),
△: still can (contact angle reduce 20 °～be less than 30 °),
X: bad (contact angle reduces to be less than 20 °).
The storage in liquid stability test of metal cleaner:
Whether clean-out system, observing clean-out system has gonorrhoea or separation if at room temperature being placed two months.
O-is stable
X-gonorrhoea/separation
Test result is shown in (embodiment 1-11) in following table:
The present invention utilizes the erosion rate of traditional indoor static lacing film (specification: 50mm * 10mm * 3mm, material are the 20# steel) weight-loss method to joined corrosion simulation solution, the H2S that the main component of corrosion simulation solution is NH4HS, NH4Cl and trace or NH3 etc.Find that embodiment 1-11 all has good corrosion mitigating effect.
1307 products that isomerous tridecanol polyoxyethylene ether in embodiment is Ningbo Le Jia chemical industry company limited, straight chain 10 carbon polyoxyethylenated alcohol are BASF XP series product, the S-50 series product that 14 carbon secondary alcohol Soxylat A 25-7s are Xuzhou rose sharpening work company limited.
After tested, compound containing sulfydryl, the result of the ability of the removal organic pollutant that the metal cleaner used containing nitronic acid and the sequestrant mixing with antioxygenation is tested out is " good " and " well ", therefore, can prove that metal cleaner of the present invention is very excellent when the clean metal surface.The aptitude tests of the removal organic pollutant by Comparative Examples find, clean-out system of the present invention just can thoroughly clean up the greasy dirt of metallic surface in the time of 60 seconds, therefore can prove that metal cleaner of the present invention is fast and effective when the clean metal surface.Metal cleaner of the present invention can clean by spray-type just can be clean by cleaning metal surface.After tested, there is the sequestrant of antioxygenation and alcohol ether the sulfydryl containing in the compound of sulfydryl is had to provide protection.Metal cleaner best results of the present invention when the mixture that metal cleaner of the present invention uses the sequestrant mixture strong containing mixture, the stability of the compound of sulfydryl, have the mixture of sequestrant of antioxygenation and an alcohol ether is used simultaneously.
Claims (9)
1. a metal cleaner, is characterized in that comprising the compounds containing thiol groups shown in following formula;
Wherein, be selected from-COOH of X ,-a kind of in OH, n is not more than 5 positive integer.
2. according to a kind of metal cleaner described in claim 1, it is characterized in that described metal cleaner, in weight part, comprises following material and weight part:
Compounds containing thiol groups 20-30;
Water 100.
3. according to a kind of metal cleaner described in claim 2, it is characterized in that, described metal cleaner also comprises alcohol ether, and described pure ether content is the 5-25 weight part.
4. a kind of metal cleaner according to claim 1, it is characterized in that, described metal cleaner also comprises strong chelating agent, and described strong chelating agent is selected from one or several in nitrilotriacetic acid(NTA) sodium, edetate, diethylenetriamine pentacarboxylic acid salt, ethylenediamine tetraacetic methene sodium phosphate, diethylene triamine pentamethylene phosphonic salt, nitrilotriacetic acid(NTA).
5. a kind of metal cleaner according to claim 4, is characterized in that, the usage quantity of described strong chelating agent is counted the 0.1%-20% of compounds containing thiol groups with mass parts.
6. according to a kind of metal cleaner described in claim 1, it is characterized in that, described metal cleaner also comprises antioxidant.
7. according to a kind of metal cleaner described in claim 6, it is characterized in that, described antioxidant is selected from one or several in lemon acid, tartrate, gluconic acid, Sodium.alpha.-hydroxypropionate, Sunmorl N 60S, sodium polyacrylate.
8. according to a kind of metal cleaner described in claim 6, it is characterized in that, the usage quantity of described antioxidant is counted the 1%-20% of sulfhydryl compound with mass parts.
9. according to a kind of metal cleaner described in claim 2, it is characterized in that, described metal cleaner also comprises the tensio-active agent of non-ionic type, and described dosage of surfactant is the 10-20 weight part.
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| CN103882461A (en) * | 2014-03-17 | 2014-06-25 | 苏州龙腾万里化工科技有限公司 | Detergent for steel meshes |
| CN104357872A (en) * | 2014-11-19 | 2015-02-18 | 柳州凯通机械有限公司 | Preparation method of cooler line detergent |
| CN106398647A (en) * | 2016-08-27 | 2017-02-15 | 合肥普庆新材料科技有限公司 | Artificial oil stain for simulating metal cleaning and preparation method thereof |
| CN106837027A (en) * | 2016-12-31 | 2017-06-13 | 马鞍山市川金属科技有限公司 | One kind is anti-to lose hood support bar |
| CN106967526A (en) * | 2017-03-29 | 2017-07-21 | 希玛石油制品（镇江）有限公司 | A kind of degreasing cleaning agent and preparation method thereof |
| CN107059027A (en) * | 2017-06-20 | 2017-08-18 | 江苏军威电子科技有限公司 | A kind of metal cleaner |
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| CN111044337A (en) * | 2019-12-20 | 2020-04-21 | 广东好顺欧迪斯科技股份有限公司 | Artificial oil stain and preparation method and application thereof |
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