WO2023131530A1 - Composition de nettoyage pour prétraitement de substrats métalliques et procédé de préparation associé et application correspondante - Google Patents

Composition de nettoyage pour prétraitement de substrats métalliques et procédé de préparation associé et application correspondante Download PDF

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Publication number
WO2023131530A1
WO2023131530A1 PCT/EP2022/087185 EP2022087185W WO2023131530A1 WO 2023131530 A1 WO2023131530 A1 WO 2023131530A1 EP 2022087185 W EP2022087185 W EP 2022087185W WO 2023131530 A1 WO2023131530 A1 WO 2023131530A1
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ether
cleaning composition
composition according
solvents
weight
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PCT/EP2022/087185
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English (en)
Inventor
Pei Hai CONG
Wen Yi HU
Yong Chang JIANG
Benjamin Delespierre
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Basf Coatings Gmbh
Basf (China) Company Limited
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Priority to CN202280087685.0A priority Critical patent/CN118510877A/zh
Publication of WO2023131530A1 publication Critical patent/WO2023131530A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5009—Organic solvents containing phosphorus, sulfur or silicon, e.g. dimethylsulfoxide
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/266—Esters or carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/024—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
    • C23G5/02854—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons characterised by the stabilising or corrosion inhibiting additives
    • C23G5/02861—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
    • C23G5/02854—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons characterised by the stabilising or corrosion inhibiting additives
    • C23G5/02883—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals

Definitions

  • the present invention relates to a cleaning composition for metal substrates pretreatment and its preparation method thereof. More specifically, the present invention relates to a cleaning composition for cleaning grease and sweat from metal substrates and its preparation method thereof.
  • Metal substrates such as pipes, plates, etc. are coated by protective films to eliminate rusting and therefore increase their service life.
  • metal substrates In order to get excellent coating films and make the binding between metal substrates and coating films durable, metal substrates have to be pretreated before coating, for example, including steps of sanding the metal substrates and cleaning the residual grease and inorganic salts from metal substrates, said grease and salts are included in fingerprints and sweat respectively.
  • the coating film is applied onto metal substrates having residual grease and salts, water from humid environment tends to penetrate the coating film and bring corrosions to metal surfaces together with sodium chloride and oxygen.
  • the mechanism of corrosion is: the coating film as a cathode, the metal substrate as an anode, and the mixture of water and sodium chloride as an electrolyte, form a cell. The corrosion will make the coating film bubble and lose its protective function such as water resistance.
  • cleaning compositions have been developed for metal substrates pretreatment and those cleaning compositions mainly include two types i.e. solvent-borne and water-borne cleaning compositions both of which have problems.
  • solvent-borne cleaning compositions When solvent-borne cleaning compositions are used, inorganic salts cannot be removed completely, while when water-borne cleaning compositions are used, water itself will cause corrosion.
  • US5,080,831A disclosed an aqueous cleaning composition comprising: (a) at least one sparingly water soluble organic solvent; (b) a solubilizing additive consisting of a surfactant and a coupler; and (c) water.
  • US5,080,831A conducted a degreasing test and the results showed that the aqueous cleaning composition can remove grease/oil from walls, metal surfaces, etc. with scrubbing.
  • US5,080,831A did not provide anti-corrosion effects on metal substrates, nor water resistance of the coating film over metal substrates.
  • CN110983355A disclosed a degreasing and anti-rusting agent for iron workpieces, comprising alkaline auxiliary agents, chelating agents, surfactants, rust inhibitors and solubilizing agents, wherein the alkaline auxiliary agents include at least one selected from a group consisting of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and sodium metasilicate pentahydrate.
  • the degreasing and anti-rusting agent comprises inorganic substances such as alkaline auxiliary agents that will remain on the metal substrates after degreasing, which will adversely affect the subsequent coating film.
  • this invention provides a cleaning composition
  • a cleaning composition comprising a) from 40% to 80% by weight of one or more alcohol solvents; b) from 5% to 20% by weight of one or more ester solvents; c) from 5% to 30% by weight of one or more ether solvents; d) from 0.5% to 5% by weight of one or more corrosion inhibitors; and e) from 5% to 30% by weight of water, wherein the weight percentage of each component is based on the total weight of the cleaning composition.
  • the present invention provides a method for preparing the cleaning composition, comprising steps of:
  • the cleaning composition of the present invention can effectively remove grease and inorganic salts from metal substrates and therefore can avoid corrosions of the metal substrate. Moreover, it is simple to prepare the clean composition and convenient to apply it onto metal surfaces.
  • the coated films After pretreatment by the invented cleaning composition, the coated films have better water resistance compared with the prior art.
  • solvents comprising a hydroxyl group in the structure can be used as alcohol solvents.
  • the alcohol solvents can include linear, branched or cyclic, substituted or unsubstituted aliphatic or aromatic alcohols, including monohydric alcohols, dihydric alcohols, trihydric alcohols and tetrahydric alcohols, preferably C1-C20 aliphatic alcohols or aromatic alcohols.
  • the aliphatic monohydric alcohols include linear or branched, substituted or unsubstituted C1-C20, preferably C2-C10 alkanols and substituted or unsubstituted C5-C20, preferably C5-C10 cycloalkanols, examples of which include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, cyclopentanol, n-hexanol, isohexanol, cyclohexanol, n-heptanol, isoheptanol, cycloheptanol, n-octanol, isooctyl alcohol, 2-ethylhexanol, cyclooc
  • the aliphatic dihydric alcohols include linear or branched, substituted or unsubstituted C2-C20, preferably C2-C10 alkanediols and substituted or unsubstituted C5-C20, preferably C5-C10 cycloalkanes diols, examples of which include, but are not limited to, ethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,4-butanediol, 2,3-butanediol, ethyl glycol, 2- (hydroxymethyl) propanol, 1 ,5-pentanediol, 1 ,3-pentanediol, 2,4-pentanediol, cyclopentane- 1 ,2- diol, propyl glycol, 2-(hydroxyethyl)propanol, 2-(hydroxymethyl)butanol, 1 ,
  • the aliphatic trihydric alcohols include linear or branched, substituted or unsubstituted C3-C20, preferably C3-C10 alkanetriols and C5-C20, preferably C5-C10 cycloalkanetriols, examples of which include, but are not limited to, propanetriol (glycerol), 1 ,2,4-butanetriol, 1 ,2,3-pentanetriol, 2,3,4-pentanetriol, 1 ,2,3-hexanetriol , 1 ,2,5-hexanetriol, 1 ,2,3-cyclohexanetriol, 1 ,2,4-cyclohexanetriol, 1 ,2,3-heptanetriol, 1 ,6,7-heptanetriol, 2,3,6- heptanetriol, 1 ,2,3-cycloheptanetriol, 1 ,2,6-cycloheptanetriol, 1 ,2,3-octanetriol, 2,
  • the aliphatic tetrahydric alcohols include pentaerythritol.
  • the aromatic alcohols include C5-C12 aralkyl alcohols, examples of which include, but are not limited to, benzyl alcohol, 1-phenylethanol, 2-phenylethanol, phenylpropanol, pyridin-1-yl methanol, pyridin-3-yl methanol, 1-pyridin-3-yl ethanol, pyridyl butanol, pyrimidin-1-yl methanol, pyrimidin-1-yl ethanol, 2-pyrimidin-3-yl propanol, furan-2-yl methanol, 2-furan-2-yl ethanol, 3-furan-3-yl propanol, 4-furan-2-yl butanol, or a mixture thereof.
  • the alcohol solvents can also include alcohols comprising other groups such as ketone groups in the structure, such as diacetone alcohol.
  • the alcohol solvents have a boiling point of below 160°C, preferably below 120°C.
  • the alcohol solvent is a mixture of ethanol and isopropanol.
  • the weight ratio of ethanol to isopropanol is in the range from 1 :10 to 10:1 , preferably from 1 :8 to 8: 1 , more preferably from 1 :5 to 5: 1 , and in some embodiments, from 1 :4 to 4: 1 , from 1 :3 to 3: 1 , from 1 :2 to 2: 1 , or about 1 :1.
  • the alcohol solvents are used in an amount of from 40% to 80%, preferably from 50% to 70%, more preferably from 55% to 65% by weight, based on the total weight of the cleaning composition.
  • solvents comprising an ester group in the structure can be used as ester solvents.
  • the ester solvents include C2-C12 alkane monocarboxylic acid C1-C12 alkyl ester, hydroxylated C2-C12 alkane monocarboxylic acid C1-C12 alkyl ester, C2-C12 alkane dicarboxylic acid di-Ci -C12 alkyl ester, C1-C12 alkane monocarboxylic acid C3-C12 alkoxyalkyl ester, C3-C12 alkoxy alkane monocarboxylic acid C1-C12 alkyl ester, tri-Ci-C4 alkyl phosphates, C5-C12 cycloalkane monocarboxylic acid C1-C12 alkyl ester, C5-C12 cycloalkane dicarboxylic acid di-Ci-Ci2 alkyl ester, carbonate, aromatic (for example, phenyl) carboxylic acid ester or a mixture thereof.
  • the C2-C12 alkane monocarboxylic acid C1-C12 alkyl esters refer to monocarboxylic acid esters formed by an alkane monocarboxylic acid having 2 to 12 carbon atoms and an alkyl monohydric alcohol having 1 to 12 carbon atoms, examples of which include, but are not limited to, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, tert-butyl acetate, n- pentyl acetate, cyclopentyl acetate, n-hexyl acetate, 3-methylcyclopentyl acetate, cyclohexyl acetate, n-heptyl acetate, 3-methylcyclohexyl acetate, 2-ethylhexyl acetate, n-nonyl acetate, isobornyl acetate, ethyl propionat
  • the hydroxylated C2-C12 alkane monocarboxylic acid C1-C12 alkyl esters refer to monocarboxylic acid ester formed by an alkane monocarboxylic acid having 2 to 12 carbon atoms and an alkyl group monohydric alcohol having 1 to 12 carbon atoms, wherein the alkyl group derived from carboxylic acid or the alkyl group derived from alcohol is substituted by at least one hydroxyl group, examples of which include, but are not limited to, 3-hydroxypropyl acetate, 3- hydroxybutyl acetate, 5-hydroxypentyl acetate, n-propyl glycolate, isopropyl glycolate, n-butyl glycolate, tert-butyl glycolate, n-pentyl glycolate, n-hexyl glycolate, 2-methylpentyl glycolate, cyclohexyl glycolate, 3-methylcyclopentyl glycolate, n-heptyl glycolate, cyclohexy
  • the C2-C12 alkane dicarboxylic acid di-Ci -C12 alkyl esters refer to dicarboxylic acid esters formed by an alkane dicarboxylic acid having 2 to 12 carbon atoms and two independently selected alkyl monohydric alcohols having 1 to 12 carbon atoms, examples of which include, but are not limited to, ethyl methyl oxalate, diethyl oxalate, ethyl propyl oxalate, ethyl isopropyl oxalate, dipropyl oxalate, propyl isopropyl oxalate, ethyl butyl oxalate, methyl pentyl oxalate, propyl butyl oxalate, butyl hexyl oxalate, dipentyl oxalate, dimethyl malonate, methyl ethyl malonate, diethyl malonate, prop
  • the C1-C12 alkane monocarboxylic acid C3-C12 alkoxyalkyl esters refer to monocarboxylic acid esters formed by an alkane monocarboxylic acid having 1 to 12 carbon atoms and an alkoxyalkyl monohydric alcohol having 3 to 12 carbon atoms, examples of which include, but are not limited to, isopropoxymethyl formate, isopropoxyethyl formate, isopropoxy tert-butyl formate, methoxypropyl acetate, ethoxymethyl acetate, ethoxypropyl acetate, propoxypropyl acetate, isopropoxymethyl acetate, isopropoxypropyl acetate, ethylene glycol ethyl ether formate, ethylene glycol butyl ether formate, ethylene glycol 2-methylbutyl ether formate, ethylene glycol amyl ether formate, ethylene glycol methyl ether acetate, ethylene glycol ethy
  • the C3-C12 alkoxy alkane monocarboxylic acid C1-C12 alkyl esters refer to monocarboxylic acid esters formed by an alkoxy alkane monocarboxylic acid having 3 to 12 carbon atoms and an alkyl monohydric alcohol having 1 to 12 carbon atoms, preferably C3-C6 alkoxy alkane monocarboxylic acid Ci-Ce alkyl ester, examples of which include, but are not limited to, ethyl 3- methoxypropionate, ethyl 3-ethoxypropionate or a mixture thereof.
  • the ester solvent is ethyl 3-ethoxypropionate.
  • the tri-Ci -C4 alkyl phosphates include, but are not limited to, trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, tri-isopropyl phosphate, tri-n-butyl phosphate, triisobutyl phosphate, methyl diethyl phosphate, dimethyl ethyl phosphate, methyl di-n-propyl phosphate, methyl ethyl n-propyl phosphate, ethyl 2-methylpropyl methyl phosphate, diethyl n-propyl phosphate, dimethyl isobutyl phosphate, diethyl n-butyl phosphate, n-propyl isobutyl n-butyl phosphate and dimethyl tert-butyl phosphate.
  • the C5-C12 cycloalkane monocarboxylic acid C1-C12 alkyl esters refer to monocarboxylic acid esters formed by a cycloalkane monocarboxylic acid having 5 to 12 carbon atoms and an alkyl monohydric alcohol having 1 to 12 carbon atoms, examples of which include, but are not limited to, hexyl cyclopentanecarboxylate, pentyl cyclohexanecarboxylate, 3-isopropylhexyl cyclohexanecarboxylate, or mixtures thereof.
  • the C5-C12 cycloalkane dicarboxylic acid di-Ci -Ci 2 alkyl esters refer to dicarboxylic acid esters formed by a cycloalkane dicarboxylic acid having 5 to 12 carbon atoms and two independently selected alkyl monohydric alcohols having 1 to 12 carbon atoms, examples of which include, but are not limited to, dibutyl 1 ,2-cyclopentane dicarboxylate, ethyl butyl 1 ,3-cyclopentane dicarboxylate, didecyl 1 ,2-cyclohexanedicarboxylate, methyl octyl 1 ,4-cyclohexanedicarboxylate, di-isononyl cyclohexanedicarboxylate or mixtures thereof.
  • carbonates include, but are not limited to, diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate, dibutyl carbonate, or mixtures thereof.
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • propyl carbonate dibutyl carbonate, or mixtures thereof.
  • aromatic (e.g., phenyl) carboxylic acid esters refer to carboxylic acid esters comprising aromatic groups, examples of which include, but are not limited to, benzyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl lactate, 2- phenoxyethyl propionate or mixtures thereof.
  • ester solvents have a boiling point of below 200°C, preferably below 160°C.
  • the amount of ester solvent used is from 5% to 20%, preferably from 8% to 15%, more preferably from 10% to 12% by weight, based on the total weight of the cleaning composition.
  • solvents comprising ether bonds in the structure can be used as ether solvents.
  • ether solvents include ethers having the general formula R 1 -O-R 2 , wherein R 1 and R 2 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, examples of which include, but are not limited to, dimethyl ether, ethyl methyl ether, diethyl ether, methyl propyl ether, di-isopropyl ether, di-n-butyl ether, methyl tert-butyl ether (MTBE) or mixtures thereof.
  • R 1 and R 2 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, examples of which include, but are not limited to, dimethyl ether, ethyl methyl ether, diethyl ether, methyl propyl ether, di-isopropyl ether, di-n-butyl ether, methyl tert-butyl ether (MTBE) or mixtures
  • the ether solvents include ethers having the general formula R 3 -O-(R 4 - O) n -R 5 , wherein R 3 is H or a hydrocarbyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, R 4 and R 5 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and n is an integer of 1-6, examples of which include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether (propylene glycol butyl ether), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, diethylene glycol monomethyl ether, ethylene
  • the ether solvent is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether (propylene glycol butyl ether) or a mixture thereof.
  • the ether solvents include cyclic ethers, examples of which include, but are not limited to, tetrahydrofuran, 2-methyltetrahydrofuran, 1 ,3-oxocyclopentane, or mixtures.
  • the ether solvents have a boiling point of below 200°C, preferably below 160°C.
  • the amount of ether solvent is from 5% to 30%, preferably from 10% to 25%, more preferably from 15% to 23% by weight, based on the total weight of the cleaning composition.
  • Solvents comprising two or more moieties of a hydroxyl group, an ester group and an ether bond in the structure can act as two or more solvents among alcohol solvents, ester solvents and ether solvents.
  • a solvent comprising a hydroxyl group and an ether bond in the structure can act as both ether solvent and alcohol solvent.
  • corrosion inhibitors can also be referred to as flash rust inhibitors or rust inhibitors.
  • the corrosion inhibitor is a polymer-based corrosion inhibitor, especially a polyacrylic acid corrosion inhibitor.
  • the corrosion inhibitors include organozinc chelates, such as NALZIN® FA 179, NALZIN® FA 379, and NALZIN® FA 579 available from ELEMENTIS.
  • the corrosion inhibitors comprise no nitrite and is a chelating zinc compound soluble in a mixture of various solvents, which shows a strong affinity for iron-containing substrates to prevent flash corrosion.
  • the corrosion inhibitor is water-soluble, it can be transformed into a non-dispersible or insoluble zinc compound during drying, such that the water sensitivity is reduced, forming an anti-corrosion passivation layer after drying, thereby improving water resistance of subsequent paint films on metal substrates.
  • the corrosion inhibitors include zinc-free rust inhibitor, such as HALOX® FLASH-X® 150, HALOX® SW-111, etc., available from HALOX.
  • the corrosion inhibitors include alkylamine-containing corrosion inhibitors, such as those raybo® series of rust inhibitors available from Raybo Chemical Company, such as raybo 60, raybo 80, raybo 90, raybo 218, especially raybo 90 and raybo 218.
  • the amount of corrosion inhibitor used is from 0.5% to 5%, preferably from 0.5% to 2%, more preferably from 0.5% to 1.5% by weight, based on the total weight of the cleaning composition.
  • the water is deionized water, demineralized water or distilled water.
  • the amount of water used is from 5% to 30%, preferably from 5% to 20%, more preferably from 8% to 15% by weight, based on the total weight of the cleaning composition.
  • the cleaning composition can further comprise additives, including but not limited to anti-corrosion auxiliary agents (for example, HALOX® 550 available from HALOX), solubilizers, antioxidants, antibacterial agents, or combinations thereof.
  • anti-corrosion auxiliary agents for example, HALOX® 550 available from HALOX
  • solubilizers for example, HALOX® 550 available from HALOX
  • antioxidants for example, HALOX® 550 available from HALOX
  • antibacterial agents for example, HALOX® 550 available from HALOX
  • the method for preparing a cleaning composition according to the present invention comprises steps of:
  • the method for preparing a cleaning composition according to the present invention is carried out at room temperature (0-40°C).
  • the cleaning compositions of the present invention can effectively remove grease and inorganic salts from metal substrates and therefore avoid corrosions of metal substrates and enable coating films a good water resistance.
  • metal substrates include but not limited to iron, aluminum alloy, copper substrates and other metal substrates.
  • the metal substrate is a galvanized sheet or an aluminum alloy sheet of an automobile body.
  • the iron substrates include tinplates, steel sheets, galvanized sheets and the like.
  • a cleaning composition comprises: a) from 50% to 70% by weight of one or more alcohol solvents, b) from 5% to 15% by weight of one or more ester solvents, c) from 15% to 25% by weight of one or more ether solvents, d) from 0.5% to 2% by weight of one or more corrosion inhibitors, and e) from 5% to 20% by weight of water, wherein the weight percentage of each component is based on the total weight of the cleaning composition.
  • a cleaning composition comprises: a) from 50 to 70% by weight of one or more alcohol solvents, b) from 5 to 15% by weight of one or more ester solvents, c) from 15 to 25% by weight of one or more ether solvents, d) from 0.5 to 2% by weight of one or more corrosion inhibitors, and e) from 5 to 20% by weight of water, wherein the weight percentage of each component is based on the total weight of the cleaning composition, and the corrosion inhibitors comprise polymer-based corrosion inhibitors.
  • a cleaning composition comprises: a) from 50% to 70% by weight of one or more alcohol solvents, b) from 5% to 15% by weight of one or more ester solvents, c) from 15% to 25% by weight of one or more ether solvents, d) from 0.5% to 2% by weight of one or more corrosion inhibitors, and e) from 5% to 20% by weight of water, wherein the weight percentage of each component is based on the total weight of the cleaning composition, and the corrosion inhibitors comprise polyacrylic acid corrosion inhibitors.
  • a cleaning composition comprises: a) from 50% to 70% by weight of one or more alcohol solvents, b) from 5% to 15% by weight of one or more ester solvents, c) from 15% to 25% by weight of one or more ether solvents, d) from 0.5% to 2% by weight of one or more corrosion inhibitors, and e) from 5% to 20% by weight of water, wherein the weight percentage of each component is based on the total weight of the cleaning composition, and the corrosion inhibitors comprise organic zinc chelates.
  • a cleaning composition comprises: a) from 50% to 70% by weight of one or more alcohol solvents, b) from 5% to 15% by weight of one or more ester solvents, c) from 15% to 25% by weight of one or more ether solvents, d) from 0.5% to 2% by weight of one or more corrosion inhibitors, and e) from 5% to 20% by weight of water, wherein the weight percentage of each component is based on the total weight of the cleaning composition, the corrosion inhibitors comprise organozinc chelates and the alcohol solvents are selected from ethanol, isopropanol or a mixture thereof.
  • a cleaning composition comprises: a) from 50% to 70% by weight of one or more alcohol solvents, b) from 5% to 15% by weight of one or more ester solvents, c) from 15% to 25% by weight of one or more ether solvents, d) from 0.5% to 2% by weight of one or more corrosion inhibitors, and e) from 5% to 20% by weight of water, wherein the weight percentage of each component is based on the total weight of the cleaning composition, the corrosion inhibitors comprise organic zinc chelates, the alcohol solvents are selected from ethanol, isopropanol or a mixture thereof, and the ester solvents are selected from ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate or a mixture thereof.
  • a cleaning composition comprises: a) from 50% to 70% by weight of one or more alcohol solvents, b) from 5% to 15% by weight of one or more ester solvents, c) from 15% to 25% by weight of one or more ether solvents, d) from 0.5% to 2% by weight of one or more corrosion inhibitors, and e) from 5% to 20% by weight of water, wherein the weight percentage of each component is based on the total weight of the cleaning composition, the corrosion inhibitors comprise organic zinc chelates, the alcohol solvents are selected from ethanol, isopropanol or a mixture thereof, the ester solvents are selected from ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate or mixtures thereof, and the ether solvents are selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether or a mixture thereof.
  • a cleaning composition comprising a) from 40% to 80% by weight of one or more alcohol solvents; b) from 5% to 20% by weight of one or more ester solvents; c) from 5% to 30% by weight of one or more ether solvents; d) from 0.5% to 5% by weight of one or more corrosion inhibitors; and e) from 5% to 30% by weight of water, wherein the weight percentage of each component is based on the total weight of the cleaning composition.
  • the cleaning composition according to embodiment 8 or 9, wherein the corrosion inhibitors comprise polymer-based corrosion inhibitors.
  • ester solvents comprise C2-C12 alkane monocarboxylic acid C1-C12 alkyl ester, hydroxylated C2-C12 alkane monocarboxylic acid C1-C12 alkyl ester, C2-C12 alkane dicarboxylic acid di-Ci -Ci 2 alkyl ester, Ci- 012 alkane monocarboxylic acid C3-C12 alkoxyalkyl ester, C3-C12 alkoxy alkane monocarboxylic acid C1-C12 alkyl ester, tri-Ci -C4 alkyl phosphates, C5-C12 cycloalkane monocarboxylic acid Ci- 012 alkyl ester, C5-C12 cycloalkane dicarboxylic acid di-Ci -C12 alkyl ester, carbonate, aromatic carboxylic acid esters or mixtures thereof.
  • ester solvents are C3-C12 alkoxy alkane monocarboxylic acid C1-C12 alkyl ester, preferably selected from ethyl 3- methoxypropionate, ethyl 3-ethoxypropionate or a mixture thereof, more preferably ethyl 3- ethoxypropionate.
  • ether solvents comprise ethers having the general formula of R 1 -O-R 2 , wherein R 1 and R 2 are each independently hydrocarbyl group having 1 to 20 carbon atoms, preferably selected from dimethyl ether, ethyl methyl ether, diethyl ether, methyl propyl ether, di-isopropyl ether, di-n- butyl ether, methyl tert-butyl ether or mixtures thereof.
  • R 1 and R 2 are each independently hydrocarbyl group having 1 to 20 carbon atoms, preferably selected from dimethyl ether, ethyl methyl ether, diethyl ether, methyl propyl ether, di-isopropyl ether, di-n- butyl ether, methyl tert-butyl ether or mixtures thereof.
  • ether solvents comprise ethers having the general formula of R 3 -O-(R 4 -O) n -R 5 , wherein R 3 is H or hydrocarbyl group having 1 to 20 carbon atoms, R 4 and R 5 are each independently hydrocarbyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 6, preferably selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, prop
  • ether solvents are selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether or a mixture thereof.
  • a method for preparing the cleaning composition according to any of embodiments 8 to 29, comprising steps of:
  • butyl acetate, propylene glycol methyl ether acetate, xylene, trimethylbenzene, and propylene glycol monobutyl ether were added to a plastic tank with stirring at room temperature and dispersed for 10 minutes until a homogeneous and clear mixed liquid is obtained, then filtered and packaged into a plastic tank and sealed for later use.
  • Test 1 was carried out without using fingerprints and artificial sweat to contaminate the tinplate, and performed as follows: (1) sanding the tinplate, (2) dusting the tinplate with a cleaning cloth, (3) cleaning contaminates on the tinplate with the cleaning composition, (4) spray coating a paint film on the cleaned tinplate, (5) drying the paint film, (6) placing the tinplate with the paint film into a constant temperature water bath at 40°C for water resistance test and recording water resistance test results (the test duration is 240 hours).
  • Test 2 was carried out under the condition of using finger prints to contaminate the tinplate, and performed as follows: (1) sanding the tinplate, (2) dusting the tinplate with a cleaning cloth, (3) cleaning contaminates on the tinplate with the cleaning composition, (4) using finger prints to contaminate the tinplate, (5) using the cleaning composition to clean the tinplate again, (6) spray coating a paint film on the cleaned tinplate, (7) drying the paint film, (8) placing the tinplate with the paint film into a constant temperature water bath at 40°C for water resistance test and recording water resistance test results (the test duration is 240 hours).
  • Test 3
  • Test 3 was carried out under the condition of using artificial sweat to contaminate the tinplate, and performed as follows: (1) sanding the tinplate, (2) dusting the tinplate with a cleaning cloth, (3) cleaning contaminates on the tinplate with the cleaning composition, (4) using artificial sweat to contaminate the tinplate, (5) using the cleaning composition to clean the tinplate again, (6) spray coating a paint film on the cleaned tinplate, (7) drying the paint film, (8) placing the tinplate with the paint film into a constant temperature water bath at 40°C for water resistance test and recording water resistance test results (the test duration is 240 hours). The results are shown in Table 2.
  • the cleaning composition prepared in Examples 1-3 of the present invention has a significantly better stain removal effect than the cleaning composition prepared in Comparative Example 1, such that the paint film has good water resistance.
  • the cleaning composition prepared in Examples 1- 3 of the present invention is more effective in removing grease and sweat than the cleaning composition prepared in Comparative Example 1 , such that the paint film has good water resistance.

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Abstract

La présente invention concerne une composition de nettoyage comprenant : a) de 40 % à 80 % en poids d'un ou plusieurs solvants alcooliques, b) de 5 % à 20 % en poids d'un ou plusieurs solvants esters, c) de 5 % à 30 % en poids d'un ou plusieurs solvants éther, d) de 0,5 % à 5 % en poids d'un ou plusieurs inhibiteurs de corrosion, et e) de 5 % à 30 % en poids d'eau, le pourcentage en poids de chaque composant étant basé sur le poids total de la composition de nettoyage. La présente invention concerne également un procédé de préparation de ladite composition de nettoyage.
PCT/EP2022/087185 2022-01-06 2022-12-21 Composition de nettoyage pour prétraitement de substrats métalliques et procédé de préparation associé et application correspondante WO2023131530A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5080831A (en) 1989-06-29 1992-01-14 Buckeye International, Inc. Aqueous cleaner/degreaser compositions
WO2000063304A1 (fr) * 1999-04-19 2000-10-26 Huntsman Petrochemical Corporation Suppresseur de peinture et de depot
US20110237483A1 (en) * 2008-12-22 2011-09-29 Woorifinechem. Co. Ltd Cleaning agent for high viscosity metalworking fluid
WO2016122911A1 (fr) * 2015-01-30 2016-08-04 The Lubrizol Corporation Composition pour le nettoyage de systèmes de distribution de carburant d'un moteur essence, systèmes d'admission d'air et chambres de combustion
CN110983355A (zh) 2019-11-04 2020-04-10 博罗县东明化工有限公司 铁材工件除油防锈剂及其除油方法
WO2020142273A1 (fr) * 2018-12-31 2020-07-09 Fourth Principle, Llc Compositions et procédés pour éliminer des revêtements de surfaces
WO2021148806A1 (fr) * 2020-01-23 2021-07-29 Reckitt & Colman (Overseas) Hygiene Home Limited Compositions de nettoyage de four et leurs procédés de fabrication et d'utilisation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5080831A (en) 1989-06-29 1992-01-14 Buckeye International, Inc. Aqueous cleaner/degreaser compositions
WO2000063304A1 (fr) * 1999-04-19 2000-10-26 Huntsman Petrochemical Corporation Suppresseur de peinture et de depot
US20110237483A1 (en) * 2008-12-22 2011-09-29 Woorifinechem. Co. Ltd Cleaning agent for high viscosity metalworking fluid
WO2016122911A1 (fr) * 2015-01-30 2016-08-04 The Lubrizol Corporation Composition pour le nettoyage de systèmes de distribution de carburant d'un moteur essence, systèmes d'admission d'air et chambres de combustion
WO2020142273A1 (fr) * 2018-12-31 2020-07-09 Fourth Principle, Llc Compositions et procédés pour éliminer des revêtements de surfaces
CN110983355A (zh) 2019-11-04 2020-04-10 博罗县东明化工有限公司 铁材工件除油防锈剂及其除油方法
WO2021148806A1 (fr) * 2020-01-23 2021-07-29 Reckitt & Colman (Overseas) Hygiene Home Limited Compositions de nettoyage de four et leurs procédés de fabrication et d'utilisation

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