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WO1995029019A1 - Procede de nettoyage de surfaces metalliques - Google Patents

Procede de nettoyage de surfaces metalliques Download PDF

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Publication number
WO1995029019A1
WO1995029019A1 PCT/US1995/004784 US9504784W WO9529019A1 WO 1995029019 A1 WO1995029019 A1 WO 1995029019A1 US 9504784 W US9504784 W US 9504784W WO 9529019 A1 WO9529019 A1 WO 9529019A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
cleaning
metal surface
drying
esters
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1995/004784
Other languages
English (en)
Inventor
Kazuhiko Mori
Yoshiyuki Kataoka
Yoshiyasu Yoneyama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Corp
Original Assignee
Henkel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Corp filed Critical Henkel Corp
Publication of WO1995029019A1 publication Critical patent/WO1995029019A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • 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

Definitions

  • This invention relates to a water-based method for cleaning metal surfac ⁇ es such as, most importantly, the surfaces of iron, zinc, aluminum, and the like. More particularly, with the goal of implementing environmental measures such as protection of the ozone layer, this invention relates to a method for cleaning metal surfaces that can replace the use of solvents, such as FreonTM, trichloro- ethane, and the like.
  • Organic solvents mainly FreonTM, trichloroethane, and the like, have here- tofore been used in the metal article cleaning operations that are frequently im ⁇ plemented as a pre-treatmentto metal working, painting, heat treatment, conver ⁇ sion treatment, and the like.
  • This practice is followed because it offers a number of advantages, such as: (1 ) strong ability to dissolve oily contaminants, (2) easy drying,
  • Cleaning with water-based cleaners typically requires the following steps: (1) cleaning, (2) a water rinse, and (3) drying. Among these steps, rusting is most readily produced in the drying step (3) because it is here that the workpiece is exposed to the highest temperatures. As a result, a supplementary process is often inserted between the water rinse and drying steps with the goal of inhibi ⁇ ting rust development. This supplementary process consists of application to the metal substrate of a corrosion-preventive agent.
  • the drying step in water-based cleaning operations generally employs techniques such as immersion in hot water prior to drying, hot-air blow drying using a stream of hot air at a temperature of at least 100° C, and vacuum drying (optionally with a heater) wherein drying is promoted by reducing the pressure in order to reduce the boiling point of the water.
  • a drying method that does not require these types of drying devices is disclosed in Japanese Pat ⁇ ent Application Laid Open [Kokai or Unexamined] Number Hei 4-76381 [76,381/ 1992]. In this method, the workpiece, after an upstream plating operation, is dried by exposure to a current of pressurized steam.
  • the present invention takes as its object the introduction of a method for cleaning metal surfaces which uses water-based cleaners, does not require spe ⁇ cial drying equipment, is free of problems such as the development of rust during and after drying, and provides an excellent drying performance, i.e., makes possible drying in as short a time period as for the use of organic solvent — a performance level hereinafter referred to simply as a high drying performance.
  • the present invention introduces a high drying perform ⁇ ance method for cleaning metal surfaces that characteristically comprises clean ⁇ ing the metal surface with a water-based cleaning bath that preferably contains 0.01 to 5, or more preferably 0.02 to 3.0, weight % of ester and/or salt of C 8 to C x fatty acid, and thereafter bringing the metal surface into contact, preferably for at least 5 seconds, with steam having a temperature of at least 80° C.
  • This invention also introduces a high drying performance method for cleaning a metal surface that characteristically comprises cleaning the metal surface with a water-based cleaning bath that preferably contains 0.01 to 5 weight % of ester and/or salt of C 8 to C 26 fatty acid, then rinsing with water, and thereafter bringing the metal surface into contact, preferably for at least 5 sec ⁇ onds, with steam having a temperature of at least 80° C.
  • the main target metals will be iron, zinc, aluminum, and the like.
  • a cleaning method comprises at least two process steps.
  • a water-repellent surface is generated by cleaning with a water-based cleaning bath or by cleaning with a water-based cleaning bath and thereafter additionally rinsing with a water rinse.
  • the second necessary process step consists of drying by contact with high-temperature steam.
  • An effective method for obtaining a water-repellent surface, after clean ⁇ ing by the water-based cleaning bath consists of treatment with a water-based cleaning bath that contains fatty acid alkali salt and/or fatty acid ester. This forms a water-repellent film through the adsorption of fatty acid anions and/or fatty acid ester on the metal surface that has been cleaned by the water-based cleaning bath.
  • One or more C 8 to C 26 fatty acid salts may be used as the fatty acid salt in the water-based cleaning bath.
  • suitable and preferred ex ⁇ amples are the sodium and potassium salts of fatty acids such as oleic acid, lauric acid, palmitic acid, stearic acid, and the like, may be used as the fatty acid salt in the water-based cleaning bath.
  • Suitable fatty acid esters are, for example, the esters of C 8 to C 26 fatty acids, preferably relatively long chain acids such as oleic acid, lauric acid, palmit ⁇ ic acid, stearic acid, and the like. Particularly preferred are esters between these fatty acids and polyhydric alcohols, as specifically exemplified by the sorbitan es ⁇ ters such as sorbitan trioleate, sorbitan monooleate, and sorbitan monolaurate.
  • the reasons for specifying a range of C 8 to C 26 for the fatty acids are as follows: An inadequate water repellency is normally generated at below C 8 , while exceeding C 26 leads to such a large add-on that a clean surface can not readily be obtained.
  • a range of 12 - 18 for the number of carbons per fatty acid mole ⁇ cule for at least some of the fatty acid salts and/or esters is more preferred, because the salts and esters of C B .
  • fatty acids may not form a satisfactorily hy- drophobic layer in some cases when used alone.
  • the concentration of fatty acid salt and fatty acid ester in the treatment bath preferably should be from 0.01 to 5 weight %.
  • An adequate water repellen ⁇ cy usually can not be developed at below 0.01 weight %, while the large amount adsorbed at above 5 weight % prevents a clean surface from being readily ob- tained.
  • the total concentration of salts and esters of C 8 to C 26 fatty acids in a water-based cleaner to be used according to this invention should be from 0.02 to 3 %.
  • Suitable long-chain fatty acid esters for the invention are by themselves poorly soluble or dispersible, and they are therefore preferably dispersed or solu- bilized through the use of anionic surfactant, such as the salts of the sulfate esters of higher alcohols, alkyl ether carboxylate salts, and of course the alkali salts of fatty acids.
  • anionic surfactant such as the salts of the sulfate esters of higher alcohols, alkyl ether carboxylate salts, and of course the alkali salts of fatty acids.
  • nonionic surfactant with a hydrophile-lipophile balance value (herein ⁇ after usually abbreviated as "HLB") in the range from 9 to 16 in addition to the fatty acid salt or fatty acid ester.
  • HLB hydrophile-lipophile balance value
  • Suitable nonionic surfactants are exemplified by polyoxyethylene surfactants such as polyoxyethylene alkyl ethers and poly- oxyethylene alkylphenyl ethers.
  • the cleaning effect can also some- times be improved by the addition of an alkali builder such as sodium carbonate, sodium phosphate, sodium hydroxide, and the like.
  • the contact angle observed for the water will be at least 70°, which is indicative of a water repellency sufficient for practical applications.
  • Much less water will remain on the surface in this case than in the case of a hydrophilic surface, and it is often possible, and is preferred, to obtain even less than about one-tenth of that adhering on a hydrophilic surface.
  • the amount of water retained on the surface of the metal workpiece is one-tenth as much as before, only one-tenth as much heat is required to evaporate the water, with the result that even the low heat capacity metal workpiece can be dried without external heating.
  • the metal workpiece Since application of the method according to the present invention causes a substantial reduction in the amount of water retained on the surface after water rinsing, the metal workpiece will dry spontaneously in a short period of time, after the input of heat by a brief contact with high-temperature steam.
  • This water rinse by temporarily drop ⁇ ping the temperature of the metal surface being treated, increases the amount of steam that subsequently condenses and thereby increases the cleaning effect.
  • the decision whether to implement a water rinse should be based on the re ⁇ quired level of surface cleanliness.
  • the water-repellent film formed on the metal surface is very thin and rep ⁇ resents only a small add-on. As a result, it usually presents no particular prob ⁇ lem to the execution of heat treatment or painting after the drying process. How ⁇ ever, it can be completely evaporated or decomposed if desired by raising the drying temperature.
  • the present invention will be explained in greater detail below with refer ⁇ ence to several examples and comparative examples of actual cleaning process ⁇ es.
  • B 1.5 g/L of the same polyoxyethylene-type nonionic surfactant as in bath
  • Drying time The time in seconds required after the start of drying for the surface of the specimen to become completely dry as visually judged was measured.
  • Rustin g The development of rusting on the surface of the specimen after drying was visually evaluated.
  • Cleanin g effect The oil remaining on the surface of the specimen after drying was measured using a surface carbon analyzer (from the Leco Company). The cleaning effect for the surface of the specimen was re ⁇ ported according to the following scale: A: less than 6 milligrams per square meter (hereinafter usually abbreviated as "mg/m 2 ") of carbon on the surface. B: at least 6 mg/m 2 but less than 10 mg/m 2 of carbon on the surface. C: at least 10 mg/m 2 but less than 20 mg/m 2 of carbon on the surface. D: at least 20 mg/m 2 of carbon on the surface.
  • Treatment process steps • Treatment process for Table 1
  • Water-based cleaning baths A, C, D, E, and G were used. Treatment was carried out with a water rinse using different steam contact times. The drying times, cleaning effects, and rusting were evaluated, and these results are report- ed in Table 2.
  • the water-based clean ⁇ ing method according to the present invention affords drying times as short as in organic solvent-based cleaning (e.g., with trichloroethane, FreonTM, and the like) even without the use of special drying facilities such as hot-air dryers or vac ⁇ uum dryers.
  • the invention method is a very practical cleaning method relative to such issues as equipment cost reduction and space savings.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)
  • Cleaning By Liquid Or Steam (AREA)

Abstract

On peut nettoyer des surfaces métalliques en les mettant en contact avec un bain de nettoyage à base d'eau contenant de 0,01 à 5 % en poids d'ester et/ou de sel d'un acide gras C8 à C26, puis en exposant la surface métallique, pendant au moins 5 secondes, à la vapeur à une température d'au moins 80 °C. L'invention se rapporte également à un procédé de nettoyage, sans solvant, de surfaces métalliques, qui offre des temps de séchage aussi courts que des solvants organiques, sans que l'on ait recours à un équipement de séchage spécial.
PCT/US1995/004784 1994-04-25 1995-04-25 Procede de nettoyage de surfaces metalliques Ceased WO1995029019A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP6/109082 1994-04-25
JP10908294A JPH07292488A (ja) 1994-04-25 1994-04-25 金属表面の乾燥性に優れた水系洗浄方法

Publications (1)

Publication Number Publication Date
WO1995029019A1 true WO1995029019A1 (fr) 1995-11-02

Family

ID=14501148

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/004784 Ceased WO1995029019A1 (fr) 1994-04-25 1995-04-25 Procede de nettoyage de surfaces metalliques

Country Status (2)

Country Link
JP (1) JPH07292488A (fr)
WO (1) WO1995029019A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3791078A (en) * 1972-10-19 1974-02-12 H Fleisher Apparatus for preparing a painted metal surface for repainting
US4153464A (en) * 1977-09-12 1979-05-08 Emery Industries, Inc. Prevention of water staining of aluminum
US4157422A (en) * 1975-08-07 1979-06-05 Emery Industries, Inc. Aluminous metal sheet
US4659488A (en) * 1985-09-18 1987-04-21 The Lubrizol Corporation Metal working using lubricants containing basic alkaline earth metal salts
US4878458A (en) * 1987-08-31 1989-11-07 Nelson Clinton D Method and apparatus for generating pressurized fluid
US5051136A (en) * 1989-02-02 1991-09-24 Nokia Mobile Phones Ltd. Procedure for washing circuit boards and means for use in said procedure
US5203927A (en) * 1990-05-01 1993-04-20 Fujitsu Limited Washing/drying method with an aqueous solution containing surfactant

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3791078A (en) * 1972-10-19 1974-02-12 H Fleisher Apparatus for preparing a painted metal surface for repainting
US4157422A (en) * 1975-08-07 1979-06-05 Emery Industries, Inc. Aluminous metal sheet
US4153464A (en) * 1977-09-12 1979-05-08 Emery Industries, Inc. Prevention of water staining of aluminum
US4659488A (en) * 1985-09-18 1987-04-21 The Lubrizol Corporation Metal working using lubricants containing basic alkaline earth metal salts
US4878458A (en) * 1987-08-31 1989-11-07 Nelson Clinton D Method and apparatus for generating pressurized fluid
US5051136A (en) * 1989-02-02 1991-09-24 Nokia Mobile Phones Ltd. Procedure for washing circuit boards and means for use in said procedure
US5203927A (en) * 1990-05-01 1993-04-20 Fujitsu Limited Washing/drying method with an aqueous solution containing surfactant

Also Published As

Publication number Publication date
JPH07292488A (ja) 1995-11-07

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