EP0151114B1 - Compositions de viscosite variable a base d'acide telles que des produits eliminant la corrosion et la graisse et des produits de polissage - Google Patents

Compositions de viscosite variable a base d'acide telles que des produits eliminant la corrosion et la graisse et des produits de polissage Download PDF

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Publication number
EP0151114B1
EP0151114B1 EP19830902583 EP83902583A EP0151114B1 EP 0151114 B1 EP0151114 B1 EP 0151114B1 EP 19830902583 EP19830902583 EP 19830902583 EP 83902583 A EP83902583 A EP 83902583A EP 0151114 B1 EP0151114 B1 EP 0151114B1
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EP
European Patent Office
Prior art keywords
weight
composition according
hydroxyethyl
composition
corrosion
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Expired
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EP19830902583
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German (de)
English (en)
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EP0151114A1 (fr
EP0151114A4 (fr
Inventor
Peter F. Dr. Lott
Reiner Jargosch
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Jargosch Reiner
Lott Peter F Dr
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Individual
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    • 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
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • 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
    • C23G5/06—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using emulsions

Definitions

  • the present invention is concerned with improved, acid-based corrosion, grease removal and polishing compositions for treating metallic surfaces and objects. More particularly, it is concerned with such compositions which are compounded so as to substantially prevent oxidation-reduction reactions that would normally take place at a metallic surface, and allow only acid attack of the oxides on the metal.
  • the compositions hereof may include, in addition to polyvinyl pyrrolidone as a viscosity control agent and inhibitor, a derivative of hydrogenated tallow as an emulsifier, and an N-substituted oxazolidine as an acid inhibitor.
  • compositions for removing corrosion from metallic surfaces and objects have long been available.
  • corrosion metal oxides
  • Such materials are acid based, i.e., they rely upon an acidic attack in order to remove corrosion.
  • the present invention overcomes the problems noted above, and provides greatly improved, flowable, aqueous, highly penetrating compositions of acidic pH which are effective for polishing and removal of corrosion from metallic surfaces, and also to degrease the same.
  • a metal cleaning composition comprising a flowable system of water, from 5 to 37% by weight of an acid selected from the group consisting of hydrochloric, sulfuric, phosphoric, nitric and mixtures thereof, from 0.5 to 5% by weight of polyvinylpyrrolidone, from 0.01 to 15% by weight of an emulsifier, from 0.01 to 20% by weight of a base metal attack inhibitor compound selected from the group consisting of N-substituted oxazolidines, the p-alkyl benzyl pyridine chlorides, phenylthiourea, 2-mercaptobenzothiazole, diortho-tolyl-thiourea, pyridine, quinoline, decylamine, the dibensyl sulfoxides, 2-butyne-1, 4-diol, 1-hexyne-3-ol, 4-ethyl-1-octyne-3- 0 I, decy
  • the base metal attack inhibitor preferably is present in an amount from 0.5 to 5% by weight.
  • the alcohol component is most preferably 1-propanol, but other alcohols could also be employed. These alcohols have an alkyl group with from 1 to 10 carbon atoms, inclusive.
  • the alcohol should be used at a level of up to 20% by weight, and most preferably at a level of about 1 to 8% by weight.
  • the water is preferably present at a level of from 30% to 90% by weight, and most advantageously at a level of from about 50% to 80% by weight.
  • the most preferred emulsifiers for use in the invention are selected from the group consisting of the derivatives of hydrogenated tallow (e.g., N, N', N'-tris (2-hydroxyethyl)-N-tallow-1, 3-diamino-propane or amine acetate hydrogenated tallow), polyoxyethylene ethers, polyoxyethylene ester alcohols, polyoxyethylene esters of mixed fatty and resin acids and mixtures thereof, although other specific types referred to hereinafter also have utility.
  • the total amount of emulsifier present in the composition should be from about 0.01 % to 15% by weight, and more preferably from about .5% to 5% by weight.
  • a viscosity control agent (thickener) is used in the compositions hereof to give variations in viscosity.
  • Such viscosity control has heretofore proved to be difficult or impossible to obtain in acidic compositions, inasmuch as most conventional thickeners tend to flocculate at low pH.
  • the control agent of the invention isopolyvinylpyrrolidone at a level of from 0.5% to 5% by weight.
  • a synergistic effect is observed by the use of the mixture of polyvinyl pyrrolidone, Ethoduomeen T/13, (Registered Trade Mark) and N-(2-hydroxyethyl)-oxazolidine as a corrosion inhibitor in preventing base metal attack, inasmuch as the attack with the preferred mixture is less than that of any of the individual corrosion inhibitors.
  • a mild abrasive such as activated silica gel (at a level of up to about 10% by weight) can be employed.
  • Perfumes and coloring agents can be added as desired.
  • the system can be modified for corrosion removal on metal surfaces having a heavy grease or oil coating by preparing a two-phase emulsified system by the addition of toluene or related organic solvents.
  • the single feature is a graphical representation depicting the extent of base metal attack when using a commercially available corrosion remover, 10% HCI and the preferred corrosion removing composition of the invention.
  • the most preferred rust removal compositions in accordance with the present invention contain commercial hydrochloric acid, commercial phosphoric acid, 1-propanol, N-(2 hydroxyethyl) oxazolidine, water, a thickening agent, and N,N', N'-tris(2-hydroxyethyl)-N-tallow-1, 3-diaminopropane as an emulsifier.
  • the following table sets forth the single most preferred rust removal composition, as well as ranges of use of the above indentified components.
  • the oxazolidine base metal inhibitor component of Table I is prepared by slowly adding, with mixing, 435.7 grams of formaldehyde to a beaker containing 564.3 grams of diethanolamine. After all formaldehyde is added, the mixture should be stirred for an additional hour.
  • a base metal inhibitor component can be produced as the reaction product of a lower aldehyde (i.e., containing from about 1-4 carbon atoms) and an alkanolamine (containing one or more alkyl group each having from about 2-8 carbon atoms).
  • a lower aldehyde i.e., containing from about 1-4 carbon atoms
  • an alkanolamine containing one or more alkyl group each having from about 2-8 carbon atoms
  • the beaker containing 590 grams of water is provided.
  • Ten grams of the Ethoduomeen T/13 hydrogenated tallow emulsifier, 270 grams hydrochloric acid, 40 grams phosphoric acid, and 50 grams of I-propanol are all added to the beaker, with continual mixing.
  • the mixture is then heated to 50°C.; and 30 grams polyvinylpyrrolidine is slowly added thereto. Mixing is continued until all of the polymer has dissolved.
  • the drawing graphically illustrates the inhibition against base metal attack provided with the preferred composition of Table I.
  • a commercially available corrosion remover sold under the designation "Naval Jelly” was tested, along with a solution of 10% hydrochloric acid, and the preferred composition thereof.
  • testing conditions were identical, and the extent of attack on a base metal substrate was measured.
  • the extent of such attack is very high with the Naval Jelly and hydrochloric acid, but is significantly lower with the preferred inhibitor composition of the invention.
  • emulsifier(s) As noted above, a number of different materials can be employed for the various components. With respect of the emulsifier(s), surfactants available from ICI Americas, Inc., Wilmington, Delaware, and Armak Chemicals Division, Chicago, Illinois, can be employed in lieu of or in addition to the preferred tallow based emulsifiers. An exemplary list of such surfactants is provided in Table III.
  • compositions of the invention are effective to remove corrosion from base metallic surfaces while substantially preventing oxidation-reduction reactions with the metal itself.
  • grease removal is enhanced by virtue of the presence of a single phase, aqueous system.
  • Use of preferred single phase system also enhances the penetration of corrosion where the latter is present.
  • Representative metals which can be cleaned and/or degreased using the compositions hereof include iron and steel, bronze, brass, copper, monel, nickel, chromium, plated metals and aluminium.
  • a cleaner for tubes of boilers may also be provided by incorporating in the formulation a high foaming agent plus thickeners such as polyvinylpyrrolidone to improve wall adherence.
  • An additive such as Arlatone G may also be included as desired to help prevent surface rerusting.
  • This type of corrosion remover is advantageous in that a small amount will cover a large surface area and does not require heating to permit the corrosion removal action to take place. Also, since the components are water soluble, removal of the corrosive remover can be performed by flushing water through the system.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

Une composition améliorée, à pénétration élevée, éliminant la rouille et/ou la graisse des surfaces métalliques est inhibée chimiquement pour empêcher sensiblement les réactions d'oxydation-réduction avec un substrat métallique et limiter l'action de la composition à une attaque chimique sur la corrosion. La composition se compose de préférence d'une dispersion à phase unique et comprend des quantités respectives d'un acide tel qu'un acide chlorhydrique et un acide phosphorique, un composé organique contenant un atome d'azote, d'oxygène ou de soufre tel que du N-(2-hydroxyéthyle) oxazolidine, un alcool ou un autre solvant organique éliminant la graisse, de l'eau et un ou plusieurs émulsifiants (par exemple un dérivé de suif hydrogéné) pour stabiliser et abaisser la tension de surface de la composition résultante. Ces compositions peuvent être obtenues sous la forme de liquides ou avec un agent régulateur de la viscosité tel qu'un polymère de vynile pyrrolidone, conférant à la composition une consistance pâteuse qui en permet une utilisation aisée sur des surfaces verticales. Dans des variantes, ces compositions peuvent comprendre un abrasif doux tel qu'un gel de silice activé.

Claims (8)

1. Composition pour le nottoyage de métaux, comprenant un système aqueux fluide, de 5 à 37% en poids d'un acide choisi dans le groupe constitué par l'acide chlorhydrique, l'acide sulfurique, l'acide phosphorique, l'acide nitrique et leurs mélanges, de 0,5 à 5% en poids de polyvinylpyrrolidone, de 0,01 à 15% en poids d'un émulsifiant, de 0,01 à 20% en poids d'un composé inhibiteur d'attaque de métal de base, choisi dans le groupe constitué par les oxazolidines N-substituées, les chlorures de p-alkyl-benzyl- pyridines, la phénylthiourée, le 2-mercaptobenzothiazole, la di-ortho-tolyl-thiourée, la pyridine, la quinoléine, la décylamine, les dibenzyl-sulfoxydes, le 2-butyne-1, 4-diol, le 1-hexyne-3-ol, le 4-éthyl-1- octyne-3-ol, la décylamine, l'amine de soja, l'octadécylamine, le chlorure de triméthyl-(alkyle de soja)-ammonium, le chlorure de trimèthyl-octadécylammonium, le chlorure de triméthyldodécylammonium, le chlorure de triméthyl-(alkyle de suif)-ammonium, le N-(alkyle de coprah)-1,3-diaminopropane, les bromures de tétraalkylammonium comprenant un groupe alkyle qui comporte au moins 10 atomes de carbone, les mono-, di- et tributylamines, l'hexaméthylène-diamine, le 2-(bis)-2-hydroxyéthyl-(amino)-1,3-propanediol, la 2-(bis)-2-hydroxyéthyl-(amino)-méthanediamine, le 1,6,8-triaza-4,10-dioxabicyclo-(5,5,0)-dodécane, et leurs mélanges, et 0-20% en poids d'un alcool comprenant un groupe alkyle qui comporte 1 à 10 atomes de carbone.
2. Composition selon la revendication 1, dans laquelle ledit émulsifiant est le N,N',N'-tris-(2-hydroxyéthyl)-N-(alkyle de suite)-1,3-diaminopropane.
3. Composition selon la revendication 1 ou 2, dans laquelle ledit composé inhibiteur est la N-(2- hydroxyéthyl)-oxazolidine.
4. Composition selon la revendication 1, dans laquelle ledit alcool est le 1-propanol.
5. Composition selon l'une quelconque des revendications précédentes, contenant 1 à 8% en poids dudit alcool.
6. Composition selon l'une quelconque des revendications précédentes, contenant 30 à 90% en poids d'eau.
7. Composition selon la revendication 6, contenant 50 à 80% en poids d'eau.
8. Composition selon la revendication 1, contenant 2 à 35% en poids d'acide chlorhydrique et jusqu'à 10% en poids d'acide phosphorique, et dans laquelle le composé inhibiteur est la N-(2-hydroxyéthyl)-oxazolidine et l'émulsifiant est le N,N',N'-tris-(2-hydroxyéthyl)-N-(alkyle de suif)-1,3-diaminopropane.
EP19830902583 1983-07-06 1983-07-06 Compositions de viscosite variable a base d'acide telles que des produits eliminant la corrosion et la graisse et des produits de polissage Expired EP0151114B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1983/001014 WO1985000379A1 (fr) 1983-07-06 1983-07-06 Compositions de viscosite variable a base d'acide telles que des produits eliminant la corrosion et la graisse et des produits de polissage

Publications (3)

Publication Number Publication Date
EP0151114A1 EP0151114A1 (fr) 1985-08-14
EP0151114A4 EP0151114A4 (fr) 1985-12-05
EP0151114B1 true EP0151114B1 (fr) 1990-04-04

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EP19830902583 Expired EP0151114B1 (fr) 1983-07-06 1983-07-06 Compositions de viscosite variable a base d'acide telles que des produits eliminant la corrosion et la graisse et des produits de polissage

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EP (1) EP0151114B1 (fr)
JP (1) JPS60501817A (fr)
DE (1) DE3381414D1 (fr)
WO (1) WO1985000379A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5460797A (en) * 1991-05-08 1995-10-24 Streck Laboratories, Inc. Method for fixing tissues and cells for analysis using oxazolidine compounds
MY139405A (en) 1998-09-28 2009-09-30 Ibiden Co Ltd Printed circuit board and method for its production
ATE407234T1 (de) * 2005-09-15 2008-09-15 Delmet Disossidazione Elettron Verfahren zum beizen von metallischen artikeln, insbesondere von fässern für nahrungsmittel
RU2532921C1 (ru) * 2013-09-12 2014-11-20 Общество с ограниченной ответственностью "СИКМО" (ООО "СИКМО") Антикоррозионное средство для мойки внутренних и наружных металлических поверхностей
RU2532919C1 (ru) * 2013-09-12 2014-11-20 Общество с ограниченной ответственностью "СИКМО" (ООО "СИКМО") Беспенное средство для мойки металлических поверхностей

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2524825A (en) * 1945-09-14 1950-10-10 Socony Vacuum Oil Co Inc Metal cleaning composition
US2737491A (en) * 1952-06-13 1956-03-06 Cities Service Res & Dev Co Method of inhibiting corrosion of metals
US2814593A (en) * 1953-12-18 1957-11-26 Gen Aniline & Film Corp Corrosion inhibition
US3113113A (en) * 1958-11-07 1963-12-03 Armour & Co Corrosion inhibitor compositions
US3575881A (en) * 1967-12-26 1971-04-20 Dow Chemical Co Method of gelling ionic liquids and gelled composition
FR2209858A3 (en) * 1972-12-07 1974-07-05 Colloides Ind Fs Liq. decarbonising and scouring compsns. - contg. polyvinyl pyrrolidone or its derivs, to prevent galvanic corrosion
US4247344A (en) * 1975-10-15 1981-01-27 Nippon Steel Corporation Rust preventing treatment of metal-plated steel materials
JPS5415485A (en) * 1977-07-06 1979-02-05 Masami Kobayashi Creamy derust detergent
US4216032A (en) * 1978-09-27 1980-08-05 Stephen Gradowski Oil composition and method for treating phosphated metal surfaces
US4325744A (en) * 1980-07-25 1982-04-20 The United States Of America As Represented By The Secretary Of The Navy Method and composition for cleaning metal surfaces with a film-forming composition

Also Published As

Publication number Publication date
EP0151114A1 (fr) 1985-08-14
WO1985000379A1 (fr) 1985-01-31
DE3381414D1 (de) 1990-05-10
JPS60501817A (ja) 1985-10-24
EP0151114A4 (fr) 1985-12-05

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