EP2665845B1 - Methods of removing rust from a ferrous metal-containing surface - Google Patents

Methods of removing rust from a ferrous metal-containing surface Download PDF

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Publication number
EP2665845B1
EP2665845B1 EP12706349.3A EP12706349A EP2665845B1 EP 2665845 B1 EP2665845 B1 EP 2665845B1 EP 12706349 A EP12706349 A EP 12706349A EP 2665845 B1 EP2665845 B1 EP 2665845B1
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EP
European Patent Office
Prior art keywords
acid
composition
weight
percent
present
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.)
Not-in-force
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EP12706349.3A
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German (de)
English (en)
French (fr)
Other versions
EP2665845A1 (en
Inventor
Michael J. Pawlik
Thor G. Lingenfelter
Nathan J. SILVERNAIL
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PPG Industries Ohio Inc
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PPG Industries Ohio Inc
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Priority to PL12706349T priority Critical patent/PL2665845T3/pl
Publication of EP2665845A1 publication Critical patent/EP2665845A1/en
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Publication of EP2665845B1 publication Critical patent/EP2665845B1/en
Not-in-force legal-status Critical Current
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Classifications

    • 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
    • C23G1/08—Iron or steel
    • 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
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • 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
    • C11D7/20—Water-insoluble oxides
    • 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
    • C11D7/265—Carboxylic acids or salts thereof
    • 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, among other things, methods for removing rust from a ferrous metal-containing surface.
  • a metal oxide layer i.e ., rust
  • a ferrous metal surface a metal oxide layer
  • steel such as mild steel used in the manufacture of various articles. Accordingly, it is often desirable to remove the metal oxide layer. Conventionally, this removal has been accomplished by treating the rusted metal surface with a strong acid, such as nitric, sulfuric, hydrochloric, or phosphoric acid. These highly acidic, corrosive and caustic chemicals are, however, often undesirable from an environmental and safety standpoint.
  • the ferrous metal to be treated is oriented in a substantially vertical fashion such as can be the case with, for example, large structures, such as storage tanks, ships and other vehicles, and bridges, among many others.
  • sprayable products are often desired for convenience and efficiency of use.
  • US 2006/079424 A1 discloses the removal of rust from a stainless steel surface by contacting the surface with a buffered acidic aqueous composition comprising urea, an acid or a blend of acids and synthetic smectite clay.
  • the present invention is directed to a method for removing rust from a ferrous metal-containing surface.
  • the method comprises contacting the surface with a composition comprising: (a) a carboxylic acid; (b) a synthetic hectorite clay; and (c) water.
  • the present invention also relates to a ferrous metal-containing surface of a substrate treated by the foregoing method.
  • certain embodiments of the present invention are directed to methods for removing rust from a ferrous metal-containing surface.
  • rust refers to a coating or film formed on a metal by oxidation or corrosion.
  • the rust that is removed in the methods of the present invention is "red rust” which, as used herein, refers to a coating or film formed on iron or steel by oxidation, as during exposure to air and/or moisture, that comprises iron (II) oxide (FeO, wüstite), alpha phase iron (III) oxide ( ⁇ -Fe 2 O 3 , hematite), beta phase iron (III) oxide ( ⁇ -Fe 2 O 3 ), gamma phase iron (III) oxide ( ⁇ -Fe 2 O 3 , maghemite), epsilon phase iron (III) oxide ( ⁇ -Fe 2 O 3 ), iron (II) hydroxide (Fe(OH) 2 ), iron (III) hydroxide (Fe(OH) 3 ), iron (III) hydroxide
  • the iron oxide that is removed in the methods of the present invention is of a type that is often referred to as "mill scale" which, as used herein, refers to a coating or film formed on iron or steel by oxidation, as during exposure to air, moisture, and/or heat, that comprises iron(II,III) oxide (Fe 3 O 4 , magnetite), alpha phase iron (III) oxide ( ⁇ -Fe 2 O 3 , hematite), iron(II) hydroxide Fe(OH) 2 , (III) hydroxide (Fe(OH) 3 , bernalite), and/or hydrated forms and combinations of any of the foregoing.
  • mill scale which, as used herein, refers to a coating or film formed on iron or steel by oxidation, as during exposure to air, moisture, and/or heat, that comprises iron(II,III) oxide (Fe 3 O 4 , magnetite), alpha phase iron (III) oxide ( ⁇ -Fe 2 O 3 , hematite), iron
  • Metal surfaces that may be treated in the methods of the present invention include, but are not limited to, surfaces constructed of cold rolled steel, hot rolled steel, steel coated with zinc metal, zinc compounds, or zinc alloys, such as electrogalvanized steel, hot-dipped galvanized steel, galvanealed steel, and steel plated with zinc alloy.
  • Surfaces constructed of mild steel may be treated in the methods of the present invention. Mild steel, as used herein, refers to low carbon steel containing less than 0.25% by weight carbon.
  • the metal surface is contacted with a composition comprising a carboxylic acid.
  • the carboxylic acid selected for use in the compositions described herein has a water solubility of > 1 g/L at 20°C.
  • Carboxylic acids suitable for use in the compositions used in the methods of the present invention include, for example, monocarboxylic acids, such as formic acid, acetic acid, propionic acid, methylacetic acid, butyric acid, ethylacetic acid, n-valeric acid, n-butanecarboxylic acid, acrylic acid, propiolic acid, methacrylic acid, palmitic acid, stearic acid, oleic acid, linolic acid, and linolenic acid; dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, lepargilic acid, sebacic acid, maleic acid, and fumaric acid; aliphatic hydroxy acids, such as glycolic acid, lactic acid, tartronic acid, glyceric acid, malic acid, tartaric acid, citramalic acid,
  • the carboxylic acid is present in the composition used in the methods of the present invention in an amount of at least 1 percent by weight, such as at least 10 percent by weight, or, in some cases, at least 15 percent by weight, with the weight percents being based on the total weight of the composition. In certain embodiments, the carboxylic acid is present in the composition used in the methods of the present invention in an amount of no more than 50 percent by weight, such as no more than 30 percent by weight, or, in some cases, no more than 25 percent by weight, with the weight percents being based on the total weight of the composition.
  • the composition that is contacted with the ferrous metal-containing surface also comprises a synthetic hectorite clay.
  • a synthetic hectorite clay in the presently described compositions produces a thickened composition with a highly shear thinning, thixotropic rheology.
  • the composition is sprayable using typical spray devices (including those mentioned below) and yet, it has been discovered, remains on the ferrous metal-containing surface, even if the surface is oriented substantially vertically, for a sufficient time to effect rust removal.
  • substantially vertically means substantially perpendicular (i.e., within ⁇ 20% from perpendicular) to the ground or other surface upon which the ferrous metal-containing surface is disposed.
  • ambient conditions refers to 23°C and atmospheric pressure.
  • Synthetic hectorite clays that are suitable for use in the compositions described herein include, for example, LAPONITE RD, LAPONITE RDS, and LAPONITE JS, including combinations thereof. As will be appreciated, each of these is a layer-structured hydrous magnesium silicate according to the chemical formula NaO 3 (Mg, Li) 3 Si 4 O 10 (F, OH) 2 .
  • LAPONITE RD is a free flowing synthetic layered silicate having a bulk density of 1,000 kg/m 3 , a surface area (BET) of 370 m 2 /g, a pH of a 2% suspension in water of 9.8, wherein the composition on a dry basis by weight is 59.5% SiO 2 , 27.5% MgO, 0.8% Li 2 O, and 2.8% Na 2 O.
  • LAPONITE RDS is also a free flowing a free flowing synthetic layered silicate having a bulk density of 1,000 kg/m 3 , a surface area (BET) of 330 m 2 /g, a pH of a 2% suspension in water of 9.7, wherein the composition on a dry basis by weight is 54.5% SiO 2 , 26.0% MgO, 0.8% Li 2 O, 5.6% Na 2 O, and 4.1% P 2 O 5 .
  • the particle size of the synthetic hectorites, such as those described above, is typically 1 to 30 nanometers in average diameter.
  • the synthetic hectorite clay is present in the composition used in the methods of the present invention in an amount of at least 1 percent by weight, such as at least 2 percent by weight, or, in some cases, at least 3 percent by weight, with the weight percents being based on the total weight of the composition. In certain embodiments, the synthetic hectorite clay is present in the composition used in the methods of the present invention in an amount of no more than 10 percent by weight, such as no more than 6 percent by weight, or, in some cases, no more than 5 percent by weight, with the weight percents being based on the total weight of the composition.
  • the composition used in the methods of the present invention further comprises a source of chloride ions.
  • a source of chloride ions can be particularly beneficial when the removal of mill scale is required or desired.
  • Suitable chloride sources include, for example, hydrochloric acid, calcium chloride, sodium chloride, ammonium chloride, and potassium chloride, among many others.
  • the chloride source is present in the composition used in the methods of the present invention in an amount of at least 1 percent by weight, such as at least 2 percent by weight, or, in some cases, at least 3 percent by weight, with the weight percents being based on the total weight of the composition. In certain embodiments, the chloride source is present in the composition used in the methods of the present invention in an amount of no more than 10 percent by weight, such as no more than 8 percent by weight, or, in some cases, no more than 6 percent by weight, with the weight percents being based on the total weight of the composition.
  • the composition used in the methods of the present invention further comprises an organic solvent, such as a water miscible organic solvent.
  • organic solvents include monoalkyl or dialkyl ethers of ethylene glycol or diethylene glycol, or a mono-, di-, or trialkyl ether of triethylene glycol and the acetate derivatives thereof.
  • the alkyl group often ranges from 1 to 4 carbon atoms.
  • Suitable examples are saturated glycols containing at least four carbon atoms or a compound containing Formula I: in which: R is independently selected from the group consisting of hydrogen, alkyl of from 1 to 4 carbon atoms and -(O)C-CH 3 ; R 1 is independently selected from the group consisting of -CH 2 , -CH 2 -CH-, -CH 2 -CH(CH 3 )-, and -CH(CH 2 OH)-; R 2 is independently selected from the group consisting of alkyl of from 1 to 4 carbon atoms, hydroxyl substituted alkyl of from 1 to 4 carbon atoms and -(O)C-CH 3 .
  • Exemplary solvents are Cellosolve (trademark for monoethyl ether of ethylene glycol), methyl Cellosolve, butyl Cellosolve, isobutyl Cellosolve, hexyl Cellosolve, Carbitol (trademark for monoethyl ether of diethylene glycol), butyl Carbitol, hexyl Carbitol, monobutyl ether of propylene glycol, monopropyl ether of propylene glycol, monomethyl ether of propylene glycol, monomethyl ether of dipropylene glycol, butoxytriglycol C 4 H 9 O(C 2 H 4 -O) 3 H, methoxytriglycol CH 3 O(C 2 H 4 -O-) 3 H, ethoxytriglycol C 2 H 5 O(C 2 H 4 O) 3 H, 1,butoxyethoxy-2-propanol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol
  • Suitable water miscible alcohols that may be employed in the present invention have from 1 to 8 carbon atoms, such as methanol, ethanol, propanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, methylamyl alcohol and the like.
  • Suitable water miscible aliphatic ketones that may be employed in the present invention are acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methoxy acetone, cyclohexanone, methyl n-amyl ketone, methyl isoamyl ketone, ethyl butyl ketone, diisobutyl ketone, isophorone, acetyl acetone (2,4-pentane dione), diacetone alcohol (CH 3 ) 2 C(OH)CH 2 C(O)CH 3 .
  • the organic solvent is present in the composition used in the methods of the present invention in an amount of at least 1 percent by weight, such as at least 2 percent by weight, or, in some cases, at least 3 percent by weight, with the weight percents being based on the total weight of the composition.
  • the chloride source is present in the composition used in the methods of the present invention in an amount of no more than 10 percent by weight, such as no more than 8 percent by weight, or, in some cases, no more than 6 percent by weight, with the weight percents being based on the total weight of the composition.
  • compositions used in the methods of the present invention may also comprise any of a variety of optional ingredients, such as colorants, surfactants, corrosion inhibitors, preservatives, fillers, abrasives, buffers, fragrances, and the like.
  • the remainder of the composition used in the methods of the present invention is typically water, such as, for example, deionized water.
  • the compositions used in the methods of the present invention are substantially free, or completely free, of strong acids that produce a by-product that is environmentally undesirable, such as phosphoric acid and/or sulfuric acid.
  • substantially free when used with reference to the absence of a strong acid in the compositions described herein means that the composition includes less than 1% by weight, such as less than 0.1% by weight, of the strong acid.
  • completely free means that there is no strong acid in the composition at all.
  • the composition used in the methods of the present invention has a low shear viscosity (As used herein, “low shear viscosity” refers to a viscosity measured on a Physica MCR301 viscometer with a CP50-1/TG spindle for 70 seconds at a shear rate of 0.01s (-1) and at 23°C.) of at least 1,000 Pa ⁇ s, such as at least 2,000 Pa ⁇ s, or, in some cases, at least 4,000 Pa ⁇ s or at least 5,000 Pa ⁇ s.
  • a low shear viscosity refers to a viscosity measured on a Physica MCR301 viscometer with a CP50-1/TG spindle for 70 seconds at a shear rate of 0.01s (-1) and at 23°C.
  • the composition used in the methods of the present invention has a high shear viscosity (As used herein, “high shear viscosity” refers to a viscosity measured on a Physica MCR301 viscometer with a CP50-1/TG spindle at a shear rate of 10 (4) s (-1) for 5 seconds at 23°C.) of no more than 0.50 Pa ⁇ s, such as no more than 0.1 Pa ⁇ s, or, in some cases, no more than 0.01 Pa ⁇ s.
  • a high shear viscosity refers to a viscosity measured on a Physica MCR301 viscometer with a CP50-1/TG spindle at a shear rate of 10 (4) s (-1) for 5 seconds at 23°C.
  • the composition used in the methods of the present invention has a pH of no more than 6.0, such as 2.0 to 5.0, or, in some cases, 3.0 to 4.0.
  • the composition is contacted with the metal containing surface by any of a variety of methods, such as by brushing, spraying, or dipping, among many other methods.
  • the compositions described herein are particularly suitable for spray application using conventional pressure pot equipment or HVLP equipment. Because of the thixotropic nature of the compositions described herein, the method of the present invention can be suitable for use with substantially vertically oriented ferrous metal-containing surface, such as can be the case with, for example, large structures, such as storage tanks, bridges, ships and other vehicles, among many others.
  • the composition is allowed to remain on the metal containing surface to remove rust to the extent desired or required.
  • Contact time often ranges from at least 5 minutes to several hours, often at least 30 minutes, in some cases at least 3 or 4 hours, depending on the severity of the rust and the temperature at which the cleaning is conducted.
  • the derusted surface may then be washed with water to remove the composition described herein, the loosened rust and dissolved rust. In some cases, more than one application of the composition described herein may be desired. Mechanically removing loose rust and scale, by wire brushing for example, prior to application of the composition described herein, may also be desired.
  • the present invention also relates to a metal surface of a substrate treated by the method of the present invention.
  • Example 1A Example 1B
  • Example 1C Example 1D
  • Example 1E Laponite RD 1 6 -- -- -- -- Klucel M 2 -- 1.5 -- -- -- Klucel H 3 -- -- 1.5 -- -- Polyvinylpyrrolidone 4 -- -- -- -- 15 -- Gelatin (Calf Skin) 5 -- -- -- -- -- -- 15
  • Deionized water 114 118.5 118.5 105 105
  • 1 Laponite RD is commercially available from Southern Clay Products, Inc.
  • the Laponite RD was incorporated into the water following the manufacturer's recommendations.
  • the citric acid was then slowly added while stirring the solution.
  • 2 Klucel M is a hydroxyl propyl cellulose (M w of about 850,000) available from Hercules Inc.
  • Example 1B the Klucel M material was sifted into the water while stirring. After the material had dissolved, the citric acid was slowly added while stirring.
  • 3 Klucel H is a hydroxyl propyl cellulose (M w of about 1,150,000) available from Hercules Inc.
  • Example 1C the Klucel H material was sifted into the water while stirring. After the material had dissolved, the citric acid was slowly added while stirring.
  • Example ID the polyvinylpyrrolidone was sifted into the water while stirring. After the material had dissolved, the citric acid was slowly added while stirring.
  • 5 The gelatin is commercially available from Sigma-Aldrich Co.
  • Example 1E the gelatin was sifted into the water while stirring. After the material had dissolved, the citric acid was slowly added while stirring.
  • Example 2A Example 2B
  • Example 2C Deionized Water 380 380 380 Laponite RD 1 20 -- -- Bentonite 2 -- 20 -- Kaolin 2 -- -- 20 Citric acid 100 100 100 1 Commercially available from Southern Clay Products, Inc. 2 Commercially available from VWR International, LLC.
  • Rusty panels were prepared as described in Example 1. The three solutions were spray applied using a garden sprayer to the panels which were disposed at an angle of approximately 80° from horizontal. After 1 hour, the panels were rinsed with water and the amount of rust removal was visually assessed. Approximately 100% of the rust was removed with the solution of Example 2A, while neither Examples 2B and 2C showed any rust removal.
  • Rusty panels were prepared as in Example 1. The three solutions were applied to the panels disposed at an angle of approximately 80° from horizontal. After 1 hour, the panels were rinsed with water and the amount of rust removal was visually assessed. Approximately 100% of the rust was removed with all three solutions.
  • Rusty panels were prepared as in Example 1. The three solutions were applied to the panels disposed at an angle of approximately 80° from horizontal. After 1 hour, the panels were rinsed with water and the amount of rust removal was visually assessed. Approximately 100% of the rust was removed with all three solutions.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
EP12706349.3A 2011-01-21 2012-01-20 Methods of removing rust from a ferrous metal-containing surface Not-in-force EP2665845B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL12706349T PL2665845T3 (pl) 2011-01-21 2012-01-20 Sposoby usuwania rdzy z powierzchni zawierającej metal żelazny

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/011,151 US20120189485A1 (en) 2011-01-21 2011-01-21 Methods of removing rust from a ferrous metal-containing surface
PCT/US2012/022004 WO2012100146A1 (en) 2011-01-21 2012-01-20 Methods of removing rust from a ferrous metal-containing surface

Publications (2)

Publication Number Publication Date
EP2665845A1 EP2665845A1 (en) 2013-11-27
EP2665845B1 true EP2665845B1 (en) 2018-03-07

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US (1) US20120189485A1 (ja)
EP (1) EP2665845B1 (ja)
JP (1) JP5693754B2 (ja)
KR (1) KR20130117853A (ja)
CN (1) CN103415651B (ja)
AU (1) AU2012207164B2 (ja)
BR (1) BR112013018680A2 (ja)
CA (1) CA2825284A1 (ja)
ES (1) ES2666452T3 (ja)
MX (1) MX2013008465A (ja)
PL (1) PL2665845T3 (ja)
SG (1) SG192055A1 (ja)
TR (1) TR201807940T4 (ja)
WO (1) WO2012100146A1 (ja)

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CN109628940B (zh) * 2019-01-21 2021-11-12 常熟理工学院 一种多羟基苯甲酸型水基中性除锈剂
KR102166122B1 (ko) 2020-04-13 2020-10-15 케이알건설 주식회사 강 교량의 녹 또는 페인트 제거방법
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DE102007039652A1 (de) * 2006-12-05 2008-06-12 Henkel Kgaa Mittel zur Behandlung harter Oberflächen
US20090197792A1 (en) * 2008-02-05 2009-08-06 Amcol International Corporation Drip resistant acidic compositions for sprayable and non-sprayable application
EP2166075A1 (en) * 2008-09-23 2010-03-24 The Procter and Gamble Company Cleaning composition

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CN103415651A (zh) 2013-11-27
CA2825284A1 (en) 2012-07-26
AU2012207164B2 (en) 2015-08-20
EP2665845A1 (en) 2013-11-27
PL2665845T3 (pl) 2018-08-31
JP5693754B2 (ja) 2015-04-01
MX2013008465A (es) 2013-12-06
ES2666452T3 (es) 2018-05-04
US20120189485A1 (en) 2012-07-26
CN103415651B (zh) 2016-10-26
WO2012100146A1 (en) 2012-07-26
JP2014508220A (ja) 2014-04-03
KR20130117853A (ko) 2013-10-28
NZ613553A (en) 2015-11-27
BR112013018680A2 (pt) 2016-10-18
TR201807940T4 (tr) 2018-06-21
SG192055A1 (en) 2013-08-30

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