WO1997006229A1 - Metal cleaning composition and process that do not damage plastic - Google Patents
Metal cleaning composition and process that do not damage plastic Download PDFInfo
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- WO1997006229A1 WO1997006229A1 PCT/US1995/009687 US9509687W WO9706229A1 WO 1997006229 A1 WO1997006229 A1 WO 1997006229A1 US 9509687 W US9509687 W US 9509687W WO 9706229 A1 WO9706229 A1 WO 9706229A1
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- 239000000203 mixture Substances 0.000 title claims abstract description 91
- 238000004140 cleaning Methods 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 19
- 239000002184 metal Substances 0.000 title claims abstract description 19
- 239000004033 plastic Substances 0.000 title claims abstract description 17
- 229920003023 plastic Polymers 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 20
- 230000006378 damage Effects 0.000 title description 5
- 239000002253 acid Substances 0.000 claims abstract description 41
- 239000004094 surface-active agent Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 239000002518 antifoaming agent Substances 0.000 claims description 32
- 239000012141 concentrate Substances 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 24
- 239000003205 fragrance Substances 0.000 claims description 20
- 239000003086 colorant Substances 0.000 claims description 19
- 150000007513 acids Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 239000002689 soil Substances 0.000 claims description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 5
- 244000005700 microbiome Species 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical class CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 239000000306 component Substances 0.000 claims 119
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- 239000004417 polycarbonate Substances 0.000 abstract description 10
- 229920000515 polycarbonate Polymers 0.000 abstract description 10
- 238000005336 cracking Methods 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 230000012010 growth Effects 0.000 abstract description 2
- 235000019645 odor Nutrition 0.000 abstract description 2
- 241000894006 Bacteria Species 0.000 abstract 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- 239000004615 ingredient Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000006260 foam Substances 0.000 description 7
- 238000013517 stratification Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 235000019799 monosodium phosphate Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical class [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 229910000755 6061-T6 aluminium alloy Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010061217 Infestation Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- -1 ether alcohols Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
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
-
- 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
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
-
- C11D2111/16—
-
- C11D2111/18—
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Detergent Compositions (AREA)
Abstract
An aqueous liquid composition containing dihydrogen phosphate salt, sulfur containing surfactant, and preferably a small amount of phosphoric acid cleans soiled metal surfaces without damaging plastic parts that come into contact with the composition and without supporting the growth of bacteria that cause unpleasant odors. The composition is particularly useful for cleaning unpainted aluminum sided rail transport cars that have polycarbonate housings insulating electrical contact points that provide motive electric power to the cars; many conventional aqueous alkaline and acid cleaners promote stress cracking of polycarbonate plastics.
Description
Description
METAL CLEANING COMPOSITION AND PROCESS THAT DO NOT DAMAGE
PLASTIC
BACKGROUND OF THE INVENTION Field ofthe Invention
This invention relates to cleaning metal surfaces, both painted and unpainted, more particularly when the metal surfaces are adjacent to elements of plastic, especially polycarbonate plastic, which is susceptible to stress cracking when repeatedly contacted with many conventional metal cleaning compositions. This invention also relates to cleaning compositions that are useful in such cleaning processes, are not overly acidic or alkaline, and are not susceptible to developing undesirable odors from micro-organ¬ isms that readily come into contact with the compositions during normal storage or use. Statement of Related Art
A very wide variety of cleaning compositions are known in the art. Few if any ofthese compositions, however, are known to be capable of fulfilling all the desiderata noted above, particularly for railroad cars that are powered by electricity. Such cars, like other railroad cars, come into contact with a wide variety of atmospheric pollutants and air-borne soils that often lead to rapid deterioration in the aesthetic appearance ofthe ex¬ teriors ofthe cars. Ordinary rail cars that do not supply their own motive power can be readily cleaned by a variety of cleaners, usually most readily by fairly highly alkaline cleaners. However, rail cars that are directly powered by electricity, a type especially frequently used in mass transit operations, generally have housings of polycarbonate plastic on their exterior surfaces to protect electrical contacts that supply power to move the cars from a "third rail", overhead power line, or the like. This plastic readily devel¬ ops stress cracks when contacted repeatedly by many alkaline solutions, including some of the most generally effective aqueous metal cleaning compositions. Such large vehicles can most conveniently be cleaned by sprayers, but it is a practical impossibility in many cases to protect any plastic parts of the exterior surface from contact with a sprayed cleaner composition, and frequent replacements ofthe plastic insulating housings are economically unacceptable.
DESCRIPTION OF THE INVENTION Object ofthe Invention
Major objects of the present invention are to provide compositions and/or pro¬ cesses that (i) effectively clean painted and unpainted metal surfaces, (ii) do not damage any plastic materials, particularly polycarbonate plastic insulating housings, that are ad¬ jacent to the metal surfaces to be cleaned, (iii) are not susceptible to becoming malodor¬ ous as a result of infestation from commonly ambient micro-organisms, and (iv) do not have a pH lower than about 3 or higher than about 9, so as to minimize the likelihood of personal injuries to workers using the cleaners. A subsidiary object is to brighten un- painted aluminum surfaces, particularly those of Type 6061 T6 aluminum, that are cleaned using the compositions. Other objects will be apparent from the description be¬ low. General Principles of Description
Except in the claims and the specific examples, or where otherwise expressly in- dicated, all numerical quantities in this description indicating amounts of material or con¬ ditions of reaction and/or use are to be understood as modified by the word "about" in describing the broadest scope ofthe invention. Practice within the numerical limits stat¬ ed is generally preferred, however. Also, unless expressly stated to the contrary: percent, "parts of, and ratio values are by weight; the term "polymer" includes "oligomer", "co- polymer", "terpolymer", and the like; the first definition or description of the meaning of a word, phrase, acronym, abbreviation or the like applies to all subsequent uses ofthe same word, phrase, acronym, abbreviation or the like and applies, mutatis mutandis, to normal grammatical variations thereof; the description of a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more ofthe members ofthe group or class are equally suitable or preferred; chemical descriptions of neutral materials apply to the materials at the time of addition to any combination specified in the description and do not necessarily preclude chemical changes to the materials as a result of reaction in the combination; specification of materials in ionic form means that the materials are supplied to prepare the composi- tions containing them in the form of soluble salts containing the ions specified and im¬ plies the presence in any composition specified to contain ionic materials of sufficient counterions to produce electrical neutrality for the composition as a whole; and any coun-
terions thus implicitly specified preferably are selected from among other constituents explicitly specified in ionic form, to the extent possible; otherwise such counterions may be freely selected, except for avoiding counterions that act adversely to the objects ofthe invention. Summary of the Invention
Liquid cleaning compositions according to the invention have a pH value between 3 and 9 and comprise, preferably consist essentially of, or more preferably consist of, water and:
(A) dihydrogen phosphate ions and (B) a component of surfactant(s), preferably resistant to attack by micro-organisms; and, optionally, one or more of:
(C) a component of acid(s) that are stronger acids than dihydrogen phosphate ions and that are not part of any ofthe preceding components;
(D) a component of antifoam agent(s), other than those that are part of any of the preceding components;
(E) odorants and/or colorants, other than those that are part of any ofthe preceding components.
These compositions according to the invention may either be working compositions, suit¬ able for direct use in cleaning, or concentrate compositions, suitable for dilution with ad- ditional water to produce a working composition.
A process according to the invention comprises at least a step of contacting a soiled metal surface with a liquid cleaning composition according to the invention as de¬ fmed herein and maintaining sufficient relative motion between the liquid cleaning com¬ position and the soiled metal surface to remove some ofthe soil from the surface by dis- solving and/or dispersing the soil in the liquid cleaning composition.
Detailed Description ofthe Invention. Including Preferred Embodiments
Compositions according to the invention preferably have no evidence of phase stratification visible to unaided normal human vision; i.e., the compositions may be cloudy or otherwise show evidence of suspended second phases, but preferably do not stratify into more than one liquid layer or contain any solid particles large enough to see individually with unaided normal human vision. If this condition is not fulfilled, there is always some danger of concentration variations due to inhomogeneity ofthe composi-
tion.
The dihydrogen phosphate ions required for component (A) can be supplied by any soluble salt including such ions. For reasons of economy, ammonium, potassium, and sodium dihydrogen phosphates are preferred, with sodium most preferred. In a working cleaning composition according to the invention, the concentration of dihydro¬ gen phosphate ions preferably is, with increasing preference in the order given, at least 1.7, 3.7, 5.7, 7.7, 9.7, 10.7, 11.7, 12.7, 13.7, 14.7, or 15.7 grams per liter (hereinafter usu¬ ally abbreviated as "g/L") and independently preferably is, with increasing preference in the order given, not more than 100, 75, 50.8, 45.8, 40.8, 35.8, 30.8, 28.8, 26.8, 25.8, 24.8, or 23.8 g/L.
Surfactant component (B) is preferably selected from anionic surfactant mole¬ cules including at least one aromatic ring and at least one sulfur atom per molecule. More preferably, this component is selected from surfactant molecules including two phenyl rings, which still more preferably are each bonded by a single bond to a single oxygen atom. Independently, in order to minimize the chance of development of malod¬ orous growths of micro-organisms in the compositions according to the invention, the surfactant molecules preferably contain, with increasing preference in the order given, at least 2, 4, 6, 7, 8, 9, or 10 percent of sulfur, most preferably in the form of at least one sulfonate group bonded to each phenyl ring in the molecule. Also, independently, the surfactants are preferably ammonium, potassium, or sodium salts, most preferably sodi¬ um salts. Another independent preference is that the average molecular weight of the surfactant component preferably is, with increasing preference in the order given, at least 200, 300, 400, 450, 500, 525, 550, or 575 and independently preferably is, with increas¬ ing preference in the order given, not more than 1500, 1000, 900, 800, 750, 700, 675, 650, or 625. The single most preferred chemical type for surfactant component (B) is sodium salts of disulfonated tetrapropylene derivatives of 1,1-oxy-bw-benzene, commer¬ cially available from Dow under the trade name DOWFAX™ 2A1.
The amount of surfactant component (B) in a working composition according to the invention preferably is at least, with increasing preference in the order given, 0.4, 0.8, 1.2, 1.6, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, or 3.2 g/L and independently preferably is, with in¬ creasing preference in the order given, not more than 15, 12, 10, 9.2, 8.2, 7.2, 6.2, 5.7, 5.3, 5.0, or 4.8 g/L. Independently, in either a concentrate or a working composition ac-
cording to the invention, the ratio of the amount of surfactant component (B) to the amount of dihydrogen phosphate ions component (A) preferably is at least, with increas¬ ing preference in the order given, 0.05:1.0, OJ 0:1.0, 0.13: 1.0, 0.15:1.0, 0.16:1.0, 0J7: 1.0, 0.18:1.0, 0.19:1.0, or 0.20:1.0 and independently preferably is not more than, with increasing preference in the order given, 0.50:1.0, 0.40:1.0, 0.35:1.0, 0.33:1.0, 0.31 :1.0,
0.29:1.0, 0.27: 1.0, 0.25:1.0, 0.24:1.0, 0.23:1.0, 0.22:1.0, or 0.21 :1.0.
The presence of optional component (C) in a composition according to the inven¬ tion is normally preferred, especially when the metal surface to be cleaned is unpainted and a brightening effect on the cleaned surface is desired. Within the broadest scope of the invention, any acidic material that is a stronger acid than dihydrogen phosphate ions may be used for component (C). However, organic acids are generally less preferred, be¬ cause they appear to be more likely to cause stress cracking of polycarbonate plastics than inorganic acids. The single most preferred material for component (C) is orthophos- phoric acid. For any particular chemical substance in component (C), the "effective num- ber of acid hydrogen atoms per molecule" is hereby defined as the number of hydrogen atoms per molecule ofthe substance that are formed by ionization, in a composition ac¬ cording to the invention, by a reaction with a higher ion product constant than that, in the same composition according to the invention, for the reaction: H2PO4 " ** HPO4 '2 + H+. Also, the "effective moles of acid" (hereinafter usually abbreviated "EMA") for any par- ticular amount ofa component (C) according to this invention with a particular composi¬ tion consisting of n distinct chemical substances, where n represents a positive integer, each of said distinct chemical substances having an effective number of acid hydrogen atoms per molecule of e„ where i represents an integer from 1 to n that denotes the i'th substance in the number of distinct chemical substances, each of said distinct chemical substances being present in a number of moles m„ is defined for later use herein by equation (1) below:
EMA = f m,.e, (1). ι =l Independently ofthe chemical nature ofthe acid, the amount of component (C) in a composition according to the invention preferably is such that the ratio ofthe EMA of component (C) to the number of moles of dihydrogen phosphate ions in component
(A) present along with component (C) in a composition according to the invention prefer¬ ably is at least, with increasing preference in the order given, 0.005:1.0, 0.015:1.0, 0.025:1.0, 0.035:1.0, 0.045:1.0, 0.050:1.0, 0.055:1.0, 0.057:1.0, 0.059:1.0, 0.061 :1.0, 0.063:1.0, or 0.065:1.0 and independently preferably is not more than, with increasing preference in the order given, 0.40: 1.0, 0.30:1.0, 0.20:1.0, 0.15:1.0, 0.10:1.0, 0.090:1.0, 0.085:1.0, 0.080:1.0, 0.075: 1.0, 0.070:1.0, or 0.067: 1.0.
Ordinarily, antifoam component (D) is not needed in a composition according to this invention, because most such compositions with preferred ingredients in preferred amounts have not been observed to be prone to excessive foaming. If antifoaming agent should be needed, the most effective ones tested have been found to be PARCOLENE®
95B concentrate, P3® Defoamer 2483, and PARCO® Defoamer 14, all available com¬ mercially from the Parker Amchem Div. of Henkel Corp., Madison Heights, Michigan, USA and FOAM BAN™ MS-30, commercially available from Ultra Additives, Inc., Paterson, New Jersey. Component (E) is not normally required for any technical reason, but may be aes¬ thetically advantageous for certain uses of compositions according to the invention.
For various reasons, it is often preferred that many ingredients used in other cleaning compositions should not be present in compositions according to the invention. Specifically, it is increasingly preferred in the order given, independently for each prefer- ably minimized type of material listed below, that compositions according to the inven¬ tion contain no more than 10, 5, 3, 2.0, 1.0, 0.60, 0.35, 0.10, 0.08, 0.04, 0.02, 0.01, 0.005, 0.002, or 0.001 percent of each of the following materials: alkali metal, alkaline earth metal, and ammonium hydroxides, monohydrogen phosphates, phosphates, condensed phosphates, and sulfates; any chemical form of any metals other than alkali and alkaline earth metals; nitrates and other oxidizing agents (the others being measured as their oxi¬ dizing stoichiometric equivalent as nitrate) that are not part of one ofthe necessary or op¬ tional components of compositions according to the invention as described above; alco¬ hols, ethers, ether alcohols, hydrocarbons, halocarbons, halohydrocarbons, aldehydes, or ketones that are not part of one ofthe necessary or optional components of composi- tions according to the invention as described above; and silicates and oxides of silicon. Independently ofthe other preferences stated above, a working composition ac¬ cording to the invention preferably has a pH value that is at least, with increasing prefer-
ence in the order given, 3J, 3.3, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0 and independently prefer¬ ably is, with increasing preference in the order given, not more than 8, 7, 6.5, 6.0, 5.8, 5.6, 5.4, 5.3, 5.2, 5.1, or 5.0.
A process according to the invention normally, primarily for convenience, is pref- erably performed at whatever ambient temperature is naturally prevailing, provided that this temperature is not too low for the cleaning composition used to remain liquid. Pref¬ erably, the cleaning composition is used at a temperature of at least, with increasing pref¬ erence in the order given, 10, 15, 20, 25, or 30 °C. Cleaning effectiveness generally in¬ creases with increasing temperature of use, up to at least 50 °C. Preferably, the use temperature is not more than 55 °C.
A concentrate composition according to the invention contains at least compon¬ ents (A) and (B) as described above and preferably also contains component (C) when the latter is desired in the working composition(s) to be made from the concentrate. More preferably, a concentrate composition according to the invention contains all ofthe components of a working composition according to the invention that are identified by letter above and are desired in the working composition(s) to be made from the concen¬ trate composition. Independently of all other preferences with respect to concentrates, the concentration in a concentrate of any component of compositions according to the in¬ vention that is identified by letter above preferably is not less than, with increasing pref- erence in the order given, 2, 3, 4, 5, 6, 7, 8, 9, or 10 times larger than any preferred con¬ centration specified above for the same component in working compositions and inde¬ pendently preferably is, with increasing preference in the order given, not more than 50, 40, 35, 30, 25, 20, 17, 15, 13, or 11 times larger than any preferred concentration speci¬ fied above for the same component in working compositions. The invention is explained in greater detail below using working examples, and the benefits ofthe invention are illustrated by comparative examples. Examples and Comparison Examples Group 1
Four possible cleaner compositions, as shown in Table IJ below, were made in concentrate form. A 5 % by volume solution in water of each of Concentrates 1.2 - 1.4 and of sodium hydroxide were made to test for evidence of damage to polycarbonate plastic. Large electrical connectors with insulating blue polycarbonate plastic housings as actually used by the Bay Area Rapid Transit System in Northern California were
Table IJ : CONCENTRATES FOR GROUP 1
Ingredient % of Ingredient in Concentrate Number:
IJ 1.2 1.3 1.4
Water 47 34 77.4 77
Sodium Dihydrogen Phosphate 47 0 16 17
Gluconic Acid 0 60 0 0
DOWFAX™ 2A1 Surfactant* 6 6 6 6
Pine Oil (odorant) 0 0 0.6 0
Visible Phase Stratification? Yes No No No
Footnote for Table 1.1
*This material is reported by its supplier to be an aqueous solution containing about 47 % of its surfactant ingredients, which are benzene, lJ-oxybis, tetrapropylene derivative, disulfonated, sodium salts.
tested by soaking in these potential working compositions, maintained at normal ambient temperatures from 20 - 25 °C for the times and with the results shown in Table 1.2 below. Concentrates IJ, 1.3, and 1.4 are according to the invention and Concentrate 1.2 is not, because it lacks dihydrogen phosphate ions. Concentrate IJ is less preferred because of its spontaneous phase stratification.
Table 1.2: EFFECT OF WORKING COMPOSITIONS ON POLYCARBONATE
Test Working Composi¬ Effect on Polycarbonate after Exposure for: tion Made From:
94 Hours 142 hours
Sodium Hydroxide Severely cracked Not further tested
Concentrate 1.2 Slightly cracked Not further tested
Concentrate 1.3 No cracking visible No cracking visible
Concentrate 1.4 No cracking visible No cracking visible
Group 2 - Foam Testing of Compositions Containing Antifoam Agents
A concentrate composition according to the invention prepared for the purposes ofthese tests had the ingredients and concentrations specified in Table 2J below.
Table 2.1 : CONCENTRATE COMPOSITION FOR GROUP 2
Ingredient Grams of Ingredient per
Kilogram of Concentrate
Composition
Tap Water 756
Anhydrous Sodium Dihydrogen Phosphate 170
75 % Aqueous Orthophosphoric Acid 14
DOWFAX™ 2A1 Surfactant 60
Ordinarily, this concentrate would be used at 5 - 20 % by volume to make wor¬ king cleaning compositions according to the invention. However, for purposes of this testing, 1 % by volume solutions were used instead, to exaggerate the foaming tendency, which is stronger in more dilute solutions. The general procedure for antifoam testing was as follows: Three (3) milliliters
(hereinafter usually abbreviated "mL") of the concentrate was diluted to 300 mL with cold tap water and shaken in a stopperred mixing cylinder with 500 mL capacity to gen¬ erate foam. Five (5) drops ofthe antifoam agent being tested were then added, and the mixture shaken again. If adequate defoaming was achieved by this addition of 5 drops of antifoam agent, enough additional antifoam agent to produce a total concentration of
1 % by volume of the antifoam agent in the mixture was then added to the mixture to check for any phase stratification or other evidence of inhomogeneity. If 5 drops of de¬ foamer were not sufficient, additional drops were added until adequate defoaming had been achieved, or until the amount of antifoam agent reached 0.25 %. If adequate de- foaming had been achieved with less than 0.25 % by volume of antifoam agent in the tot¬ al mixture, enough antifoam agent to bring its concentration to 1 % was then added to check for any phase stratification or other evidence of inhomogeneity.
The antifoam agents tested are shown in Table 2.2, and the foam testing results, keyed to the identifying numbers given in Table 2.2, are described below after the Table..
Table 2.2: ANTIFOAM AGENTS TESTED
Trade Name of Antifoam Agent Supplier of Antifoam Agent No.
PARCO® Defoamer 14 Parker Amchem Div. of Henkel Corp. 1
P3® Defoamer 2483 Parker Amchem Div. of Henkel Corp. 2
10 % Aqueous Solution of FOAM Ultra Additives, Inc., Paterson, NJ 3 BAN™ MS-575
PARCOLENE® 95B Parker Amchem Div. of Henkel Corp. 4
ANTAROX™ LF-222 Rhόne-Poulenc 5
PLURONIC™ L-61 Rhόne-Poulenc 6
BEVELOID™ 6244 Rhόne-Poulenc 7
FOAM BAN™ MS-30 Ultra Additives, Inc., Paterson, NJ 8
Test Results:
1. Good defoaming with 5 drops. Raising antifoam agent to 1 % produced scum floating on the surface and made the bulk ofthe liquid opaque.
2. Good defoaming with 5 drops, better than with antifoam agent 1. Raising anti¬ foam agent to 1 % produced white solid scum floating on the surface and made the bulk ofthe liquid translucent.
3. Good defoaming requires 8 drops. Raising antifoam agent to 1 % did not pro¬ duce any visible phase stratification, and the liquid remained clear.
4. Very good defoaming with 5 drops, even better than antifoam agent 2. Raising antifoam agent to 1 % produced a small oily spot floating on the surface and made the bulk ofthe liquid substantially opaque.
5. Little or no defoaming effect even at 0.25 %.
6. Little or no defoaming effect even at 0.25 %.
7. Good defoaming required 8 drops. Raising antifoam agent to 1 % produced a slight scum floating on the surface.
8. Very good defoaming with 5 drops. Raising antifoam agent to 1 % made the bulk ofthe liquid translucent, but there was no evidence of phase stratification.
Claims
1. A process of cleaning a soiled metal surface, which may or may not be covered with a protective organic coating and which is in a fixed spatial position with respect to at least one plastic surface, by contacting the soiled metal surface with an aqueous liquid cleaning composition and maintaining relative motion between the liquid cleaning com¬ position and the soiled metal surface to remove at least some ofthe soil from the metal surface by dissolving and/or dispersing the soil in the liquid cleaning composition, the contacting of the soiled metal surface being by a method that also results in contacting at least part of the plastic surface with respect to which the soiled metal surface is in a fixed spatial position, wherein the improvement comprises utilizing as the aqueous liquid cleaning composition a composition that has a pH value in the range from about 3 to about 9 and consists essentially of water and:
(A) dihydrogen phosphate ions and
(B) a surfactant component of selected from the group consisting of surfactants that are resistant to attack by micro-organisms.
2. A process according to claim 1 , wherein the aqueous cleaning composition con¬ sists essentially of water and:
(A) from about 1.7 to about 50.8 g/L of dihydrogen phosphate ions; and
(B) from about 0.4 to about 12 g/L ofa surfactant component selected from the group consisting of surfactant molecules including at least one aromatic ring and at least one sulfur atom per molecule; and optionally, one or more of:
(C) an acid component selected from the group consisting of acids that are stronger acids than dihydrogen phosphate ions and that are not part of any ofthe preced¬ ing components; (D) a component of antifoam agent(s), other than those that are part of any of the preceding components; (E) odorants, colorants, or both odorants and colorants, other than those that are part of any ofthe preceding components, wherein the ratio of the amount of component (B) to the amount of component (A) is from about 0.05 : 1.0 to about 0.5:1.0.
l l
3. A process according to claim 2, wherein, in the aqueous liquid cleaning composi¬ tion, (i) the amount of component (A) is from about 3.7 to about 45.8 g/L, (ii) the amount of component (B) is from about 0.8 to about 8.2 g/L, and (iii) the ratio ofthe amount of component (B) to the amount of component (A) is from about 0.10:1.0 to about 0.40:1.0.
4. A process according to claim 3, wherein the aqueous cleaning composition con¬ sists essentially of water and:
(A) from about 5.7 to about 40.8 g/L of dihydrogen phosphate ions;
(B) from about 1.2 to about 7.2 g/L of a surfactant component selected from the group consisting of surfactant molecules including at least two phenyl rings per molecule and at least 4 % by weight of sulfur; and
(C) an acid component selected from the group consisting of acids that are stronger acids than dihydrogen phosphate ions and that are not part of any ofthe preced¬ ing components; and optionally, one or more of:
(D) a component of antifoam agent(s), other than those that are part of any ofthe pre- ceding components;
(E) odorants, colorants, or both odorants and colorants, other than those that are part of any of the preceding components, wherein the ratio of the amount of component (B) to the amount of component (A) is from about 0.13:1.0 to about 0.35:1.0 and the ratio ofthe effective moles of acid in com- ponent (C) to the number of moles of component (A) is from about 0.015:1.0 to about 0.35:1.0.
5. A process according to claim 4, wherein, in the aqueous liquid cleaning composi¬ tion, (i) the amount of component (A) is from about 7.7 to about 35.8 g/L, (ii) the amount of component (B) is from about 1.6 to about 6.2 g/L, (iii) the ratio of the amount of component (B) to the amount of component (A) is from about 0.15:1.0 to about 0.33:1.0, and (iv) the ratio ofthe effective moles of acid in component (C) to the number of moles of component (A) is from about 0.025:1.0 to about 0.15:1.0.
6. A process according to claim 5, wherein the aqueous cleaning composition consists essentially of water and: (A) from about 9.7 to about 30.8 g/L of dihydrogen phosphate ions;
(B) from about 2.0 to about 5.7 g/L of a surfactant component selected from the group consisting of surfactant molecules including at least two phenyl rings per molecule and at least 6 % by weight of sulfur; and
(C) an acid component selected from the group consisting of acids that are stronger acids than dihydrogen phosphate ions and that are not part of any ofthe preced- ing components; and optionally, one or more of:
(D) a component of antifoam agent(s), other than those that are part of any of the preceding components;
(E) odorants, colorants, or both odorants and colorants, other than those that are part of any ofthe preceding components, wherein the ratio of the amount of component (B) to the amount of component (A) is from about OJ 6 : 1.0 to about 0.31 :1.0 and the ratio of the effective moles of acid in com¬ ponent (C) to the number of moles of component (A) is from about 0.035:1.0 to about 0.10:1.0.
7. A process according to claim 6, wherein, in the aqueous liquid cleaning composi- tion, (i) the amount of component (A) is from about 10.7 to about 28.8 g/L, (ii) the amount of component (B) is from about 2.2 to about 5.3 g/L, (iii) the ratio ofthe amount of component (B) to the amount of component (A) is from about 0.17:1.0 to about 0.29:1.0, and (iv) the ratio ofthe effective moles of acid in component (C) to the number of moles of component (A) is from about 0.045:1.0 to about 0.090:1.0. 8. A process according to claim 7, wherein the aqueous cleaning composition consists essentially of water and:
(A) from about 11.7 to about 26.
8 g/L of dihydrogen phosphate ions;
(B) from about 2.4 to about 5J g/L of a surfactant component selected from the group consisting of surfactant molecules including at least two phenyl rings, each bonded directly to a single oxygen atom, per molecule and at least 7 % by weight of sulfur in the form of a sulfonate moiety bonded to each phenyl ring in the molecule; and
(C) an acid component selected from the group consisting of acids that are stronger acids than dihydrogen phosphate ions and that are not part of any ofthe preced- ing components; and optionally, one or more of:
(D) a component of antifoam agent(s), other than those that are part of any of the preceding components; (E) odorants, colorants, or both odorants and colorants, other than those that are part of any ofthe preceding components.
9. A process according to claim 8, wherein, in the aqueous liquid cleaning composi- tion, (i) the amount of component (A) is from about 12.7 to about 25.8 g/L, (ii) the amount of component (B) is from about 2.6 to about 5J g/L, (iii) the ratio ofthe amount of component (B) to the amount of component (A) is from about 0.18:1.0 to about 0.27:1.0, and (iv) the ratio ofthe effective moles of acid in component (C) to the number of moles of component (A) is from about 0.050:1.0 to about 0.085:1.0.
10. A process according to claim 5, wherein the aqueous cleaning composition con¬ sists essentially of water and:
(A) from about 13.7 to about 24.8 g/L of dihydrogen phosphate ions;
(B) from about 2.8 to about 4.8 g/L of a surfactant component selected from the group consisting of surfactant molecules having a molecular weight in the range from about 400 to about 800 and including at least two phenyl rings, each directly bonded to a single oxygen atom, per molecule and at least 8 % by weight of sulfur in the form ofa sulfonate moiety bonded to each phenyl ring in the mole¬ cule; and
(C) orthophosphoric acid; and optionally, one or more of: (D) a component of antifoam agent(s), other than those that are part of any of the preceding components; (E) odorants, colorants, or both odorants and colorants, other than those that are part of any ofthe preceding components.
11. A process according to claim 10, wherein, in the aqueous liquid cleaning compo- sition, (i) the amount of component (A) is from about 15.7 to about 23.8 g/L, (ii) the amount of component (B) is from about 3.2 to about 4.8 g/L, (iii) the ratio ofthe amount of component (B) to the amount of component (A) is from about 0.19:1.0 to about 0.22:1.0, (iv) the ratio ofthe effective moles of acid in component (C) to the number of moles of component (A) is from about 0.059:1.0 to about 0.080:1.0, and (v) component (B) is selected from molecules which have a molecular weight from about 550 to about
650 and contain at least about 9 % of sulfur.
12. A concentrate composition useful for preparing an aqueous liquid composition for use in a process according to claim 1 by dilution with water, said concentrate compo¬ sition consisting essentially of water and:
(A) from about 10.4 to about 200 g/L of dihydrogen phosphate ions; (B) from about 2.4 to about 72 g/L of a surfactant component selected from the group consisting of anionic surfactant molecules including at least two phenyl rings per molecule and at least 4 % by weight of sulfur; and
(C) an acid component selected from the group consisting of acids that are stronger acids than dihydrogen phosphate ions and that are not part of any ofthe preced- ing components; and optionally, one or more of:
(D) a component of antifoam agent(s), other than those that are part of any of the preceding components;
(E) odorants, colorants, or both odorants and colorants, other than those that are part of any ofthe preceding components, wherein the ratio of the amount of component (B) to the amount of component (A) is from about 0.13:1.0 to about 0.35:1.0 and the ratio ofthe effective moles of acid in com¬ ponent (C) to the number of moles of component (A) is from about 0.015:1.0 to about 0.30:1.0.
13. A concentrate composition according to claim 12, wherein (i) the amount of com- ponent (A) is from about 30.8 to about 180 g/L, (ii) the amount of component (B) is from about 5.4 to about 60 g/L, (iii) the ratio of the amount of component (B) to the amount of component (A) is from about 0.15:1.0 to about 0.33:1.0, and (iv) the ratio ofthe effect¬ ive moles of acid in component (C) to the number of moles of component (A) is from about 0.025 : 1.0 to about 0.15:1.0.
14. A concentrate composition according to claim 13 , consisting essentially of water and:
(A) from about 58.2 to about 170 g L of dihydrogen phosphate ions;
(B) from about 5.0 to about 50 g/L of a surfactant component selected from the group consisting of surfactant molecules including at least two phenyl rings per mole- cule and at least 6 % by weight of sulfur; and
(C) an acid component selected from the group consisting of acids that are stronger acids than dihydrogen phosphate ions and that are not part of any ofthe preced¬ ing components; and optionally, one or more of: (D) a component of antifoam agent(s), other than those that are part of any of the preceding components; (E) odorants, colorants, or both odorants and colorants, other than those that are part of any ofthe preceding components, wherein the ratio of the amount of component (B) to the amount of component (A) is from about OJ 6: 1.0 to about 0.31:1.0 and the ratio ofthe effective moles of acid in com¬ ponent (C) to the number of moles of component (A) is from about 0.035:1.0 to about 0.10:1.0.
15. A concentrate composition according to claim 4, wherein (i) the amount of com¬ ponent (A) is from about 60 to about 170 g/L, (ii) the amount of component (B) is from about 13.2 to about 52 g/L, (iii) the ratio ofthe amount of component (B) to the amount of component (A) is from about 0J 7: 1.0 to about 0.29: 1.0, and (iv) the ratio ofthe effect- ive moles of acid in component (C) to the number of moles of component (A) is from about 0.045:1.0 to about 0.090:1.0.
16. A concentrate composition according to claim 15, wherein the aqueous cleaning composition consists essentially of water and:
(A) from about 77 to about 170 g/L of dihydrogen phosphate ions; (B) from about 15 to about 49 g/L of a surfactant component selected from the group consisting of surfactant molecules including at least two phenyl rings, each bonded directly to a single oxygen atom, per molecule and at least 7 % by weight of sulfur in the form of a sulfonate moiety bonded to each phenyl ring in the molecule; and (C) an acid component selected from the group consisting of acids that are stronger acids than dihydrogen phosphate ions and that are not part of any ofthe preced¬ ing components; and optionally, one or more of: (D) a component of antifoam agent(s), other than those that are part of any of the preceding components; (E) odorants, colorants, or both odorants and colorants, other than those that are part of any ofthe preceding components.
17. A process according to claim 16, wherein (i) the amount of component (A) is from about 127 to about 165 g/L, (ii) the amount of component (B) is from about 18 to about 44 g/L, (iii) the ratio ofthe amount of component (B) to the amount of component (A) is from about OJ 8: 1.0 to about 0.27: 1.0, and (iv) the ratio ofthe effective moles of acid in component (C) to the number of moles of component (A) is from about 0.050: 1.0 to about 0.085:1.0.
18. A concentrate composition according to claim 17, consisting essentially of water and:
(A) from about 137 to about 165 g/L of dihydrogen phosphate ions; (B) from about 24 to about 44 g/L ofa surfactant component selected from the group consisting of surfactant molecules having a molecular weight in the range from about 400 to about 800 and including at least two phenyl rings, each directly bonded to a single oxygen atom, per molecule and at least 8 % by weight of sulfur in the form ofa sulfonate moiety bonded to each phenyl ring in the mole- cule; and
(C) orthophosphoric acid; and optionally, one or more of:
(D) a component of antifoam agent(s), other than those that are part of any of the preceding components;
(E) odorants, colorants, or both odorants and colorants, other than those that are part of any of the preceding components.
19. A concentrate composition according to claim 18, wherein (i) the amount of com¬ ponent (A) is from about 147 to about 165 g/L, (ii) the amount of component (B) is from about 28 to about 36 g/L, (iii) the ratio ofthe amount of component (B) to the amount of component (A) is from about 0.19:1.0 to about 0.22: 1.0, (iv) the ratio of the effective moles of acid in component (C) to the number of moles of component (A) is from about
0.059:1.0 to about 0.080:1.0, and (v) component (B) is selected from molecules which have a molecular weight from about 550 to about 650 and contain at least about 9 % of sulfur.
20. A concentrate composition according to claim 19, wherein component (B) is se¬ lected from sodium salts of disulfonated tetrapropylene derivatives of 1,1-oxybisbenzene.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1995/009687 WO1997006229A1 (en) | 1995-08-08 | 1995-08-08 | Metal cleaning composition and process that do not damage plastic |
| US08/817,023 US5932020A (en) | 1995-08-08 | 1995-08-08 | Metal cleaning composition and process that do not damage plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1995/009687 WO1997006229A1 (en) | 1995-08-08 | 1995-08-08 | Metal cleaning composition and process that do not damage plastic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1997006229A1 true WO1997006229A1 (en) | 1997-02-20 |
Family
ID=22249564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1995/009687 WO1997006229A1 (en) | 1995-08-08 | 1995-08-08 | Metal cleaning composition and process that do not damage plastic |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO1997006229A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5998348A (en) * | 1997-02-28 | 1999-12-07 | Henkel Corporation | Concentrate for a dihydrogen phosphate-based metal cleaning composition that does not damage plastic |
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|---|---|---|---|---|
| US3717590A (en) * | 1970-12-17 | 1973-02-20 | R Fetty | Liquid water-soluble detergent compositions |
| US3725224A (en) * | 1971-06-30 | 1973-04-03 | Rohr Industries Inc | Composition for electrolytic descaling of titanium and its alloys |
| US4705665A (en) * | 1985-04-26 | 1987-11-10 | A. E. Staley Manufacturing Company | Method for inhibiting oxidation of ferrous metals with alkyl glycosides and composition for cleaning ferrous metals |
| US4873174A (en) * | 1988-02-03 | 1989-10-10 | Hoechst Celanese Corporation | Method of using developer-finisher compositions for lithographic plates |
| US5077008A (en) * | 1986-02-06 | 1991-12-31 | Steris Corporation | Anti-microbial composition |
| GB2273300A (en) * | 1992-12-10 | 1994-06-15 | Kao Corp | Hard surface cleaning compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3717590A (en) * | 1970-12-17 | 1973-02-20 | R Fetty | Liquid water-soluble detergent compositions |
| US3725224A (en) * | 1971-06-30 | 1973-04-03 | Rohr Industries Inc | Composition for electrolytic descaling of titanium and its alloys |
| US4705665A (en) * | 1985-04-26 | 1987-11-10 | A. E. Staley Manufacturing Company | Method for inhibiting oxidation of ferrous metals with alkyl glycosides and composition for cleaning ferrous metals |
| US5077008A (en) * | 1986-02-06 | 1991-12-31 | Steris Corporation | Anti-microbial composition |
| US4873174A (en) * | 1988-02-03 | 1989-10-10 | Hoechst Celanese Corporation | Method of using developer-finisher compositions for lithographic plates |
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| US5998348A (en) * | 1997-02-28 | 1999-12-07 | Henkel Corporation | Concentrate for a dihydrogen phosphate-based metal cleaning composition that does not damage plastic |
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