US3518098A - Metal protecting preparations - Google Patents
Metal protecting preparations Download PDFInfo
- Publication number
- US3518098A US3518098A US377391A US3518098DA US3518098A US 3518098 A US3518098 A US 3518098A US 377391 A US377391 A US 377391A US 3518098D A US3518098D A US 3518098DA US 3518098 A US3518098 A US 3518098A
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- United States
- Prior art keywords
- polishing
- cleaning
- nickel
- copper
- preparation
- 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.)
- Expired - Lifetime
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- 229910052751 metal Inorganic materials 0.000 title claims description 43
- 239000002184 metal Substances 0.000 title claims description 43
- 238000002360 preparation method Methods 0.000 title description 24
- 238000005498 polishing Methods 0.000 claims description 33
- 229910052709 silver Inorganic materials 0.000 claims description 24
- 239000004332 silver Substances 0.000 claims description 24
- 238000004140 cleaning Methods 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 19
- 238000005494 tarnishing Methods 0.000 claims description 16
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical compound OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008199 coating composition Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 36
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 23
- 229910052759 nickel Inorganic materials 0.000 description 18
- 238000007792 addition Methods 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- -1 stearyl thioglycollate Chemical compound 0.000 description 14
- 239000000843 powder Substances 0.000 description 12
- 230000001681 protective effect Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- 238000005282 brightening Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-M 2-sulfanylpropanoate Chemical compound CC(S)C([O-])=O PMNLUUOXGOOLSP-UHFFFAOYSA-M 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- LFHBOSSJYCHNBJ-UHFFFAOYSA-N octadecyl 2-sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)S LFHBOSSJYCHNBJ-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 239000010458 rotten stone Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- 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
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3472—Organic compounds containing sulfur additionally containing -COOH groups or derivatives thereof
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
- C23F11/161—Mercaptans
-
- 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
- C23G1/10—Other heavy metals
-
- 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
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3427—Organic compounds containing sulfur containing thiol, mercapto or sulfide groups, e.g. thioethers or mercaptales
Definitions
- a preparation for polishing silver which comprises a mild abrasive and an antitarnish agent, with the latter constituted by a mercaptan consisting of a straight chain alkyl primary thiol containing 12 to 20 carbon atoms.
- Such a preparation when used for cleaning and polishing silver causes an invisible protective coating to be formed on the cleaned metal surface which confers substantial protection against tarnishing as long as .the coating remains intact reducing the frequency with which the silver requires to be cleaned.
- the anti-tarnishing component of the previously proposed preparation is in some respects lacking in desirable properties and the invention seeks to produce a metal treating preparation which employs as its protective ingredient a medium which besides being economical in cost offers the advantages of low toxicity, great stability resulting in a durable protection for the metal, and having a less objectionable odor than the mercaptan of the previous proposal.
- a cleaning or polishing preparation for metal surfaces containing silver, copper or nickel comprising a cleaning or polishing medium in admixture with a protective medium consisting of an ester of a mercapto carboxylic acid. It is found that such a preparation is very effective in use and relatively economical to pro prise besides offering other advantages referred to herein.
- the protective medium may be admixed with a cleaning medium consisting of a physically acting abrasive or one consisting of or comprising a chemically reactive tarnish remover.
- the cleaning or polishing preparation may take the form of a liquid preparation adapted for application in the manner of a metal polish or a complex forming detarnishing solution or it may be in the form of a paste or cream. Further if desired the cleaning or polishing preparation may be provided in the form of a powder or a semi-solid block suitable for application to a bufling wheel, or it may be impregnated into fiber, fabric or braid normally used for cleaning or polishing operations being held therein either as a powder or as a semi-solid.
- the invention also comprises a metal treating preparation for acting on metal surfaces containing silver, copper or nickel comprising a surface treating medium in admixture with a protective medium consisting of an ester of a mercapto carboxylic acid.
- a metal treating preparation may consist of a pickling, detarnishing, brightening, de-scaling or etching bath.
- any such bath may be caused to have tarnish inhibiting properties.
- the invention further comprises a metal treating liquid protective preparation suitable for addition to a treatment bath for acting on surfaces containing silver, copper or nickel to impart tarnish inhibiting properties, such preparation consisting of a solution in an organic solvent of an ester of a mercapto carboxylic acid.
- the substance used to form the protective medium may be any ester of a mercapto carboxylic acid within an appropriate range of such esters.
- the general formula for such an ester is where R is a group derived from an alcohol of the general form C H OH (aliphatic alcohol) or one derived from an aromatic phenol or aromatic alcohol or from a glycol.
- R is a group derived from an alcohol of the general form C H OH (aliphatic alcohol) or one derived from an aromatic phenol or aromatic alcohol or from a glycol.
- R is a group derived from an alcohol of the general form C H OH (aliphatic alcohol) or one derived from an aromatic phenol or aromatic alcohol or from a glycol.
- the most effective ones of the compounds in which R is derived from an aliphatic alcohol are those having from 8 to 22 carbon atoms in the group R.
- One such compound found to be particularly useful is stearyl thioglycollate.
- a liquid polishing preparation suitable for use on surfaces containing silver, copper or nickel contains the following substances in admixture:
- Polishing powder Percent for example diatomaceous earth 20 Ethyl alcohol 20 Stearyl thioglycollate 2.5 Phosphoric acid (as stabiliser) approx. 0.2
- the stearyl thioglycollate is melted and heated to a temperature of approximately 100 C. and is then added to the alcohol. Sufficient of the polishing powder is then added with vigorous stirring until a fairly viscous mixture is obtained. Continuous stirring with a high shear action some water is added and then alternate additions of pol ishing powder and water are made until the mixture is complete.
- the resultant mixture has a dispersion of thiogly-collate on the surface of the polishing powder which is in turn homogeneously dispersed in the aqueous alcoholic liquid.
- the phosphoric acid is then stirred homogeneously into the mixture which is thereupon ready for bottling.
- bentonite may be incorporated in the proportion of about 2 to 4% by Weight.
- the bentonite may be incorporated by forming it to a gel with part of the water. This gel may be added to the viscous mixture aforesaid before the addition of water thereto.
- Acids other than phosphoric acid may be used in place of phosphoric acid to form a stabiliser, although phosphoric acid is preferred for this purpose.
- the stabilising effect is employed to prolong the shelf life of the liquid product.
- the mercapto-propionate is first warmed with an equal weight of detergent paste and the resulting liquid is added to the dry ingredients whilst being stirred. The formation of the stiff paste ensures homogenising of the final product. Afterwards the liquid content is added slowly whilst the mixture is stirred.
- EXAMPLE 3 An emulsion polish for metal surfaces as aforesaid is made up from the following ingredients:
- the emulsion polish is prepared substantially as in the Example 1 above.
- a solvent based paste polish (as opposed to a water based paste polish such as in Example 2) is made up from the following ingredients:
- a cleaning and polishing powder for use on metal surfaces as aforesaid comprises the following:
- Grams Polishing powder e.g. kieselguhr, aluminum oxide '98 Stearyl thioglycollate 62 These constituents are thoroughly blended by grinding. The resulting preparation may be used as such or may be incorporated into a suitable polishing cloth or braid etc.
- a liquid protective preparation which may be added in a small proportion to a pickling, detarnishing, brightening, de-scaling or etching bath for acting on surfaces containing silver, copper or nickel, to impart tarnish inhibiting properties is formed by dissolving stearyl thioglycollate in isopropyl alcohol in the proportion of 2.5% by weight.
- EXAMPLE 7 An emulsion type dipping solution being a protective preparation suitable for treating metal surfaces as above mentioned by immersion therein or for adding in a small proportion to various kinds of baths as in Example 6 is made up of the following constituents:
- a solid polishing composition suitable for mechanical application comprises the following:
- a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H COOR wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufficient to protect the metal surface against tarnishing.
- a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel and which contains an abrasive
- the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H -COO-R wherein n is l or 2 and R is C H wherein n is 8 to 22, in an amount sufficient to protect the metal surface against tarnishing.
- a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel and which contains a tarnish remover
- the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufficient to protect the metal surface against tarnishing.
- a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel and which contains a pickling, detarnishing, brightening, descaling or etching agent
- the improvement which. comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H -C-OOR wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufficient to protect the metal surface against tarnishing.
- a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel in cream form
- the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H C-OOR wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufiicient to protect the metal surface against tarnishing.
- a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel in powder form
- the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H COO-R wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufiicient to protect the metal surface against tarnishing.
- a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel in liquid form the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H COOR wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufficient to protect the metal surface against tarnishing.
- a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel in paste form
- the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H -COOR wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufficient to protect the metal surface against tarnishing.
- a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel in semi-solid block form
- the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H COOR wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufiicient to protect the metal surface against tarnishing.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Detergent Compositions (AREA)
Description
United States Patent 3,518,098 lVIETAL PROTECTING PREPARATIONS Ian Alastair Moncrietf Ford, West Hagley, Bernard Carlton Cox, Oadby, and James Coward Thornton, Mountsorrel, England, assignors to J. Goddard & Sons Limited, Leicester, England No Drawing. Filed June 23, 1964, Ser. No. 377,391 Claims priority, application Great Britain, June 25, 1963, 25,235/63 Int. Cl. C09g 1/02 U.S. Cl. 1063 13 Claims This invention is for improvements in or relating. to metal protecting preparations and is concerned more particularly with a metal treating preparation which incorporates a medium by which a cleaned metal surface is protected so as to retain its cleaned state for a prolonged period. The invention is particularly concerned with preparations for cleaning metal surfaces containing silver, copper or nickel, and has for one of its objects to provide an effective preparation which is capable of being prepared in a simple manner and incorporates relatively inexpensive ingredients.
A preparation for polishing silver has already been proposed which comprises a mild abrasive and an antitarnish agent, with the latter constituted by a mercaptan consisting of a straight chain alkyl primary thiol containing 12 to 20 carbon atoms. Such a preparation when used for cleaning and polishing silver causes an invisible protective coating to be formed on the cleaned metal surface which confers substantial protection against tarnishing as long as .the coating remains intact reducing the frequency with which the silver requires to be cleaned. The anti-tarnishing component of the previously proposed preparation is in some respects lacking in desirable properties and the invention seeks to produce a metal treating preparation which employs as its protective ingredient a medium which besides being economical in cost offers the advantages of low toxicity, great stability resulting in a durable protection for the metal, and having a less objectionable odor than the mercaptan of the previous proposal.
In accordance with the invention in one form there is provided a cleaning or polishing preparation for metal surfaces containing silver, copper or nickel, comprising a cleaning or polishing medium in admixture with a protective medium consisting of an ester of a mercapto carboxylic acid. It is found that such a preparation is very effective in use and relatively economical to pro duce besides offering other advantages referred to herein.
The protective medium may be admixed with a cleaning medium consisting of a physically acting abrasive or one consisting of or comprising a chemically reactive tarnish remover. The cleaning or polishing preparation may take the form of a liquid preparation adapted for application in the manner of a metal polish or a complex forming detarnishing solution or it may be in the form of a paste or cream. Further if desired the cleaning or polishing preparation may be provided in the form of a powder or a semi-solid block suitable for application to a bufling wheel, or it may be impregnated into fiber, fabric or braid normally used for cleaning or polishing operations being held therein either as a powder or as a semi-solid.
The invention also comprises a metal treating preparation for acting on metal surfaces containing silver, copper or nickel comprising a surface treating medium in admixture with a protective medium consisting of an ester of a mercapto carboxylic acid. Such metal treating preparation may consist of a pickling, detarnishing, brightening, de-scaling or etching bath. Thus by the incorporation of the protective medium any such bath may be caused to have tarnish inhibiting properties.
Patented June 30, 1970 The invention further comprises a metal treating liquid protective preparation suitable for addition to a treatment bath for acting on surfaces containing silver, copper or nickel to impart tarnish inhibiting properties, such preparation consisting of a solution in an organic solvent of an ester of a mercapto carboxylic acid.
In practising the invention the substance used to form the protective medium may be any ester of a mercapto carboxylic acid within an appropriate range of such esters. The general formula for such an ester is where R is a group derived from an alcohol of the general form C H OH (aliphatic alcohol) or one derived from an aromatic phenol or aromatic alcohol or from a glycol. The most effective ones of the compounds in which R is derived from an aliphatic alcohol are those having from 8 to 22 carbon atoms in the group R. One such compound found to be particularly useful is stearyl thioglycollate.
Particular examples illustrating how the invention can be carried into effect will now be given, the proportions of the constituents indicated being reckoned by weight.
EXAMPLE 1 A liquid polishing preparation suitable for use on surfaces containing silver, copper or nickel contains the following substances in admixture:
Polishing powder Percent for example diatomaceous earth 20 Ethyl alcohol 20 Stearyl thioglycollate 2.5 Phosphoric acid (as stabiliser) approx. 0.2
Water up to In preparing the preparation according to this example the stearyl thioglycollate is melted and heated to a temperature of approximately 100 C. and is then added to the alcohol. Sufficient of the polishing powder is then added with vigorous stirring until a fairly viscous mixture is obtained. Continuous stirring with a high shear action some water is added and then alternate additions of pol ishing powder and water are made until the mixture is complete. The resultant mixture has a dispersion of thiogly-collate on the surface of the polishing powder which is in turn homogeneously dispersed in the aqueous alcoholic liquid. The phosphoric acid is then stirred homogeneously into the mixture which is thereupon ready for bottling. Advantageously, to improve the stability of the suspension, bentonite may be incorporated in the proportion of about 2 to 4% by Weight. The bentonite may be incorporated by forming it to a gel with part of the water. This gel may be added to the viscous mixture aforesaid before the addition of water thereto.
Acids other than phosphoric acid (for example acetic acid or hydrochloric acid) may be used in place of phosphoric acid to form a stabiliser, although phosphoric acid is preferred for this purpose. The stabilising effect is employed to prolong the shelf life of the liquid product.
EXAMPLE 2 A polishing paste for metal surfaces as aforesaid is made up as follows:
Percent Polishing powder 20 Detergent paste 40 Stearyl mercapto-propionate 2.5 Phosphoric acid (as stabiliser) approx. 0.2
Water up to 100%.
In preparing the paste the mercapto-propionate is first warmed with an equal weight of detergent paste and the resulting liquid is added to the dry ingredients whilst being stirred. The formation of the stiff paste ensures homogenising of the final product. Afterwards the liquid content is added slowly whilst the mixture is stirred.
EXAMPLE 3 An emulsion polish for metal surfaces as aforesaid is made up from the following ingredients:
The emulsion polish is prepared substantially as in the Example 1 above.
EXAMPLE 4 A solvent based paste polish (as opposed to a water based paste polish such as in Example 2) is made up from the following ingredients:
Percent Stearyl thioglycollate 3 Diatomaceous earth 15 Alcohol 4 Hydrocarbon solvent 66 Gelling agent 12 The stearyl thioglycollate is dissolved in the hydrocarbon solvent together with the gelling agent and thoroughly mixed. The alcohol is then added and homogeneousl mixed. Finally the diatomaceous earth is stirred into the mixture.
EXAMPLE 5 A cleaning and polishing powder for use on metal surfaces as aforesaid comprises the following:
Grams Polishing powder e.g. kieselguhr, aluminum oxide '98 Stearyl thioglycollate 62 These constituents are thoroughly blended by grinding. The resulting preparation may be used as such or may be incorporated into a suitable polishing cloth or braid etc.
EXAMPLE 6 A liquid protective preparation which may be added in a small proportion to a pickling, detarnishing, brightening, de-scaling or etching bath for acting on surfaces containing silver, copper or nickel, to impart tarnish inhibiting properties is formed by dissolving stearyl thioglycollate in isopropyl alcohol in the proportion of 2.5% by weight.
EXAMPLE 7 An emulsion type dipping solution being a protective preparation suitable for treating metal surfaces as above mentioned by immersion therein or for adding in a small proportion to various kinds of baths as in Example 6 is made up of the following constituents:
Parts Stearyl thioglycollate 3 Ethoxylated fatty alcohol (fatty alcohol/ethylene oxide condensate) 3 Phosphoric acid 0.2
Water 94 EXAMPLE 8 A dipping solution of organic solvent type suitable for use in similar manner to Examples 6 and 7 is prepared by dissolving stearyl thioglycollate in a hydrocarbon solvent in the proportion of 2% thioglycollate to 98% solvent.
4 EXAMPLE 9 A solid polishing composition suitable for mechanical application comprises the following:
Parts Higher fatty acid (e.g. stearic acid) 19 Microcrystalline wax 8 Triethanolarnine l Polishing powder, e.g. tripoli powder 8O Lauryl thioglycollate 12 What we claim is:
1. In a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel, the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H COOR wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufficient to protect the metal surface against tarnishing.
2. In a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel and which contains an abrasive, the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H -COO-R wherein n is l or 2 and R is C H wherein n is 8 to 22, in an amount sufficient to protect the metal surface against tarnishing.
3. In a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel and which contains a tarnish remover, the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufficient to protect the metal surface against tarnishing.
4. In a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel and which contains a pickling, detarnishing, brightening, descaling or etching agent, the improvement which. comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H -C-OOR wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufficient to protect the metal surface against tarnishing.
5. In a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel in cream form, the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H C-OOR wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufiicient to protect the metal surface against tarnishing.
6. In a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel in powder form, the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H COO-R wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufiicient to protect the metal surface against tarnishing.
7. In a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel in liquid form, the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H COOR wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufficient to protect the metal surface against tarnishing.
8. In a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel in paste form, the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H -COOR wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufficient to protect the metal surface against tarnishing.
9. In a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel in semi-solid block form, the improvement which comprises the addition of an ester of a mercapto carboxylic acid of the formula HSC H COOR wherein n is 1 or 2 and R is C H wherein n is 8 to 22, in an amount sufiicient to protect the metal surface against tarnishing.
10. In a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel, the improvement which comprises the addition of stearyl thioglycollate in an amount suflicient to protect the metal surface against tarnishing.
11. In a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel, the improvement which comprises the addition of stearyl mercapto propionate in an amount suificient to protect the metal surface against tarnishing.
12. In a cleaning, polishing or coating composition for protecting metal surfaces containing silver, copper or nickel, the improvement which comprises the addition of lauryl thioglycollate in an amount suflicient to protect the metal surface against tarnishing.
13. In a cleaning, polishing or coating composition for treating silver surfaces, the improvement which consists in the inclusion of a proportion of the octadecyl ester of a thiocarboxylic acid having the formula:
HSC H COOH wherein n is 1 or 2, sufficient to inhibit tarnishing of the silver.
References Cited UNITED STATES PATENTS 2,841,501 7/1958 Murphy 106-3 XR 2,947,599 8/1960 Ennis. 3,248,235 4/1966 Pryor 1063 JULIUS FROME, Primary Examiner L. B. HAYES, Assistant Examiner US. Cl. X.R.
Claims (1)
1. IN A CLEANING, POLISHING OR COATING COMPOSITION FOR PROTECTING METAL SURFACES CONTAINIG SILVER, COPPER OR NICKEL, THE IMPROVEMENT WHICH COMPRISES THE ADDITION OF AN ESTER OF A MERCAPTO CARBOXYLIC ACID OF THE FORMULA HSCNH2N-C-OO-R WHEREIN N IS 1 OR 2 AND R IS CNH2N+1 WHEREIN N IS 8 TO 22, IN AN AMOUNT SUFFICIENT TO PROTECT THE METAL SURFACE AGAINST TARNISHING.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB25235/63A GB1070383A (en) | 1963-06-25 | 1963-06-25 | Improvements in or relating to metal protecting preparations |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3518098A true US3518098A (en) | 1970-06-30 |
Family
ID=10224398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US377391A Expired - Lifetime US3518098A (en) | 1963-06-25 | 1964-06-23 | Metal protecting preparations |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3518098A (en) |
| DE (1) | DE1519159A1 (en) |
| GB (1) | GB1070383A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4305779A (en) * | 1980-05-28 | 1981-12-15 | The United States Of America As Represented By The United States Department Of Energy | Method of polishing nickel-base alloys and stainless steels |
| US4459158A (en) * | 1982-09-29 | 1984-07-10 | Phillips Petroleum Company | Sulfur based metal cleaners |
| US4640713A (en) * | 1984-11-19 | 1987-02-03 | S. C. Johnson & Son, Inc. | Tarnish remover/metal polish formulation comprising a metal iodide, an acid, and water |
| US5487792A (en) * | 1994-06-13 | 1996-01-30 | Midwest Research Institute | Molecular assemblies as protective barriers and adhesion promotion interlayer |
| US6361872B1 (en) | 1998-05-15 | 2002-03-26 | Metal Coatings International Inc. | Metal surface treatment agents, methods of treating metal surfaces and pre-coated steel substrates |
| GB2412666A (en) * | 2004-03-30 | 2005-10-05 | Cole Paul Gilbert | Water-based metal treatment composition |
| US20070039665A1 (en) * | 2003-03-31 | 2007-02-22 | Johns Peter G | Enhancing silver tarnish-resistance |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2841501A (en) * | 1957-04-17 | 1958-07-01 | James G Murphy | Silver polish |
| US2947599A (en) * | 1955-07-05 | 1960-08-02 | Little Inc A | Corrosion inhibitors |
| US3248235A (en) * | 1961-09-28 | 1966-04-26 | Minnesota Mining & Mfg | Anti-tarnish composition for coppercontaining surfaces |
-
1963
- 1963-06-25 GB GB25235/63A patent/GB1070383A/en not_active Expired
-
1964
- 1964-06-23 US US377391A patent/US3518098A/en not_active Expired - Lifetime
- 1964-06-25 DE DE19641519159 patent/DE1519159A1/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2947599A (en) * | 1955-07-05 | 1960-08-02 | Little Inc A | Corrosion inhibitors |
| US2841501A (en) * | 1957-04-17 | 1958-07-01 | James G Murphy | Silver polish |
| US3248235A (en) * | 1961-09-28 | 1966-04-26 | Minnesota Mining & Mfg | Anti-tarnish composition for coppercontaining surfaces |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4305779A (en) * | 1980-05-28 | 1981-12-15 | The United States Of America As Represented By The United States Department Of Energy | Method of polishing nickel-base alloys and stainless steels |
| US4459158A (en) * | 1982-09-29 | 1984-07-10 | Phillips Petroleum Company | Sulfur based metal cleaners |
| US4640713A (en) * | 1984-11-19 | 1987-02-03 | S. C. Johnson & Son, Inc. | Tarnish remover/metal polish formulation comprising a metal iodide, an acid, and water |
| US5487792A (en) * | 1994-06-13 | 1996-01-30 | Midwest Research Institute | Molecular assemblies as protective barriers and adhesion promotion interlayer |
| US6361872B1 (en) | 1998-05-15 | 2002-03-26 | Metal Coatings International Inc. | Metal surface treatment agents, methods of treating metal surfaces and pre-coated steel substrates |
| US20070039665A1 (en) * | 2003-03-31 | 2007-02-22 | Johns Peter G | Enhancing silver tarnish-resistance |
| GB2412666A (en) * | 2004-03-30 | 2005-10-05 | Cole Paul Gilbert | Water-based metal treatment composition |
| US20070277906A1 (en) * | 2004-03-30 | 2007-12-06 | Middlesex Silver Co., Limited | Water-Based Metal Treatment Composition |
| GB2412666B (en) * | 2004-03-30 | 2008-10-08 | Paul Gilbert Cole | Water-based metal treatment composition |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1070383A (en) | 1967-06-01 |
| DE1519159A1 (en) | 1969-06-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: FIRST WISCONSIN FINANCAL CORPORATION, 622 NORTH CA Free format text: SECURITY INTEREST;ASSIGNOR:MERTZ EINHORN INVESTORS-I, INC.;REEL/FRAME:004565/0689 Effective date: 19860219 |