US2753304A - Lubricating composition - Google Patents

Lubricating composition Download PDF

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US2753304A
US2753304A US536786A US53678655A US2753304A US 2753304 A US2753304 A US 2753304A US 536786 A US536786 A US 536786A US 53678655 A US53678655 A US 53678655A US 2753304 A US2753304 A US 2753304A
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soap
oil
sulfonated
borax
water
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US536786A
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Gilbert H Orozco
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Pennsylvania Salt Manufacturing Co
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Pennsylvania Salt Manufacturing Co
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M111/00Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/02Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a non-macromolecular organic compound
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02Water
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06Metal compounds
    • C10M2201/062Oxides; Hydroxides; Carbonates or bicarbonates
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    • C10M2201/085Phosphorus oxides, acids or salts
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    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/10Compounds containing silicon
    • C10M2201/102Silicates
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/14Synthetic waxes, e.g. polythene waxes
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/16Paraffin waxes; Petrolatum, e.g. slack wax
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    • C10M2205/17Fisher Tropsch reaction products
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/021Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/287Partial esters
    • C10M2207/289Partial esters containing free hydroxy groups
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40Fatty vegetable or animal oils
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40Fatty vegetable or animal oils
    • C10M2207/404Fatty vegetable or animal oils obtained from genetically modified species
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08Amides
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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    • C10M2215/082Amides containing hydroxyl groups; Alkoxylated derivatives
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    • C10M2215/28Amides; Imides
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    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/10Phosphatides, e.g. lecithin, cephalin
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    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/02Groups 1 or 11
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/24Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/241Manufacturing joint-less pipes
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/242Hot working
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/243Cold working
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
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    • C10N2040/244Metal working of specific metals
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/244Metal working of specific metals
    • C10N2040/245Soft metals, e.g. aluminum
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
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    • C10N2040/244Metal working of specific metals
    • C10N2040/246Iron or steel
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    • C10N2040/00Specified use or application for which the lubricating composition is intended
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    • C10N2040/247Stainless steel
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    • C10N2060/00Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/04Oxidation, e.g. ozonisation

Definitions

  • This invention relates to an improved lubricating composition for forming on metal stock, to be drawn or otherwise formed, a dry, homogeneous, self-adherent and tenacious lubricating and protective coating and particularly to an improved lubricating composition of which the principal lubricating ingredients are watensoluble soaps and one or more water-soluble inorganic waterliberating and glass-forming materials, of which all, or a major part, is an alkali metal borate.
  • the present invention also is an improvement on the composition disclosed in U. S. Letters Patent No. 2,530,- 837, issued to Orozco and Hendricks on November 21, 1950, and Reissue No. 23,184, issued to Roland A. Whitbeck on December 20, 1949.
  • the present improved composition relates to the type of lubricant commonly referred to as dry lubricant which is applied as an aqueous solution to the metal stock by dipping, spraying, or similar operation, and caused, or permitted, to dry thereon so as to form on the stock a dry, homogeneous, self-adherent, and tenacious protective and lubricating film as a result of which the dry coated stock can be subjected to pressure die forming operations and the like without the addition of other lubricating and cooling agents.
  • compositions comprising water-soluble soap and one or more water-soluble, inorganic, water-liberating and glass-forming materials provide an effective coating for the metal stock during the desired drawing operations.
  • compositions are generally used on large production lines in which many pieces of stock are continuously passing through the aqueous solutions to receive the coating.
  • Some difiiculty has occurred in this mass method of coating in that the organic and inorganic materials tend to draw out of the bath unevenly. This is objectionable since the ratio of organic to inorganic material will continuously change with the resulting coated stock possessing a coating that may contain a ratio of ingredients that is undesirable.
  • the coupling agent, or combined coupling and plasticizing agent, or mixture of individual coupling and individual plasticizing agents, are added primarily to maintain the bath in uniform condition as the bath is drawn out or used up due to its application to the stock by dipping, spraying, and the like.
  • the coupler or combined coupler and plasticizer the ratios of organic to inorganic material in the bath changes continuously during the application of the bath to the stock and it is very difficult to maintain a relatively constant ratio of organic to inorganic material in the bath by adding one or the other and proportionate amounts of water.
  • the more equal draw out of the bath as a result of using a coupler or combined plasticizer and coupler appears to be due to a combined chemical and physical efiect and the reduction of innerfacial tension.
  • the plasticizing effect apparently increases the adherence and pliability and coating which is beneficial in preventing dislodgment of the coating in intial stages of the draw in the dies. Instead, the plasticized coating will remain in place on the stock during operation of the die and thus will be carried into the proper place between the working faces of the die and stock.
  • the plasticizing effect also assists in effecting uniform draw out of the bath. Again it eliminates the tendency of the coating to rub off as the stock drags across the cavity edges near the entrance of the female die.
  • composition of the present invention comprises water-soluble high titre soap of which the melting point of the fatty acid content is at least about 36 C. or more and, in addition thereto, a larger amount of an alkali metal borate, in combination with a small amount of water-soluble coupling material and preferably both coupling and plasticizing material which may be a combined coupler and plasticizer or may be a mixture of a separate coupler and a separate plasticizer.
  • composition is to be one to perform stepwise lubrication as set forth in the above-identified Orozco and Hendricks patent, one or more other water soluble, inorganic, water-liberating and glass-forming compounds, preferably alkali metal salts may be substituted for part of the borate though the total of such additional compounds should be maintained at less than the total amount of borax.
  • the preferred water-soluble soaps to be employed in the formulation of compositions and in accordance with the present invention are high titre soaps, and particularly high titre soaps in which the mixed saponifiable fatty acid content thereof possesses a melting point of at least about 36 C.
  • any water-soluble soaps that will provide the desired lubricity and will permit the formation of the necessary dry homogeneous coating of the completed composition without material moisture pick-up can. be employed.
  • the agent to impart the coupling and plasticizing properties to the composition may be in the form of a single compound having both these characterisics or a separate coupler and a separate plasticizing agent may be employed.
  • the coupler and plasticizer are employed in the ratio of about 4 parts of plasticizer to about 1 part coupler. The total amount of the two agents will be used within the range above set forth.
  • the combined plasticizer and coupler is about 20% coupler and about 80% plasticizer, this being about 1 to 4 ratio of coupling effect to plasticizing effect.
  • separate couplers are usually 100% couplers whereas separate plasticizers have about the same plasticizing effect as a combined plasticizer and coupler. Therefore, when separate coupling and separate plasticizing agents are used, the separate plasticizer is about /5 of the total of the two with the coupler being about /5 of the total.
  • the active lubricating ingredients of the composition and their functions when applied to the stock are clearly set forth in detail in the Orozco and Hendricks and Whitbeck patents hereinbefore identified. These patents give in detail the particular ingredients to be employed as well as the manner in which the particular proportions may be varied for the most economical and efficient operation relative to the particular draw.
  • the high titre soap employed is one having a melting point of at least about 36 C.
  • there are a great many high titre soaps having melting points well above 36 C. such as, for example, hydrogenated palm oil soap, hydrogenated tallow soap, stearin flux soap, triple-pressed. tallow soap, cocoa butter soap, coaceric soap, Japanic soap, and borneo tallow soap, etc.
  • the preferred soaps are tallow soap or palm oil soap having a melting point of at least about 36 C. or more, or any high titre soap having a melting point ranging from about 36 C. up. A titre of at least 41 C. is preferred for heavy draws. It is to be understood that a single soap may be used or it may be admixed with one or more other and additional soaps.
  • the water-soluble, inorganic, water-liberating, and glass-forming materials may be in the form of a single compound, this single compound being an alkali metal borate and preferably borax. That is to say, for many types of drawing operations, the alkali metal borate will be the sole inorganic lubricating ingredient. However, when stepwise lubrication is required as described in detail in the Orozco patent, one or more inorganic, water-soluble, water-liberating and glass-forming materials will be used.
  • these additional inorganic materials will be alkali metal salts such as, for example, sodium (mono-, di-, and tri-) phos- .4 phate, potassium (mono-, di-, and tri-), sodium carbonate, potassium carbonate, boric (ortho, meta and pyro) acid, sodium silicate, potassium silicate, etc.
  • alkali metal salts such as, for example, sodium (mono-, di-, and tri-) phos- .4 phate, potassium (mono-, di-, and tri-), sodium carbonate, potassium carbonate, boric (ortho, meta and pyro) acid, sodium silicate, potassium silicate, etc.
  • a single compound having both coupling and plasticizing properties in the blended'composition.
  • An illustrative class of materials possessing this dual function are sulfonated animal and vegetable oils and sulfonated unsaturated fatty acid derivatives thereof.
  • Sulfonated mineral oil compounds in most circumstances are of no utility due to their inability to be effectively incorporated in the composition when in solution, although salts of sulfonated mineral oil derivatives, such as, for example, mahogany soaps, can be employed in the composition since this particular class of materials may be incorporated into the ultimate composition with little difficulty.
  • sulfonated vegetable oils which may be employed are as follows: castor, palm, palm kernel, oliverape seed, mustard seed, tea seed, sun flower seed, and coconut.
  • sulfonated animal oils and fats that may be used are tallow, neats-foot oil, lard oil, cod, herring, and whale oils, sperm, wool grease, oleicacid, ricinoleic, linoleic, etc.
  • the preferred material is a sulfonated vegetable oil with particular preference to be had for sulfonated castor oil.
  • This compound is about 20% coupler and plasticizer. If, for example, three parts of sulfonated castor oil is specified in a particular formula and a substitution is to be made therefor of a separate coupler and a separate plasticizer, the three parts would be made up of /2 part of coupler and 2 /2 parts of plasticizer.
  • any surface active agent may be used.
  • These compounds known as surface active agents are alkali metal salts of sulfates of long-chain alcohols, metal salts of sulfates of glyceridcs, alkylaryl metal sulfonates, pentaerythritol monocsters, esters of sulfosuccinic acid, sulfated aliphatic esters, and metal salts of sulfonated esters of aromatic-hydrocarbons.
  • surface active agents are sodium lauryl sulfate, sodium cetyl sulfate, sodium oleyl sulfate, potassium lauryl sulfate, sodium giyceryl monoiaurate sulfate, dioctyl sodium sulfosuccinate, diceryl potassium sulfosuccinate, sodium keryl benzene sulfonate, sodium oleyl naphthalene sulfonate, and dihexyl sodium suitosuccinate.
  • surface active agents are sodium lauryl sulfate, sodium cetyl sulfate, sodium oleyl sulfate, potassium lauryl sulfate, sodium giyceryl monoiaurate sulfate, dioctyl sodium sulfosuccinate, diceryl potassium sulfosuccinate, sodium keryl benzene sulfonate, sodium oleyl naphthalene
  • any of the vegetable and animal fats may be employed. That is to say, any of the oils which, when sulfonated, can be used as combined couplers and pissticizers may, if emulsified, but not sulfonated, be used as a plasticizer only.
  • plasticizers may be saponifled oxygenated petroleum derivatives, water-soluble glycols, amorphous or microcrystalline waxes, etc. may be used. Of these materials, animal wool fat and rape seed oil are preferred.
  • Example 1 Parts Tallow soap 15 Borax 83 Sulfonated castor oil 2
  • Example 2 Palm oil soap 6
  • Borax 82 Sulfonated castor oil 2
  • Example 3 Palm oil soap 19.5
  • Borax 80 Sulfonated castor oil .5
  • Example 9 Tallow soap 22 Borax 75 Sulfonated castor oil 3
  • Example 10 Palm oil soap 17 Borax 78 Sulfonated castor oil 5
  • Example 11 Palm oil soap 17 Potassium borate 79.5 Sulfonated cotton seed oil 3.5
  • Example 12 Tallow soap Potassium borate 84 Lithium borate Sulfonated cotton seed oil 1
  • Example 13 Tallow soap 15.5 Lithium borate -o 84 Sulfonated palm kernel oil .5
  • Example 14 Parts Stearin flux soap 22 Borax 77 Sulfonated castor oil 1
  • Example 15 Hydrogenated tallow soap l9 Borax 78.5 Sulfonated coconut oil 2.5
  • Example 16 Hydrogenated palm oil soap 24 Borax 73 Sulfonated coconut oil 3 Sulfonated mustard seed oil
  • Example 17 Triple-pressed tallow soap 20
  • Example 18 Cocoa butter soap 19.5 Potassium borate Sulfonated lard oil .5
  • Example 19 Stearin flux soap 27 Lithium borate 72 Sulfonated tallow oil 1
  • Example 20 Coaceric soap 16
  • Borax 82.5 Sulfonated castor oil 1.5
  • Example 22 Borneo tallow soap 21 Borax 75 Lithium borate Sulfonated herring oil 4
  • Stearic acid soap 20 Borax 79 Sulfonated sperm oil 1
  • Example 24 Stearin flux soap 22
  • Stearic acid soap Borax 74 Lithium borate Sulfonated whale oil 4 Sulfonafed sperm oil
  • Example 25 Borneo tallow soap 18 Triple-pressed palm oil soap Borax 80 Sulfonated herring oil; 2
  • Example 26 Stearin flux soap 21 Borax 78 Sulfonated castor oil 1 vems-s04 7 Example 27 Parts Tallow soap 22 Borax 1 55 Potassium carbonate 2'1 Sulfonated sperm oil 2 Example 28 Tallow soap 19 Stearin fiux soap Boric acid '70 Borax l Sulfonated oleic acid .5
  • Example 30 Cocoa butter soap 15 Lithium borate 83 Sulfouated ricinoleic acid 2
  • Example 32 Palm oil soap 20 Borax 57 Sodium silicate 5 Potassium carbonate 15 Sulfonatcd castor oil 3
  • Example 33 Tallow soap 15 Borax a- 45 Sodium carbonate 15 Sodium silicate Trisodium phosphate 12 Sulfonated cast'or oil 3
  • Example 34 Tallow soap Borax 40 Boric acid Potassium carbonate 22 Sulfonated castor oil 2
  • Example 36 Palm oil soap 22 Tallow soap Borax 55 Sodium silicate 5 Boric acid 8 Potassium carbonate 8 Sulfonated corn oil 2
  • Example 38 Parts Japanic so'ap 20 Potassium borate 65 Sodium carbonate 5 Potassium phosphate 5 Boric acid 4 Mahogany soap Sulfonated oleic acid "i 1
  • Example 39 Tallow soap 12
  • Borax 86 Sodium lauryl sulfate Cottonseed oil ..i 2
  • Example 40 Palm oil soap 20 Borax 77 Sodium octyl sulfatesperm oil i 3
  • Palm oil soap Tallow soap 16 Potassium borate 80
  • Stearin flux soap 24 Potassium borate Lithium borate .i Dioctyl sodium sulfosuccinate Animal wool fat i 1
  • Hydrogenated tallow soap 18 Borax 77 Pentaerythrital monostearate Corn oil "i 5
  • Example 44 Hydrogenated palm oilsoap l5 Borax Potassium borate n ⁇ Pentaerythrital monolaurate Palm oil l i
  • Example 46 Coaceric soap 14.5 Potassium borate 82 Sodium ricinoelyl sulfate Coconut oil .i
  • Example 48 Stearin flux soap Stearic acid soap 20 Borax 77 Sodium lauryl sulfate Palm kernel oil i 3
  • Example 49 Borneo tallow soap 11 Japanic soap Lithium borate 87 Potassium cetyl sulfate 2 Lecithin appease Example 50.
  • the resultant solution is applied to the stock to be drawn in any suitable manner such, for example, as by dipping, after which the coated stock is permitted to dry or is dried by the application of heat so as to form on the stock a dry, homogeneous, selfadherent, lubricating film which is very tenacious and which remains on the stock under normal storage conditions, both protecting it during storage and providing all the lubricant that is necessary when the stock is subsequently drawn.
  • the thinnest coating consistent with proper lubrication is desirable.
  • the dry mix is used in an amount of about two ounces per gallon of water.
  • the dry mix may be used in an amount as high as two pounds per gallon.
  • composition or film By the term consisting essentially of as used herein in defining the coating composition or film, it is meant to define a composition or film containing the claimed ingredients, in the relative proportions stated as the possible and actual constituents of the composition or film, but it is not meant to exclude the presence of minor amounts of conventional compounds or ingredients, the
  • a coating material for admixture with water for coating a piece of blank metal stock in forming thereon a self-adherent dry homogeneous lubricating and protecting film consisting essentially of the following lubricating ingredients Parts Water-soluble, high titre soap having a melting point of at least about 36 C 10 to 30 Water-soluble, inorganic, water liberating and glass forming material of: which at least a major part thereof is an alkali metal borate 70 to 90 Coupling and plasticizing material selected from the groups consisting of the following: /2 to 5 A.
  • Coupling and plasticizing material in the form of at least two compounds, at least one compound being selected from each of the following groups 1.
  • Coupling agent Surface active, water-soluble,
  • alkali metal salts or" organic compounds containing a sulfa-group in the molecule
  • Plasticizing agent Vegetable oils and animal oils.
  • a coating material in accordance with claim 1 wherein the coupling and plasticizing material is a sulfonated vegetable oil.
  • a coating material in accordance with claim 1 wherein the coupling and plasticizing material is a sulfonated animal oil.
  • a coating material in accordance with claim 1 wherein the coupling and plasticizing material is a sulfonated unsaturated fatty acid derived from animal oil and vegetable oil.
  • a coating material in accordance with claim 1 wherein the coupling and plasticizing material is sulfonated castor oil.
  • a coating material in accordance with claim 1 wherein the coupling and plasticizing material is sulfonated cottonseed oil.
  • a coating material in accordance with claim 1 wherein the coupling and plasticizing material is sulfonated corn oil.
  • a coating composition in accordance with claim 1 wherein the coupling agent is an alkali metal organic sulfonate.
  • a coating composition in accordance with claim 1 wherein the coupling agent is an alkali metal salt of a sulfate of an aliphatic alcohol.
  • a coating composition in accordance with claim 1 wherein the coupling agent is sodium lauryl sulfate.
  • a coating material for admixture with water for coating a piece of blank metal stock and forming thereon a self-adherent, dry, homogeneous lubricating and protecting film consisting essentially of the following ingredients by weight:
  • Parts A-water-soluble soap 10 to 30 Water-soluble, inorganic, water liberating and glass forming material of which at least a major part thereof is an alkali metal borate 70 to 90 Coupling and plasticizing material selected from the groups consisting of the following: /2 to 5
  • A. Combined coupling and plasticizing material in the form of at least one compound selected from the group consisting of sulfonated vegetable oils, sulfonated animal oils, and sulfonated unsaturated fatty acid derived from animal oil and vegetable oil; a
  • Coupling agent Surface active, water-soluble alkali metal salts of organic compounds containing a sulfo-group in the molecule; 2.
  • Plasticizingtagent Vegetable oils and animal oils.

Description

LUBRICATING COMPOSITION Gilbert H. Orozco, Euclid, Ohio, assignor to Pennsylvania Salt Manufacturing Co., Philadelphia, Pa., a corporation of Pennsylvania No Drawing. Application September 26, 1955, Serial No. 536,786
Claims. (Cl. 252-18) This invention relates to an improved lubricating composition for forming on metal stock, to be drawn or otherwise formed, a dry, homogeneous, self-adherent and tenacious lubricating and protective coating and particularly to an improved lubricating composition of which the principal lubricating ingredients are watensoluble soaps and one or more water-soluble inorganic waterliberating and glass-forming materials, of which all, or a major part, is an alkali metal borate.
The present invention also is an improvement on the composition disclosed in U. S. Letters Patent No. 2,530,- 837, issued to Orozco and Hendricks on November 21, 1950, and Reissue No. 23,184, issued to Roland A. Whitbeck on December 20, 1949.
The present improved composition relates to the type of lubricant commonly referred to as dry lubricant which is applied as an aqueous solution to the metal stock by dipping, spraying, or similar operation, and caused, or permitted, to dry thereon so as to form on the stock a dry, homogeneous, self-adherent, and tenacious protective and lubricating film as a result of which the dry coated stock can be subjected to pressure die forming operations and the like without the addition of other lubricating and cooling agents. As disclosed in the above-enumerated patents, compositions comprising water-soluble soap and one or more water-soluble, inorganic, water-liberating and glass-forming materials provide an effective coating for the metal stock during the desired drawing operations. Such compositions are generally used on large production lines in which many pieces of stock are continuously passing through the aqueous solutions to receive the coating. Some difiiculty has occurred in this mass method of coating in that the organic and inorganic materials tend to draw out of the bath unevenly. This is objectionable since the ratio of organic to inorganic material will continuously change with the resulting coated stock possessing a coating that may contain a ratio of ingredients that is undesirable.
It is impractical to attempt to adjust or correct the bath for this constant change of ratio of ingredients due to the fact that the coating operation is continuous. Such an adjustment would require the taking of a sample of the bath and a resulting analysis thereof to determine the ratio of the ingredients. This procedure would be lengthy and by the time it would be completed, a large number of pieces of stock would have been passed through the bath with a possible further changing of the ratio of the ingredients. Similarly, the shutting down of the production line to take the sample and resulting analysis thereof would be economically unfeasible. Moreover, the maintenance of the bath at a constant ratio of organic to inorganic material usually is beyond the skill of the ordinary workman.
It has been found that by the addition of a coupling agent, or coupling and plasticizing agent, to the composition the aqueous solution thereof draws out uninited States Patent 0 "ice formly, thus maintaining a uniform ratio of organic to inorganic material both in the bath and on the coated stock. The coupler alone has a marked effect upon maintenance of uniformity of the draw out of the bath and this is further enhanced by the presence in the bath of a plasticizer either as a separate material or in the form of a combined coupling and plasticizing material. In addition, and as a secondary effect, not only is the resultant coat on the stock more uniform in the ratio of organic to inorganic material, but it also appears to have a better consistency resulting in a more uniform drawing operation. Moreover, as a result of the use of this improved composition, the initial bath as used up can be increased from time to time merely by adding more of the original composition and a proportional amount of water so that the danger of changing the ratio of organic to inorganic material is eliminated.
The coupling agent, or combined coupling and plasticizing agent, or mixture of individual coupling and individual plasticizing agents, are added primarily to maintain the bath in uniform condition as the bath is drawn out or used up due to its application to the stock by dipping, spraying, and the like. Without the coupler or combined coupler and plasticizer the ratios of organic to inorganic material in the bath changes continuously during the application of the bath to the stock and it is very difficult to maintain a relatively constant ratio of organic to inorganic material in the bath by adding one or the other and proportionate amounts of water. The more equal draw out of the bath as a result of using a coupler or combined plasticizer and coupler appears to be due to a combined chemical and physical efiect and the reduction of innerfacial tension. The plasticizing effect apparently increases the adherence and pliability and coating which is beneficial in preventing dislodgment of the coating in intial stages of the draw in the dies. Instead, the plasticized coating will remain in place on the stock during operation of the die and thus will be carried into the proper place between the working faces of the die and stock. The plasticizing effect also assists in effecting uniform draw out of the bath. Again it eliminates the tendency of the coating to rub off as the stock drags across the cavity edges near the entrance of the female die.
The composition of the present invention comprises water-soluble high titre soap of which the melting point of the fatty acid content is at least about 36 C. or more and, in addition thereto, a larger amount of an alkali metal borate, in combination with a small amount of water-soluble coupling material and preferably both coupling and plasticizing material which may be a combined coupler and plasticizer or may be a mixture of a separate coupler and a separate plasticizer. If the composition is to be one to perform stepwise lubrication as set forth in the above-identified Orozco and Hendricks patent, one or more other water soluble, inorganic, water-liberating and glass-forming compounds, preferably alkali metal salts may be substituted for part of the borate though the total of such additional compounds should be maintained at less than the total amount of borax.
While as indicated above and in the patents hereinbefore enumerated, the preferred water-soluble soaps to be employed in the formulation of compositions and in accordance with the present invention are high titre soaps, and particularly high titre soaps in which the mixed saponifiable fatty acid content thereof possesses a melting point of at least about 36 C., it is to be understood that any water-soluble soaps that will provide the desired lubricity and will permit the formation of the necessary dry homogeneous coating of the completed composition without material moisture pick-up can. be employed.
Range, Preferred,
parts parts Water-soluble high titre soap having a melting point of at least about 36 C 10'to 3O 20 Water-soluble, inorganic, water-liberating and glass-forming material of which all, or a major part, is an alkali metal borate 70 to 90 80 Coupling and plastieizing material to 1 As hereinbefore indicated, the agent to impart the coupling and plasticizing properties to the composition may be in the form of a single compound having both these characterisics or a separate coupler and a separate plasticizing agent may be employed. When separate agents are used, the coupler and plasticizer are employed in the ratio of about 4 parts of plasticizer to about 1 part coupler. The total amount of the two agents will be used within the range above set forth. in determining the ratio of separate couplers and plasticizers to each other to provide essentially the equivalent of a combined plasticizer and coupler, it is to be noted that the combined plasticizer and coupler is about 20% coupler and about 80% plasticizer, this being about 1 to 4 ratio of coupling effect to plasticizing effect. However, separate couplers are usually 100% couplers whereas separate plasticizers have about the same plasticizing effect as a combined plasticizer and coupler. Therefore, when separate coupling and separate plasticizing agents are used, the separate plasticizer is about /5 of the total of the two with the coupler being about /5 of the total.
The active lubricating ingredients of the composition and their functions when applied to the stock are clearly set forth in detail in the Orozco and Hendricks and Whitbeck patents hereinbefore identified. These patents give in detail the particular ingredients to be employed as well as the manner in which the particular proportions may be varied for the most economical and efficient operation relative to the particular draw. Generally, the high titre soap employed is one having a melting point of at least about 36 C. However, there are a great many high titre soaps having melting points well above 36 C. such as, for example, hydrogenated palm oil soap, hydrogenated tallow soap, stearin flux soap, triple-pressed. tallow soap, cocoa butter soap, coaceric soap, Japanic soap, and borneo tallow soap, etc. The preferred soaps are tallow soap or palm oil soap having a melting point of at least about 36 C. or more, or any high titre soap having a melting point ranging from about 36 C. up. A titre of at least 41 C. is preferred for heavy draws. It is to be understood that a single soap may be used or it may be admixed with one or more other and additional soaps.
As indicated in the above patents, the water-soluble, inorganic, water-liberating, and glass-forming materials may be in the form of a single compound, this single compound being an alkali metal borate and preferably borax. That is to say, for many types of drawing operations, the alkali metal borate will be the sole inorganic lubricating ingredient. However, when stepwise lubrication is required as described in detail in the Orozco patent, one or more inorganic, water-soluble, water-liberating and glass-forming materials will be used. In general, these additional inorganic materials will be alkali metal salts such as, for example, sodium (mono-, di-, and tri-) phos- .4 phate, potassium (mono-, di-, and tri-), sodium carbonate, potassium carbonate, boric (ortho, meta and pyro) acid, sodium silicate, potassium silicate, etc.
As hereinbefore indicated, it is preferred to employ a single compound having both coupling and plasticizing properties in the blended'composition. An illustrative class of materials possessing this dual function are sulfonated animal and vegetable oils and sulfonated unsaturated fatty acid derivatives thereof. Sulfonated mineral oil compounds in most circumstances are of no utility due to their inability to be effectively incorporated in the composition when in solution, although salts of sulfonated mineral oil derivatives, such as, for example, mahogany soaps, can be employed in the composition since this particular class of materials may be incorporated into the ultimate composition with little difficulty.
Illustrative examples of sulfonated vegetable oils which may be employed are as follows: castor, palm, palm kernel, oliverape seed, mustard seed, tea seed, sun flower seed, and coconut.
Among the sulfonated animal oils and fats that may be used are tallow, neats-foot oil, lard oil, cod, herring, and whale oils, sperm, wool grease, oleicacid, ricinoleic, linoleic, etc.
Of the foregoing compounds possessing both coupling and plasticizing characteristics, the preferred material is a sulfonated vegetable oil with particular preference to be had for sulfonated castor oil. This compound is about 20% coupler and plasticizer. If, for example, three parts of sulfonated castor oil is specified in a particular formula and a substitution is to be made therefor of a separate coupler and a separate plasticizer, the three parts would be made up of /2 part of coupler and 2 /2 parts of plasticizer.
When a separate coupler is to be employed, any surface active agent may be used. These compounds known as surface active agents are alkali metal salts of sulfates of long-chain alcohols, metal salts of sulfates of glyceridcs, alkylaryl metal sulfonates, pentaerythritol monocsters, esters of sulfosuccinic acid, sulfated aliphatic esters, and metal salts of sulfonated esters of aromatic-hydrocarbons. Specific examples of such surface active agents are sodium lauryl sulfate, sodium cetyl sulfate, sodium oleyl sulfate, potassium lauryl sulfate, sodium giyceryl monoiaurate sulfate, dioctyl sodium sulfosuccinate, diceryl potassium sulfosuccinate, sodium keryl benzene sulfonate, sodium oleyl naphthalene sulfonate, and dihexyl sodium suitosuccinate. For a complete list, including the above compounds, as Well as fatty acid amides and esters known as surface active agents, reference is to be had to the article published in Industrial and Engineering Chemistry," vol. 35, pp. 126-130, which gives a complete listing of com mereially available surface active agents as well as identifying such agents chemically. Of these surface active agents the alkali metal salts of sulfates of long-chain alcohols containing from about 8 to 18 carbon atoms are preferred. As a separate plasticizer to be employed in conjunction with one of the above-mentioned surface active agents, any of the vegetable and animal fats may be employed. That is to say, any of the oils which, when sulfonated, can be used as combined couplers and pissticizers may, if emulsified, but not sulfonated, be used as a plasticizer only. A rather detailed list of such oils is given hereinbefore and, if unsulfonated, may be used as the plasticizer. Other plasticizers may be saponifled oxygenated petroleum derivatives, water-soluble glycols, amorphous or microcrystalline waxes, etc. may be used. Of these materials, animal wool fat and rape seed oil are preferred.
Having described in detail the ingredients to be employed in formulating the composition of the present invention, it therefore becomes convenient to give a number of illustrative working examples of finished compositions which illustrate the present invention. In the following examples, the ratios given are by weight.
Example 1 Parts Tallow soap 15 Borax 83 Sulfonated castor oil 2 Example 2 Palm oil soap 6 Tallow soap 10 Borax 82 Sulfonated castor oil 2 Example 3 Palm oil soap 19.5 Borax 80 Sulfonated castor oil .5
Example 4 Palm oil soap 15 Borax 82.5 Sulfonated oleic acid 2.5
Example 5 Tallow soap 20.5 Borax 78 Sulfonated corn oil 1.5
Example 6 Palm oil soap 22 Borax 74 Sulfonated castor oil 4 Sulfonated rape seed oil Example 7 Tallow soap 22.5 Borax 73 Sulfonated corn oil 4 5 Sulfonated palm oil Example 8 Palm oil soap a- 19 Tallow soap Borax 80.5 Sulfonated olive oil .5
Example 9 Tallow soap 22 Borax 75 Sulfonated castor oil 3 Example 10 Palm oil soap 17 Borax 78 Sulfonated castor oil 5 Example 11 Palm oil soap 17 Potassium borate 79.5 Sulfonated cotton seed oil 3.5
Example 12 Tallow soap Potassium borate 84 Lithium borate Sulfonated cotton seed oil 1 Example 13 Tallow soap 15.5 Lithium borate -o 84 Sulfonated palm kernel oil .5
Example 14 Parts Stearin flux soap 22 Borax 77 Sulfonated castor oil 1 Example 15 Hydrogenated tallow soap l9 Borax 78.5 Sulfonated coconut oil 2.5
Example 16 Hydrogenated palm oil soap 24 Borax 73 Sulfonated coconut oil 3 Sulfonated mustard seed oil Example 17 Triple-pressed tallow soap 20 Hydrogenated palm oil soap Potassium borate Sulfonated tallow oil 5 Example 18 Cocoa butter soap 19.5 Potassium borate Sulfonated lard oil .5
Example 19 Stearin flux soap 27 Lithium borate 72 Sulfonated tallow oil 1 Example 20 Coaceric soap 16 Borax 82.5 Sulfonated castor oil 1.5
Example 21 Japanic soap 19 Potassium borate Borax Sulfonated cod oil 3.5
Example 22 Borneo tallow soap 21 Borax 75 Lithium borate Sulfonated herring oil 4 Example 23 Stearic acid soap 20 Borax 79 Sulfonated sperm oil 1 Example 24 Stearin flux soap 22 Stearic acid soap Borax 74 Lithium borate Sulfonated whale oil 4 Sulfonafed sperm oil Example 25 Borneo tallow soap 18 Triple-pressed palm oil soap Borax 80 Sulfonated herring oil; 2
Example 26 Stearin flux soap 21 Borax 78 Sulfonated castor oil 1 vems-s04 7 Example 27 Parts Tallow soap 22 Borax 1 55 Potassium carbonate 2'1 Sulfonated sperm oil 2 Example 28 Tallow soap 19 Stearin fiux soap Boric acid '70 Borax l Sulfonated oleic acid .5
Example 29 Palm oil soap '15 Borax 51 Trisodium phosphate 15 Potassium carbonate 18.5 Sulfonated castor oil .5
Example 30 Cocoa butter soap 15 Lithium borate 83 Sulfouated ricinoleic acid 2 Example 31 Japanic soap l7 Borax 51.5 Sodium silicate l0 Boric acid a 8 Sodium phosphate 12 Sulfonated oleic acid W} 1 Sulfonated linoleic acid Example 32 Palm oil soap 20 Borax 57 Sodium silicate 5 Potassium carbonate 15 Sulfonatcd castor oil 3 Example 33 Tallow soap 15 Borax a- 45 Sodium carbonate 15 Sodium silicate Trisodium phosphate 12 Sulfonated cast'or oil 3 Example 34 Tallow soap Borax 40 Boric acid Potassium carbonate 22 Sulfonated castor oil 2 Example 35 Palm oil soap 20 Borax -2 39 Disodium phosphate 15 Boric acid 10 Potassium carbonate 12 Mahogany soap 4 Example 36 Palm oil soap 22 Tallow soap Borax 55 Sodium silicate 5 Boric acid 8 Potassium carbonate 8 Sulfonated corn oil 2 Example 37 Triple-pressed tallow soap 17.5 Borax 44 Trisodium phosphate 20 Potassium carbonate 15 Sulfonated sperm oil 3.5
Example 38 Parts Japanic so'ap 20 Potassium borate 65 Sodium carbonate 5 Potassium phosphate 5 Boric acid 4 Mahogany soap Sulfonated oleic acid "i 1 Example 39 Tallow soap 12 Borax 86 Sodium lauryl sulfate Cottonseed oil ..i 2
Example 40 Palm oil soap 20 Borax 77 Sodium octyl sulfate Sperm oil i 3 Example 41 Palm oil soap Tallow soap 16 Potassium borate 80 Sodium glyceryl monolaurate sulfate Rape seed oil n} 4 Example 42 Stearin flux soap 24 Potassium borate Lithium borate .i Dioctyl sodium sulfosuccinate Animal wool fat i 1 Example 43 Hydrogenated tallow soap 18 Borax 77 Pentaerythrital monostearate Corn oil "i 5 Example 44 Hydrogenated palm oilsoap l5 Borax Potassium borate n} Pentaerythrital monolaurate Palm oil l i Example 45 Cocoa butter soap a l7 Borax Sodium fi-oleylethane sulfonate Tallow 0a---- .i 3
Example 46 Coaceric soap 14.5 Potassium borate 82 Sodium ricinoelyl sulfate Coconut oil .i
Example 47 Borneo tallow soap 13.5 Lithium borate 36 Neats-foot oil Sodium keryl benzene sulfonate .i
Example 48 Stearin flux soap Stearic acid soap 20 Borax 77 Sodium lauryl sulfate Palm kernel oil i 3 Example 49 Borneo tallow soap 11 Japanic soap Lithium borate 87 Potassium cetyl sulfate 2 Lecithin appease Example 50.
. Parts Tallow soap .l 18 Coaceric soap Borax 81 Potassium borate Dilauryl potassium sulfosuccinate 1 Rape seed oil Example 51 lapanic soap 13 Palm oil soap Borax 65.5 Boric acid 8 Potassium carbonate 10 Sodium octyl naphthalene sulfonate u} 3 5 Wool fat Example 52 Palm oil soap l5 Borax 40 Boric acid c- 18 Potassium carbonate 24 Rape seed oil m} 3 Sodium lauryl sulfate Example 53 Tallow soap 22.5 Borax 60 Trisodium phosphate 15 Pentaerythritol monostearate 2 5 Herring oil Example 54 Palm oil soap 2O Tallow soap Borax 52 Sodium silicate 8 Disodium phosphate 10 Boric acid 5 Sodium fi-oleylethane sulfonate 5 Cottonseed oil Example 55 Cocoa butter soap Potassium borate 48.5 Sodium carbonate 15 Potassium phosphate 15 Sodium silicate 5 Sodium lauryl sulfate 1.5 Rape seed oil Example 56 Palm oil soap 18 Borax 65 Boric acid: 15 Sodium ricinoleyl sulfate 2 Palm oil Example 57 Tallow soap 22 Borax 55 Trisodium phosphate 12 Potassium carbonate 8 Pentaerythritol monolaurate 3 Cod fish oil Example 58 Japanic soap 15 Tallow soap Borax 50 Boric acid 6 Potassium carbonate Sodium silicate 5 Sodium octyl sulfate 4 Whale oil Example 59 v 1 Parts Palm oil soap 24.5 Borax 53 Disodium phosphate 8 Boric acid 5 Sodium carbonate 8 Dioctyl sodium sulfosuccinate 15 Rape seed oil Example 60 Palm oil soap 13 Tallow soap Potassium borate 60 Trisodium phosphate 15 Potassium carbonate 6.5 Sodium silicate 5 Sodium glyceryl monolaurate sulfate 5 Lecithin The composition is dissolved in water in an amount ranging from one ounce of the dry mix to two pounds of the dry mix per gallon of water, depending upon the particular characteristics of the stock, dies and draw. The resultant solution is applied to the stock to be drawn in any suitable manner such, for example, as by dipping, after which the coated stock is permitted to dry or is dried by the application of heat so as to form on the stock a dry, homogeneous, selfadherent, lubricating film which is very tenacious and which remains on the stock under normal storage conditions, both protecting it during storage and providing all the lubricant that is necessary when the stock is subsequently drawn.
An increase in the soap content above the lower limit provides better lubrication at lower temperatures and pressures whereas an increase in the borate content or mixture of borate and other inorganic materials provides better lubrication at the higher pressures and temperatures. On the other hand, an excess of soap over that required for a particular draw may result in building up of a relatively hard putty-like mass on the working surfaces of the dies with resultant scoring and :marring of the stock and interference with the mechanical operations of the dies, ejectors, and operating mechanisms. An excess of soap above the upper limit recited results in a tacky coating or film having low or little adherence to the stock.
An excess of the borate or mixture for a particular draw produces a film which is apt to flake off, or fail to operate properly in that the stock, because of lack of lubrication initially, becomes scored before a high enough pressure and temperature are reached to render the borate fully operative. Moreover, an excess of borate above the upper limit recited results in coating which is dusty, or causes a dusty condition in the dies, and which has insufficient plasticity and adherence.
Many coexisting factors must be considered in choosing the proportions of ingredients in the dry mix and the density of the solution for a given draw. These include, for example, the type of metal, its thickness, surface condition, ductility and other physical characteristics; the type of dies, die tolerance or clearance and surface or finish; and the depth and complexity of the draw; the speed of the presses and length of stroke.
In general, for stock having a high polish or mirror finish and for stainless steels a very thin coating is required as the adherence of thinner films is greater than that of the thicker films. Deep draws and resultant high pressures and temperatures usually indicate the higher borate to soap ratio than lighter draws and lower temperatures and pressures. Rough surface stock requires a relatively thick coat in that the surface cavities of the stock as well as the surface projections should be well coated. New dies or dies with close clearance require a thinner film than older dies or dies with more clearance.
The thinnest coating consistent with proper lubrication is desirable.
Accordingly, for the thinnest films, such as used for highly polished or stainless steels, the dry mix is used in an amount of about two ounces per gallon of water. For the coarsest films, such as used for rough finished stock, the dry mix may be used in an amount as high as two pounds per gallon. A few trials with any particular stock of steel or other metal in the particular dies to be used will demonstrate the film thickness and ratio of ingredients that may be used for optimum results for the particular metal and draw.
By the term consisting essentially of as used herein in defining the coating composition or film, it is meant to define a composition or film containing the claimed ingredients, in the relative proportions stated as the possible and actual constituents of the composition or film, but it is not meant to exclude the presence of minor amounts of conventional compounds or ingredients, the
use of which is common practice in the lubrication of metals during forming operations.
The present application is a continuation-in-part of my now abandoned co-pending application Serial No. 251,455, filed October 15, 1951, which, in turn, is a continuation of my now abandoned application Serial No. 53,376, filed October 7, 1948.
Having described the invention, I claim:
1. A coating material for admixture with water for coating a piece of blank metal stock in forming thereon a self-adherent dry homogeneous lubricating and protecting film consisting essentially of the following lubricating ingredients Parts Water-soluble, high titre soap having a melting point of at least about 36 C 10 to 30 Water-soluble, inorganic, water liberating and glass forming material of: which at least a major part thereof is an alkali metal borate 70 to 90 Coupling and plasticizing material selected from the groups consisting of the following: /2 to 5 A. Combined coupling and plasticizing material in the form of at least one compound selected from the group consisting of sulfonated vegetable oils, sulfonated animal oils, and sulfonated unsaturated fatty acid derived from animal oil and vegetable oil;
B. Coupling and plasticizing material in the form of at least two compounds, at least one compound being selected from each of the following groups 1. Coupling agent: Surface active, water-soluble,
alkali metal salts or" organic compounds containing a sulfa-group in the molecule;
2. Plasticizing agent: Vegetable oils and animal oils.
2. A coating material in accordance with claim 1 wherein the coupling and plasticizing material is a sulfonated vegetable oil.
3. A coating material in accordance with claim 1 wherein the coupling and plasticizing material is a sulfonated animal oil.
4. A coating material in accordance with claim 1 wherein the coupling and plasticizing material is a sulfonated unsaturated fatty acid derived from animal oil and vegetable oil.
5. A coating material in accordance with claim 1 wherein the coupling and plasticizing material is sulfonated castor oil.
6. A coating material in accordance with claim 1 wherein the coupling and plasticizing material is sulfonated cottonseed oil.
7. A coating material in accordance with claim 1 wherein the coupling and plasticizing material is sulfonated corn oil.
8. A coating composition in accordance with claim 1 wherein the coupling agent is an alkali metal organic sulfate.
9. A coating composition in accordance with claim 1 wherein the coupling agent is an alkali metal organic sulfonate.
10. A coating composition in accordance with claim 1 wherein the coupling agent is an alkali metal salt of a sulfate of an aliphatic alcohol.
11. A coating composition in accordance with claim 1 wherein the coupling agent is sodium lauryl sulfate.
12. A coating composition'in accordance with claim 1 wherein the coupling agent is sodium keryl benzene sulfonate.
.13. A coating composition in accordance with claim 1 wherein the coupling agent is dioctyl sodium sulfosuccinate.
14. A coating material for admixture with water for coating a piece of blank metal stock and forming thereon a self-adherent, dry, homogeneous lubricating and protecting film consisting essentially of the following ingredients by weight:
Parts Waterssolublehigh .titre soap having a melting point of atleast about 36 C 10 to 30 Borax to Sulfonated castor oil /2 to 5 .lSQA coating material for admixture with water for coating a piece of blank metal stock in forming thereon a self-adherent dry homogeneous lubricating and protecting film consisting essentially of the following lubricating ingredients:
Parts A-water-soluble soap 10 to 30 Water-soluble, inorganic, water liberating and glass forming material of which at least a major part thereof is an alkali metal borate 70 to 90 Coupling and plasticizing material selected from the groups consisting of the following: /2 to 5 A. Combined coupling and plasticizing material in the form of at least one compound selected from the group consisting of sulfonated vegetable oils, sulfonated animal oils, and sulfonated unsaturated fatty acid derived from animal oil and vegetable oil; a B. Coupling and plasticizing material in the form of at least two compounds, at least one compound being selected from each of the following groups- 1. Coupling agent: Surface active, water-soluble alkali metal salts of organic compounds containing a sulfo-group in the molecule; 2. Plasticizingtagent: Vegetable oils and animal oils.
References Cited in the .file ofthis patent UNITED STATES PATENTS

Claims (3)

1. COUPLING AGENT: SURFACE ACTIVE, WATER-SOLUBLE ALKALI METAL SALTS OF ORGANIC COMPOUNDS CONTAINING A SULFO-GROUP IN THE MOLECULE;
2. PLASTICIZING AGENT: VEGETABLE OILS AND ANIMAL OILS.
15. A COATING MATERIAL FOR ADMIXTURE WITH WATER FOR COATING A PIECE OF BLANK METAL STOCK IN FORMING THEREON A SELF-ADHERENT DRY HOMOGENEOUS LUBRICATING AND PROTECTING FILM CONSISTING ESSENTIALLY OF THE FOLLOWING LUBRICATING INGREDIENTS:
US536786A 1955-09-26 1955-09-26 Lubricating composition Expired - Lifetime US2753304A (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2964472A (en) * 1955-11-08 1960-12-13 Pennsalt Chemicals Corp Metal forming lubricant and method of making same
US2990610A (en) * 1956-05-16 1961-07-04 Phoenix Rheinrohr Ag Metal treating process employing a heat-resistant lubricant composed of alkali metalborate and alkali metal phosphate
US4138348A (en) * 1973-06-16 1979-02-06 Deutsche Texaco Aktiengesellschaft Lubricant for use in non-chip metal forming
US4289637A (en) * 1978-12-07 1981-09-15 United States Borax & Chemical Corp. Mineral oil soluble borate compositions
US20140151321A1 (en) * 2012-11-30 2014-06-05 Corning Incorporated Glass containers with improved strength and improved damage tolerance
US9988174B2 (en) 2012-06-07 2018-06-05 Corning Incorporated Delamination resistant glass containers
US10065884B2 (en) 2014-11-26 2018-09-04 Corning Incorporated Methods for producing strengthened and durable glass containers
US10117806B2 (en) 2012-11-30 2018-11-06 Corning Incorporated Strengthened glass containers resistant to delamination and damage
US10273049B2 (en) 2012-06-28 2019-04-30 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US10899659B2 (en) 2014-09-05 2021-01-26 Corning Incorporated Glass articles and methods for improving the reliability of glass articles
US11963927B2 (en) 2020-08-18 2024-04-23 Corning Incorporated Glass containers with delamination resistance and improved damage tolerance

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US2252385A (en) * 1939-02-15 1941-08-12 Gilron Products Co Method of machining articles and solution therefor
US2326387A (en) * 1940-07-31 1943-08-10 Montgomery H A Co Drawing composition and method of making the same
US2352811A (en) * 1941-06-27 1944-07-04 Standard Oil Co Lubricant
US2578586A (en) * 1949-08-11 1951-12-11 Gilron Products Company Composition for forming a dry, homogeneous, self-adherent, lubricating film on metal stock
US2609594A (en) * 1949-10-18 1952-09-09 Gilron Products Company Method of producing vitreous enamelled metal articles

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2252385A (en) * 1939-02-15 1941-08-12 Gilron Products Co Method of machining articles and solution therefor
US2326387A (en) * 1940-07-31 1943-08-10 Montgomery H A Co Drawing composition and method of making the same
US2352811A (en) * 1941-06-27 1944-07-04 Standard Oil Co Lubricant
US2578586A (en) * 1949-08-11 1951-12-11 Gilron Products Company Composition for forming a dry, homogeneous, self-adherent, lubricating film on metal stock
US2609594A (en) * 1949-10-18 1952-09-09 Gilron Products Company Method of producing vitreous enamelled metal articles

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2964472A (en) * 1955-11-08 1960-12-13 Pennsalt Chemicals Corp Metal forming lubricant and method of making same
US2990610A (en) * 1956-05-16 1961-07-04 Phoenix Rheinrohr Ag Metal treating process employing a heat-resistant lubricant composed of alkali metalborate and alkali metal phosphate
US4138348A (en) * 1973-06-16 1979-02-06 Deutsche Texaco Aktiengesellschaft Lubricant for use in non-chip metal forming
US4289637A (en) * 1978-12-07 1981-09-15 United States Borax & Chemical Corp. Mineral oil soluble borate compositions
US10273048B2 (en) 2012-06-07 2019-04-30 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US9988174B2 (en) 2012-06-07 2018-06-05 Corning Incorporated Delamination resistant glass containers
US11124328B2 (en) 2012-06-07 2021-09-21 Corning Incorporated Delamination resistant glass containers
US11608290B2 (en) 2012-06-28 2023-03-21 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US10787292B2 (en) 2012-06-28 2020-09-29 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US10273049B2 (en) 2012-06-28 2019-04-30 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US10507164B2 (en) 2012-11-30 2019-12-17 Corning Incorporated Glass containers with improved strength and improved damage tolerance
US10307333B2 (en) 2012-11-30 2019-06-04 Corning Incorporated Glass containers with delamination resistance and improved damage tolerance
US10307334B2 (en) 2012-11-30 2019-06-04 Corning Incorporated Glass containers with delamination resistance and improved damage tolerance
US20140151321A1 (en) * 2012-11-30 2014-06-05 Corning Incorporated Glass containers with improved strength and improved damage tolerance
US10786431B2 (en) 2012-11-30 2020-09-29 Corning Incorporated Glass containers with delamination resistance and improved damage tolerance
US10117806B2 (en) 2012-11-30 2018-11-06 Corning Incorporated Strengthened glass containers resistant to delamination and damage
US10813835B2 (en) 2012-11-30 2020-10-27 Corning Incorporated Glass containers with improved strength and improved damage tolerance
US10023495B2 (en) * 2012-11-30 2018-07-17 Corning Incorporated Glass containers with improved strength and improved damage tolerance
US11951072B2 (en) 2012-11-30 2024-04-09 Corning Incorporated Glass containers with improved strength and improved damage tolerance
US10899659B2 (en) 2014-09-05 2021-01-26 Corning Incorporated Glass articles and methods for improving the reliability of glass articles
US11807570B2 (en) 2014-09-05 2023-11-07 Corning Incorporated Glass articles and methods for improving the reliability of glass articles
US10065884B2 (en) 2014-11-26 2018-09-04 Corning Incorporated Methods for producing strengthened and durable glass containers
US11963927B2 (en) 2020-08-18 2024-04-23 Corning Incorporated Glass containers with delamination resistance and improved damage tolerance

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