US3770633A - Anti icing and lubricating coating compositions - Google Patents

Abstract

ANTI-ICING COATING MATERIALS ADAPTED FOR APPLICATION TO AYN SURFACE WHICH IT IS DESIRED TO MAINTAIN FREE FORM ICE, FROZEN SNOW OR SLUXH, AND LUBRICATING COATING MATERIALS ADAPTED FOR APPLICATION TO THE BOTTOMS OF SKIS AND THE LIKE WHICH MAINTAIN THEIR LUBRICATING CHARACTERISTICS OVER WIDE RANGES OF SNOW CONDITIONS AND TEMPERATURES. A SUITABLE ANTI-ICING CONTING COMPOSITIONS COMPRISES THE COMBINATION BY WEIGHT PERCENT OF; (1) 15-80% OF A LUBRICANT SELECTED FROM THE GROUP CONSISTING OF GREASE, MINERAL OIL AND POLYETHYLENE GLYCOL, (2) 1-20% OF SILICA, (3) 110% OF A TRIALKYL SUBSTITUTED PHENOL, (4) 1-20% OF AN ORGANO POLYSILOXANE AND (5) FROM 0.5 TO 10% OF A BINDER AND PLASTICIZER SELECTED FORM THE GROUP CONSISTING OF PRIMARY, SECONDARY AND TERTIARY AMINES, AZOLES, AZOLINES, OXAZOLINES, GLYOXALINES, AZINES, OXAZINES, INDOLES AND MORPHOLINES.

Description

United States Patent Office 3,770,633a Patented Nov. 6, 1973 3,770,633 ANTI-ICING AND LUBRICATING COATING COMPOSITIONS Danforth Holley, Grosse Pointe Shores, and John W. Nika, Leonard, Mich, assignors to Danforth Holley, Grosse Pointe Shores, Mich. N Drawing. Filed Nov. 2, 1971, Ser. No. 194,901 Int. Cl. Cm 1/10, 3/02, 5/02 US. Cl. 252 28 7 Claims ABSTRACT OF THE DISCLOSURE Anti-icing coating materials adapted for application to ayn surface which it is desired to maintain free from ice, frozen snow or slush, and lubricating coating materials adapted for application to the bottoms of skis and the like which maintain their lubricating characteristics over wide ranges of snow conditions and temperatures.

A suitable anti-icing coating composition comprises the combination by weight percent of; (1) -80% of a lubricant selected from the group consisting of grease, mineral oil and polyethylene glycol, (2) 120% of silica, (3) 1- 10% of a trialkyl substituted phenol, (4) 1-20% of an organo polysiloxane and (5) from 0.5 to 10% of a binder and plasticizer selected from the group consisting of primary, secondary and tertiary amines, azoles, azolines, oxazolines, glyoxalines, azines, amides, oxazines, indoles and morpholines.

BACKGROUND OF THE INVENTION Field of the invention The present invention relates to compositions of matter which inhibit ice or slush formation and act as lubricant coatings,when applied to a base surface.

Description of the prior art In winter sports such as skiing and snowmobiling, a persistent problem of icing and freezing of various exposed surfaces is encountered. Thus, for example, after a few minutes of skiing the snow and slush which are unavoidably sprayed and splattered onto the boots and safety release bindings of the skier can freeze or turn to ice. This in effect freezes shut the safety release bindings and prevents them from performing their designed function of coming undone upon the application of a predetermined force. Because of this malfunction due to the ice formation on or freezing of the release bindings, serious injuries may result when a skier suffers a fall or other accident. In snowmobiling ice, slush, and frozen snow can form on the bogey wheels of the snowmobile with the resultant difiiculties of loss of speed and maneuverability. Extremely large deposits of ice or frozen snow on the bogey or drive wheels of snowmobiles can even totally immobilize the snowmobile.

By the application of a coating of the anti-icing composion of the present invention, the above described problems are eliminated. A thin layer of the anti-icing material prevents the formation of ice on the base material regardles of the nature of the base material. It has also been found that snow and slush do not adhere to an article coated with the anti-icing composition of the present invention.

As is well known in the art, it is necessary to apply a coating of wax or the like to the undersides of skis in order to get good skiing. In the past it has been necessary to apply a different type of wax for different snow conditions. Thus, it was necessary to apply one type of wax wh'en ski- .ing in extremely cold weather and dry snow conditions. When the weather changed, as for example when it got warmer, the snow conditions also changed, the snow becoming wetter and heavier. It was then necessary to physically remove the old wax coating from the skis and to apply a new wax appropriate for the changed conditions. The removal of one wax coating and the substitution therefor of another wax coating was a tedious and time consuming process.

With the ski-coating composition of the present invention it is not necessary to use a different coating for each of several different snow conditions. It has been found that the lubricating material of the present invention when applied as a coating to the surface of the skis which is in contact with the snow acts equally well in all types of snow conditions and over a wide range of temperatures. Thus, it only requires a single application of a coating of the lubricating material of the present invention and the skier is ready to ski in wet snow, dry snow, or any other type of snow condition without the necessity of changing the coating with varying snow and temperature conditions.

SUMMARY OF THE INVENTION In accordance with the present invention there is provided an anti-icing composition adapted for application to a base surface as a coating which prevents ice formation and keeps snow from adhering to said surface. This material consists essentially of an anti-oxidant, a lubricant, a binder and plasticizer which comprises nitrogen containing organic compounds containing eight or more carbon atoms, a siloxane, and silica. Also in accordance with the present invention, there is provided a lubricating composition adapted for application to skis as an all-weather and all-snow condition lubricant coating. This material consists essentially of a siloxane, a lubricant, fluoroand chlorocarbons, silica, and a plasticizer and binder consisting of ethylene glycol monoethyl ricinoleate and ethylene glycol monobutyl ether laurate.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In one preferred embodiment, the anti-icing material of the present invention contains the following proportions of ingredients:

Percent by weight The binder and plasticizer is a nitrogen containing organic compound containing eight or more carbon atoms. These nitrogen containing compounds can be aliphatic, aromatic, and heterocyclic. Examples of suit-able aliphatic compounds are primary, secondary and tertiary amines such as 2-ethylhexylamine, dialkylhydroxylamine, 3-di-namylaminopropylamine, di(2-ethylhexylamine), dodecylamine, didodecylamine, dioctadecylamine, trihexylamine, tridimethyl amino methyl phenol, and tri-n-amylamine. Aromatic amines such as the following can be employed: phenyl ethanolamine, 4,4'-methylene dianiline, diethylaniline, phenyl ethanolamine, p-phenetidine, diphenylamine, benzedine, and S-pentadecyl phenol. The heterocyclic nitrogen compounds are illustrated by substituted azoles, azolines, oxazolines, glyoxaline, azines, oxazines, indoles, and morpholines having eight or more carbon atoms. Of particular value are the substituted oxazolines of high molecular weight, especially those having a weight of at least 300, an example of which are the acyloxymethyl oxazolines which have the general structural formula:

H JCH OCOR1 2 in which the R substituents are identical and are selected from the group consisting of alkyl and aryl, R is selected from the group consisting of hydrogen, alkyl and acyloxy methyl. Other examples of high molecular weight oxazolines, which includes the 2-oxazoliues which may be represented by the following structural formula:

in which the substituents R and R represent hydrogen, alkyl, aryl, or acyloxy alkyl, and R and R represent hydrogen or alkyl, are 2-pentyl-4,5-dimethyl-4-(hexanooxyethyl) 2 oxazoline, 2 pentyl 4 bis (hexanooxy methyl-2-oxazoline, 2-nonyl-4-ethyl-4-caproxy methyl-2- oxazoline, and 2-ethyl-4-methyl-4-propionoxy methyl-2- oxazoline.

The substituted oxazolines are well-known substances which may be prepared in accordance with the methods taught in U.S. Pats. 2,372,409, 2,372,410 and 2,504,951. Other examples of the heterocyclic nitrogen containing compounds are phenylmorpholine and l-hydroxyethyl-Z- heptadecenyl glyoxalidine. Examples of suitable amides are n-hexadecane amide, n-octadecane amide, stearamide, n-phenylacetamide, and n-methyl-n-ethylbenzamide. As can be seen, the appropriate amides are both aliphatic and aromatic amides containing eight or more carbon atoms. It will be understood that the particular compounds may be classified in one or more of the above groups and that the binder and plasticizer can consist of only one particular compound or it can be a mixture of various compounds.

The optimum percentage of the lubricant is from fifty to seventy percent by weight of the composition. The lubricant can be any of the known lubricating substances which provide a viscous fluid film or gel. Thus, the lubricant can be a grease, such as petrolatum, or an oil. However, mineral oil, particularly white mineral oil, and polyethylene glycols have been found to be of particular value as lubricants. As is well known in the art, white mineral oil, also known as paraflin oil and liquid petrolatum, is a mixture of liquid hydrocarbons from petroleum and has a density of from between .83 to .90. It is insoluble in water or alcohol but is soluble in benzene chloroform, ether, carbon disulphide, petrol, ether, and oils.

The anti-oxidant is present in from 0.1 to by weight of the composition with the optimum percentage being .5 to 1%. The anti-oxidant should preferably be a trisubstituted phenol, 2,6-di-tert butyl 4-methyl phenol has been found to be particularly valuable.

The fillers can comprise from 5 to 95% by weight of the composition, with the optimum percentage being 25 The filler that has been found to be especially useful is mineral oil. Also present in the composition is silica, SiO in the optimum percentage range of 5-15% by weight of the composition. The silica is present as an inert material from providing a variety of rheological effects in the liquid media of the composition, particularly to give a smooth dispersion. The siloxane is present in an optimum percentage of from 5 to 15% by weight of the composition. The siloxanes are well known in the art and are silicone or polysiloxane polymers which can be represented by the following structural formula:

EXAMPLE I Lbs. Ucon Fluid LB1715 Ional 1.5 White mineral oil 52 Silicone (dimethyl polysiloxane) 27 Cab-O-Sil 30 2-ethylhexylamine 5 The Ucon Fluid LB-1715 is a polyalkylene glycol fluid lubricant manufactured by the Union Carbide Corpora- .tion. The I0n0l is an anti-oxidant, more specifically ditert butyl 4 methyl phenol manufactured by the Shell Chemical Corp. Cab-O-Sil is a silica (Si0 produced by Cabot Corporation, having the following typical properties:

Particle size range micron .0l5-.020 Total surface area (BET nitrogen adsorption) sq. meters/gram" 190 Loose bulk density lbs./cu. ft 2.2 Moisture content percent max 1.5 Silica content (moisture-free basis) percent 99.7-99.9

The dimethyl polysiloxane is in the form of a fluid having a viscosity of 10,000 centistokes.

A mixture of the (l) Ucon fluid (polyalkylene glycol), (2) Ional (di-tert butyl 4-methyl phenol), (3) white mineral oil, (4) polysiloxane, (5) Cab-O-Sil (SiO and (6) amine or amide is made in the usual manner, preferably in the order shown above. The ingredients are then mixed until the mixture is smooth and the Ional, which comes in crystalline form, is dissolved. This should be approximately ten minutes. In order to insure that the composition is homogeneous throughout, the mixture may be subjected to a pressure of 12,000 p.s.i.

The following compositions, similar to that in Example 1 but employing a different nitrogen containing organic compound and different polysiloxanes are:

EXAMPLE V Lbs. Polyalkylene glycols 200 Di-tert butyl 4-methyl phenol 1.5 Mineral oil 40 Dimethyl polysiloxane 27 Silica 30 Dioctadecylamine 5 EXAMPLE VI Lbs. Polyalkylene glycols 190 Tri-substituted phenol 1.5 Mineral oil 52 Methyl phenyl polysiloxane 27 Silica 30 Indole 5 EXAMPLE VII Lbs. Polyalkylene glycols 150 Di-tert butyl 4-methy1 phenol 1 Mineral oil 92 Diethyl polysiloxane 27 Silica 30 Stearamide 5 EXAMPLE VIII Lbs. Polyalkylene glycols 200 Di-tert butyl 4-methyl phenol 2 Mineral oil 70 Ethyl phenyl polysiloxane 30 Silica 33 Laurylamine 6 The anti-icing material can be applied as a liquid by means of a brush, cloth, or other manual means. Alternatively, the coating can be applied as an aerosol spray. In this latter embodiment the base material, which has been described in the foregoing examples, is mixed with a suitable propellant such as Freon. As is well known, Freon is a trademark of E. I. du Pont de Nemours & Co. for a group of fiuorochloromethanes and ethanes.

To make the product available as an aerosol spray approximately ten percent of the base mixture is added to ninety percent of a fluorochloromethane propellant in an appropriate container. The propellant can comprise either a single compound or a mixture of compounds. In a preferred embodiment of the present invention the propellant comprises a mixture of ten percent base compound, 45 percent Freon 11 (trichloromonofluoromethane), and 45 percent Freon 12 (dichlorodifluoromethane).

Whether it is applied as a liquid or as a spray, the antiicing material dries to a colorless, hard and non-tacky coating which repels snow and slush and prevents the formation of ice on the coated article.

Another embodiment of the invention comprises an allweather lubricant coating material for the bottom of s-kiis. The coating materials in accordance with this invention contain the following proportions of ingredients:

Percent by weight Organo polysiloxane 20-70 Silica 1-10 Halogen substituted alkanes 15-35 Fluorocarbons 1-20 Binder and plasticizer 1-20 has a specific gravity at 25 C. of 0.985, a melting point of -10 to -15 C., and the formula 11 2a z) z a a Although the preferred mixture is 60 percent to 40 percent, this can be varied to some extent. Thus, it has been found that a mixture comprising 40 percent ethylene glycol monoethyl ether ricinoleate and 60 percent ethylene glycol monobutyl ether laurate will give satisfactory results.

The organo polysiloxane is preferably dimethylpolysiloxane fluid with a preferred viscosity of 1,000 centistokes, although other polysiloxanes such as methyl phenyl polysiloxane, diethyl polysiloxane, and ethyl phenyl polysiloxane can be used with satisfactory results. The optimum percentage of siloxane is from 40-50 percent by weight of the composition with the best results being achieved when the concentration of the siloxane is approximately 50 percent.

Cab-O-Sil, which is a product of the Cabot Corporation, is used to provide the silica. The optimum percentage of silica is in the range of five percent by weight of the composition.

It should be noted that the optimum percentage of the halogen substituted alkanes is from 20-30 percent by weight of the composition, and the halogen substituted alkane should preferably be a tri halogen substituted alkane. The three halogen groups should preferably be attached to the same carbon atom in the alkane and, although any of the alkanes and halogens such as tribromomethane, trichloropropane, triiodoethane, trifluoroethane will work, exceptionally satisfactory results have been obtained with 1,1,l-trichloroethane.

The fluorocarbons are provided by Teflon and Vydac, with Teflon being present in .5-10 percent of the composition by weight and Vydax being present in .5-10 percent of the composition by weight. Teflon is produced by the E. I. du Pont de Nemours Company and consists essentially of polytetra-fluoroethylene. As is well known in the art, the tetrafiuoroethylene polymer is made by pyrolysis of chlorodifluoromethane and emulsion polymerization catalyzed by oxygen of the tetrafluoroethylene.

wherein n is about 1000. Vydax AR is produced by the E. I. du Pont de Nemours Company and is essentially a tetrafluoroethylene telomer dispersion in Freon and/or toluene and acts as a lubricant.

It has been found that polytetrafluoroethylene, when applied as a coating to the bottom of skis provides excellent lubrication in conditions of relatively warm weather and Wet or moist snow. However, in extremely cold weather when the snow is dry, skis coated with polytetrafluoroethylene will not slide on the snow. In extremely cold weather and dry snow conditions, it has been found that silicone provides an excellent lubricating coating for skis. Attempts to make a combined silicone-- polytetrafluoroethylene coating have failed because the two compounds are not miscible. By adding the ethylene glycol monoethyl ether ricinoleate and ethylene glycol monobutyl ether laurate to the silicone polytetrafluoroethylene system the two compounds become miscible and blend into a homogeneous mixture. The halide substituted alkanes and tetrafluoroethylene telomer are added to give increased lubrication to the system. The silica gives a smoother dispersion as well as providing solid particles which act as a multitude of tiny ball bearings when the coated ski surface comes in contact with the snow, either artificial or natural and even many snow substitutes such as plastic chips, artificial grass and the like.

The following specific examples of formulations in accordance with this invention are illustrative only and should not be construed as limiting the scope of the invention:

60 percent ethylene glycol monoethyl ether ricinoleate and 40 percent ethylene glycol monobutyl ether laurate 10 (Cab-O-Sil HS-S) silica 1,1,l-trichloroethane 25 EXAMPLE X The same formulation as Example IX except 60 percent ethylene glycol monobutyl ether laurate and 40 percent ethylene glycol monoethyl ether ricinoleate were used.

EXAMPLE XI The same formulation as Example IX except methyl phenyl polysiloxane was used.

A mixture of the (1) polysiloxane, (2) polytetrafluoroethylene, (3) tetrafluoroethylene telomer, (4) ethylene glycol monoethyl ether ricinoleate and ethylene glycol monobutyl ether laurate, (5) silica, (6) tri-halogen substituted alkane is made in the usual manner, preferably in the order shown. The ingredients are then mixed until the mixture is smooth. In order to insure a homogeneous composition, the mixture may be subjected to a pressure of 12,000 p.s.i. for a short period of time. The composition, which at this point is a liquid, is applied to the bottoms of skis or the like and allowed to dry to a hard solid layer.

The lubricating material can be applied as a liquid or as a spray. In the spray form the base material, which has been described above, is mixed with a suitable propellant such as any of the fluorochloromethanes and ethanes. To make the product available as an aerosol spray, approximately ten percent of the base mixture is added to 90 percent of a fluorochloromethane and/or ethane propellant, under pressure, in an appropriate container.

In another embodiment of the invention, a coating material is formulated which is adapted for all-weather cross-country skiing. In cross-country skiing it is particularly important to have skis which will allow the skier ease of forward movement but will at the same time prevent the skier from slipping or sliding backwards, as for example when standing on an upwardly inclined surface such as a hill.

It has been found that the lubricating coating described above, to which is added a small amount of a nitrogen containing organic compound containing eight or more carbon atoms, which are described above, has the unusual and unexpected property of allowing ease of movement in a forward direction but prevents unwanted and unexpected rearward slippage. Thus, once a skier pushes himself into motion from a static position, the skis coated with the modified coating travel quite easily over any type of snow. However, when the skier is in a static or unmoving position, the coating prevents any accidental or unwarranted slipping or sliding.

The following examples provide illustrations of the foregoing material:

60 percent ethylene glycol monoethyl ether ricinoleate and 40 percent ethylene glycol monobutyl ether laurate 40 percent Z-ethylhexylamine 2.

In place of the trichloroethane, any of the trihalogen substituted alkanes such as previously mentioned can be used. The dimethylpolysiloxane can be replaced by the equally effective methyl phenyl polysiloxanes, diethylpolysiloxanes and ethylphenyl polysiloxanes. The Z-ethylhexylamine can be replaced by any amine or amide containing eight or more carbon atoms.

Although Example XII sets forth the most preferred proportions of the ingredients, it has been found that the ingredients can be present in the following ranges and still produce an effective lubricant coating composition:

Percent by weight Organo polysiloxane 20-70 Silica 1-10 Halogen substituted alkanes 15-35 Fluorocarbons 1-20 Ethylene glycol monoethyl ether ricinoleate and ethylene glycol monobutyl ether l-10 Amine or amide containing at least eight carbon atoms 1-7 What is claimed is:

1. An anti-icing surface coating composition comprising a mixture of from about 15 to about percent by weight of at least one lubricant selected from the group consisting of grease, mineral oil, and polyethylene glycol, from about one to about 20 percent by weight of silica, from about one to about 10 percent by weight of an anti-oxidant comprising a trialkyl substituted phenol, from about one to about 20 percent by weight of an organo polysiloxane selected from the group consisting of dimethyl polysiloxane, methylphenyl polysiloxane, diethyl polysiloxane, or ethylphenyl polysiloxane, and from about .5 to about 10 percent by weight of a binder and plasticizer, said binder and plasticizer comprising a nitrogen containing organic compound containing at least eight carbon atoms selected from the group consisting of primary amines, secondary amines, tertiary amines, azoles, azolines, oxazolines, glyoxalines, azines, oxazines, amides, indoles and morpholines.

2. The composition in accordance with claim 1, and further including about 5% of a tetrafiuoroethylene telomer dispersion in at least one compound selected from the group consisting of toluene and Freon.

3. A surface coating lubricant composition comprising from about 20% to about 70% by weight of an organo polysiloxane selected from the group consisting of dimethylpolysiloxane, methyl phenyl polysiloxane, diethyl polysiloxane, and ethylphenyl polysiloxane, from about 1% to about 10% by weight of silica, from about 15% to about 35% by weight of a halogen substituted lower alkane, from about .5% to about 20% by weight of tetrafluoroethylene polymer, and from about 1% to about 20% by weight of a binder and plasticizer comprising at least one member of the class consisting of ethylene glycol monoethyl ether ricinoleate and ethylene glycol monobutyl ether laurate.

4. A surface coating composition as defined in claim 3 and further including about 5% of a tetrafiuoroethylene telomer dispersion in at least one compound selected from the class consisting of toluene and Freon.

5. A surface coating composition as defined in claim 3 wherein about 10% of said composition is mixed with about of a Freon propellant for dispensing said composition from a container as an aerosol.

6. A surface coating composition as defined in claim 1 wherein about 10% of said composition is mixed with about 90% of a Freon propellant for dispensing said composition from a container as an aerosol.

7. A surface coating composition as defined in claim 3 and further including from about 1 percent to about 7 percent of a binder and plasticizer, said binder and plasticizer comprising a nitrogen containing organic compound containing at least eight carbon atoms selected from the group consisting of amines, azoles, azolines, oxazolines,

- 1 glyoxalines, azines, indoles, amides, oxazines, and mor- 3,132,071 5/1964 King et a1. 25228 X pholines. 3,453,210 7/1969 Wright 2s2 -2s References Cited DANIEL E. Y A UNITED STATES PATENTS A H N g Exammer 2,523,281 9/1950 Currie 106-3 5 8815mm Xammer 3,067,262 12/1962 Brady 252--S8 x 3,069,280 12/1962 Spiegler 2s2 ssx