US3042638A - Artificial snow - Google Patents

Artificial snow Download PDF

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US3042638A
US3042638A US11919A US1191960A US3042638A US 3042638 A US3042638 A US 3042638A US 11919 A US11919 A US 11919A US 1191960 A US1191960 A US 1191960A US 3042638 A US3042638 A US 3042638A
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percent
composition
agent
flocking
artificial snow
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US11919A
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Charles A Dragotta
Jr Albert C Cereghino
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Kraft Inc
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Kraft Inc
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/24Materials not provided for elsewhere for simulating ice or snow

Definitions

  • the present invention generally relates to decorative compositions and, more particularly, it relates to attificial snow compositions which can be sprayed.
  • compositions are commercially available in aerosol containers and they are widely used during the Christmas season eachlyear.
  • Such compositions usually comprise 'a flocking agent which produces snow-like material and which may be a resin or the like; a solvent or dispersant for such flocking agent; and a pressurized propellant; the composition being packaged in a pressurized can commonly known as an aerosol .container.
  • the flocking agent takes the form of flock or snowlike particles which are directed against and which more or less adhere to the object to be decorated.
  • the container can be subjected to cold conditions when transported from the store to the home. It is, therefore, desirable that the composition be fluid at lowtemperatures.
  • the presently available artificial snow compositions generally do not spray properly when temperatures are below about 70 F. At lower temperatures, these compositions set up so that they can not be effectively sprayed, either because the nozzle of the containers become clogged or the product becomes too viscous.
  • an improved artificial snow composition suitable for spraying from an aerosol container or the like has now been discovered and it can be satisfactorily sprayed at temperatures substantially below the previous limit of about 70 F.
  • the improved composition of this invention can be satisfactorily sprayed at much lower temperatures while providing an excellent flock simulating snow. Accordingly, the utility and commercial acceptability of the artificial snow composition are substantially improved over presently available compositions. Furthermore, the improved utility is economically obtained with commercially available constituents for the composition.
  • a primary object of the present invention is to provide an improved artificial snow composition and ingredients therefor.
  • a still further object of the invention is the provision of an artificial snow composition capable of providing high quality flock at low cost, and at relatively low temperatures, which composition can be readily dispensed from an aerosol container or the like.
  • the composition of the present invention basically includes a flocking agent, a fluidizing agent, a propellant, and a binding agent.
  • the fluidizing agent has mutual solubility with the flocking agent, and is believed to provide particle size control for the flocking agent and to efiect uniform dispersion of the flocking agent in the composition.
  • the fluidizing agent is a compound having oleophilic groups and groups with afiinity for liquid propellant so as to provide certain mixing properties with propellant and oil.
  • the flocking agent is present in a concentration of between about 1 and about 20 percent by weight of the composition.
  • percent and parts are used to mean percent or parts by weight.
  • the flocking agent may be any suitable fatty acid or glyceride which are solid up to temperatures of about F.
  • the fatty acid will be one, or a mixture of two or more fatty acids, having a relatively high molecular weight, that is, fatty acids which have a carbon chain length of at least about 12 carbon atoms, but preferably not more than about 22 carbon atoms. While such fatty acids may be saturated or unsaturated and may contain any suitable subsidiary groups, for example, hydroxy groups or the like, they will usually be saturated rather than unsaturated.
  • Particularly effective flocking agents are palmitic acid and stearic acid, especially when utilized together in a mixture in which the palmitic acid accounts for approximately 70 percent by weight of the mixture and the Stearic acid approximately 30 percent by weight of the mixture. It will. be understood that other mixtures of these two fatty acids and other fatty acids are also suitable, as before indicated.
  • the fluidizing agent coacts with the flocking agent and, in accordance with this invention, is present with the flocking agent at a level of between about 5 percent and about 15 percent by weight of the flocking agent.
  • this fluidizing agent includes oleophilic and propellant-philic groups, and accordingly, may have emulsitying properties.
  • the fluidizing agent be an ester of a short chain (1 to 4 carbon atoms) (polyhydric alcohol) and a long chain (12 to 22 carbon atoms) fattyacid.
  • esters which may be .used include ethyl palmitate, methyl stearate, ethyl myristate and methyl oleate. Methyl ricinoleate is also contemplated, as well as methyl and ethyl linoleate.
  • suitable esters is not intended to be exhaustive and equivalent compounds will be readily suggested to those skilled in the art.
  • fluidizing agent comprises between about 1 and about 20 percent by weight of the flocking agent.
  • the mixture of the flocking agent and the fluidizing agent is to a large extent responsible for the substantial reduction in the minimum temperature at which the artificial snow composition can be used effectively from an aerosol container.
  • an artificial composition were utilized which did not include the indicated mixture, such as that described, of these agents, the improved results with respect to the minimum temperature of effective operation. of the artificial snow composition would be lost.
  • either ingredient of the mixture were used alone, the effective results would not be obtained.
  • the binding agent is, for the purposes of the present invention, any suitable resin binder such as those utilized in conventional artificial snow compositions.
  • the binding agent will be a synthetic resinous polymer, such as polyvinyl acetate, the methacrylates or the like.
  • the binding agent will be present at a level of between about .25 percent and about 2 percent of the final snow compositon.
  • the level is desirably minimized to reduce cost and to maintain the fluidity of the composition at low temperatures while, at the same time providing bonding properties.
  • the binding agent should be White or translucent so as not to afilect the snow effect of the composition.
  • a solvent for the bonding agent which is miscible with or dispersible in the flocking agent is also present in the composition.
  • concentration of the solvent will depend primarily upon the amount of resin which needs to be solubilized and the solvent power of the particular solvent. The amount and selection of the solvent is within the skill of the art. However, the solvent should not be inflammable or deleterious to humans, paint, or other things which may be sprayed.
  • a particularly satisfactory solvent is methylene chloride.
  • the composition of the invention further comprises a propellant.
  • propellants conventionally used with aerosol containers will be used in the composition of this invention.
  • propellant should be non-toxic and be capable of spraying the composition.
  • Propellants particularly contemplated in connection with this invention are Freons which arerecognized in the art as a class of polyhalogenated lower alkanes. Since these compounds are so well known in the art for propellants in aerosol containers, a further description of these compounds is not believed to be required. While other propelling gases may be used, such as nitrogen and carbon dioxide, such propellants are generally not satisfactory as propellants of the composition of this invention.
  • propellant should be used to effect the spraying of the contents in the aerosol container and, in general, the propellant will comprise from about 60 percent to about 90 percent of the composition of the invention.
  • Example I The composition of this invention is prepared by first preparing a blend of fatty materials comprising methyl palmitate and a fatty acid mixture comprising palmitic Twelve pounds of this blend of fatty materials is com- I bined with three pounds of a solubilized resin solution.
  • the resin solution is prepared by mixing one pound of polyvinyl acetate with two pounds of methylene chloride.
  • the fatty materials and this solubilized resin may be mixed together.
  • four parts of the fatty components are introduced into an aerosol container and, to this is added one part of the resin solution.
  • the container is then filled with about 21 parts of a Freon propellant, under pressure, in accordance with the usual practice in the art.
  • composition therefore, comprises the following ingredients:
  • Example 11 As another example of this invention, the same ingredients are used as specified in Example I, except that ethyl palmitate is substituted for the methyl palmitate in the manufacture of the compound.
  • Example 111 As another example of this invention, the same formula as in Example I is used, except that methyl stearate is utilized in place of the methyl palmitate.
  • Example IV In accordance with this example, the same ingredients re employed as in Example 1, except that the fatty materials comprise palmitic acid alone, in place of a mixture of stearic and palmitic acids.
  • Example V In accordance with this example, the same ingredients are used as in Example I, except that the fatty materials comprise about 12 percent of methyl palmitate, about 62 percent palmitic acid and about 26 percent stearic acid.
  • the composition of the invention is discharged from the aerosol container through the usual nozzle on to a surface which is to be decorated. This is in accord with the well known practice for effecting decorations with these artificial snows.
  • a principal feature of this invention is in the utilization of a particular mixture of fatty materials, the mixture comprising fatty acids in combination with esters having hydrophilic and oleophilic groups.
  • ester not only provides improved dispersion and distribution of the fatty acid product, but, in addition, provides fluidity to the product at a much lower temperature than is provided by the artifical snow products presently available.
  • An improved artificial snow composition comprising, in combination, a flocking agent comprising between about 1 percent and about 20 percent of said composition, said flocking agent including a long chain fatty acid having from between 12 and 22 carbon atoms, a fluidizing agent in an amount of between about 1 percent and 20 percent of said flocking agent, said fluidizing agent being an ester of a short chain polyol having from 1 to 4 carbon atoms and a long chain fatty acid having from 12 to 22 carbon atoms, a propellant comprising polyhalogenated lower alkanes in an amount of about 60 percent and percent of said composition, a binding agent comprising synthetic resin polymer in an amount of about between .25 percent and 2 percent of said composition, and a solvent for said binding agent which is miscible with said flocking agent.
  • An improved artificial snow composition comprising, in combination, a flocking agent comprising between about 1 percent and about 20 percent of said composition, said flocking agent comprising a mixture of pahnitic acid and stearic acid, a fluidizing agent in an amount of between about 1 percent and 20 percent of said flocking agent, said fluidizing agent being methyl palmitate, a polyhalogenated lower alkane refrigerant propellant in an amount of about 60 percent and 90 percent of said composition, polyvinylacetate in an amount of about between .25 percent and 2 percent of said composition, and a solvent for said binding agent which is miscible with said flocking agent.
  • An improved artificial snow composition compris- 6 ing, in combination, a mixture of palmitic acid and stearic m HIIt f a ut 1 Percent Of d mp i i and t acid, the palmitic acid comprising about 70 percent and ylene chloride in an amount of about 2 percent of said the stearic acid comprising about 30 percent of said mixcomposition for dissolving said polyvinyl acetate.
  • said mixture comprising about 12 percent of said composition, a fluidizing agent in an amount of about 5 7 References Cited in the file of this Patent 10 percent of said mixture of fatty acids, said fiuidizing UNITED STATES PATENTS agent being methyl palnntate, a propellant COmPllSlIlg polyhalogenated lower alkanes in an amount of about 85 2,659,704 Kerr, Nov. 17, 1953 percent of said composition, polyvinyl acetate in an

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

United States Patent 6 3,042,638 ARTIFICIAL SNOW Charles A. Dragotta, Bergenfield, and Albert C. Cereghino, Jr., Livingston, N .J assignors to National Dairy Products Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Feb. 29, 1960, Ser. No. 11,919 3 Claims. (Cl. 260-23) The present invention generally relates to decorative compositions and, more particularly, it relates to attificial snow compositions which can be sprayed.
Various artificial snow compositions are commercially available in aerosol containers and they are widely used during the Christmas season eachlyear. Such compositions usually comprise 'a flocking agent which produces snow-like material and which may be a resin or the like; a solvent or dispersant for such flocking agent; and a pressurized propellant; the composition being packaged in a pressurized can commonly known as an aerosol .container. When the composition is sprayed from the container, the flocking agent takes the form of flock or snowlike particles which are directed against and which more or less adhere to the object to be decorated.
' Inasmuch as one of the principal uses of the artificial snow compositions is in the decoration of Christmas trees, Christmas wreaths, windows and the like,- and it is frequently desirable to be able to spray outdoors. Furthermore, the container can be subjected to cold conditions when transported from the store to the home. It is, therefore, desirable that the composition be fluid at lowtemperatures. In this connection, the presently available artificial snow compositions generally do not spray properly when temperatures are below about 70 F. At lower temperatures, these compositions set up so that they can not be effectively sprayed, either because the nozzle of the containers become clogged or the product becomes too viscous. Accordingly, most manufacturers of artificial snow compositions, which are dispersed by means of a propellant from an aerosol container, indicate on the container the required temperature conditions for proper use of the composition. As previously indicated, such temperature conditions restrict the use, and types and manners of application of the generally available compositions.
However, an improved artificial snow composition suitable for spraying from an aerosol container or the like has now been discovered and it can be satisfactorily sprayed at temperatures substantially below the previous limit of about 70 F. In this connection, it has been found that the improved composition of this invention can be satisfactorily sprayed at much lower temperatures while providing an excellent flock simulating snow. Accordingly, the utility and commercial acceptability of the artificial snow composition are substantially improved over presently available compositions. Furthermore, the improved utility is economically obtained with commercially available constituents for the composition.
Accordingly, a primary object of the present invention is to provide an improved artificial snow composition and ingredients therefor. A still further object of the invention is the provision of an artificial snow composition capable of providing high quality flock at low cost, and at relatively low temperatures, which composition can be readily dispensed from an aerosol container or the like.
It is also a primary object of the present invention to provide improved ingredients for an artificial snow composition which can be readily sprayed from an aerosol container or the like, said ingredients aiding in the low temperature, snow-making effectiveness of such composition.
e CC
Further objects and advantages of the present invention will be apparent from a study of the following detailed description.
The composition of the present invention basically includes a flocking agent, a fluidizing agent, a propellant, and a binding agent. The fluidizing agent has mutual solubility with the flocking agent, and is believed to provide particle size control for the flocking agent and to efiect uniform dispersion of the flocking agent in the composition. As will be indicated hereinafter, the fluidizing agent is a compound having oleophilic groups and groups with afiinity for liquid propellant so as to provide certain mixing properties with propellant and oil.
Now referring more specifically to the flocking agent of the present invention, the flocking agent is present in a concentration of between about 1 and about 20 percent by weight of the composition. As used herein the terms percent and parts are used to mean percent or parts by weight. The flocking agent may be any suitable fatty acid or glyceride which are solid up to temperatures of about F. Accordingly, the fatty acid will be one, or a mixture of two or more fatty acids, having a relatively high molecular weight, that is, fatty acids which have a carbon chain length of at least about 12 carbon atoms, but preferably not more than about 22 carbon atoms. While such fatty acids may be saturated or unsaturated and may contain any suitable subsidiary groups, for example, hydroxy groups or the like, they will usually be saturated rather than unsaturated.
Particularly effective flocking agents are palmitic acid and stearic acid, especially when utilized together in a mixture in which the palmitic acid accounts for approximately 70 percent by weight of the mixture and the Stearic acid approximately 30 percent by weight of the mixture. It will. be understood that other mixtures of these two fatty acids and other fatty acids are also suitable, as before indicated.
The fluidizing agent coacts with the flocking agent and, in accordance with this invention, is present with the flocking agent at a level of between about 5 percent and about 15 percent by weight of the flocking agent. As before indicated, this fluidizing agent includes oleophilic and propellant-philic groups, and accordingly, may have emulsitying properties.
A number of suitable substances are available for use as the fluidizing agent. However, it is preferred that the fluidizing agent be an ester of a short chain (1 to 4 carbon atoms) (polyhydric alcohol) and a long chain (12 to 22 carbon atoms) fattyacid.
Tests have demonstrated the superior properties of methyl palmitate as the fluidizing agent. Other esters which may be .used include ethyl palmitate, methyl stearate, ethyl myristate and methyl oleate. Methyl ricinoleate is also contemplated, as well as methyl and ethyl linoleate. The indicated list of suitable esters is not intended to be exhaustive and equivalent compounds will be readily suggested to those skilled in the art.
It should be understood that a compatible mixture of two or more of the indicated fluidizing agents can be utilized, so long as the fluidizing agent comprises between about 1 and about 20 percent by weight of the flocking agent.
The mixture of the flocking agent and the fluidizing agent is to a large extent responsible for the substantial reduction in the minimum temperature at which the artificial snow composition can be used effectively from an aerosol container. Thus, if an artificial composition were utilized which did not include the indicated mixture, such as that described, of these agents, the improved results with respect to the minimum temperature of effective operation. of the artificial snow composition would be lost. Moreover, if either ingredient of the mixture were used alone, the effective results would not be obtained.
The binding agent is, for the purposes of the present invention, any suitable resin binder such as those utilized in conventional artificial snow compositions. In most instances the binding agent will be a synthetic resinous polymer, such as polyvinyl acetate, the methacrylates or the like.
The binding agent will be present at a level of between about .25 percent and about 2 percent of the final snow compositon. The level is desirably minimized to reduce cost and to maintain the fluidity of the composition at low temperatures while, at the same time providing bonding properties. The binding agent should be White or translucent so as not to afilect the snow effect of the composition.
A solvent for the bonding agent which is miscible with or dispersible in the flocking agent is also present in the composition. The concentration of the solvent will depend primarily upon the amount of resin which needs to be solubilized and the solvent power of the particular solvent. The amount and selection of the solvent is within the skill of the art. However, the solvent should not be inflammable or deleterious to humans, paint, or other things which may be sprayed. A particularly satisfactory solvent is methylene chloride.
As before indicated, the composition of the invention further comprises a propellant. It is contemplated that propellants conventionally used with aerosol containers will be used in the composition of this invention. Of course, such propellant should be non-toxic and be capable of spraying the composition. Propellants particularly contemplated in connection with this invention are Freons which arerecognized in the art as a class of polyhalogenated lower alkanes. Since these compounds are so well known in the art for propellants in aerosol containers, a further description of these compounds is not believed to be required. While other propelling gases may be used, such as nitrogen and carbon dioxide, such propellants are generally not satisfactory as propellants of the composition of this invention.
Sufficient propellant should be used to effect the spraying of the contents in the aerosol container and, in general, the propellant will comprise from about 60 percent to about 90 percent of the composition of the invention.
Example I The composition of this invention is prepared by first preparing a blend of fatty materials comprising methyl palmitate and a fatty acid mixture comprising palmitic Twelve pounds of this blend of fatty materials is com- I bined with three pounds of a solubilized resin solution. The resin solution is prepared by mixing one pound of polyvinyl acetate with two pounds of methylene chloride. The fatty materials and this solubilized resin may be mixed together. On the other hand, in commercial operations, four parts of the fatty components are introduced into an aerosol container and, to this is added one part of the resin solution. The container is then filled with about 21 parts of a Freon propellant, under pressure, in accordance with the usual practice in the art.
This composition, therefore, comprises the following ingredients:
12 percent fatty materials 3 percent resin solution 85 percent Freon propellant This solution could be sprayed at below 50 F. and set up at about 47 F. As before indicated, presently available commercial compositions become viscous and unsprayable at considerably higher temperatures.
Example 11 As another example of this invention, the same ingredients are used as specified in Example I, except that ethyl palmitate is substituted for the methyl palmitate in the manufacture of the compound.
Example 111 As another example of this invention, the same formula as in Example I is used, except that methyl stearate is utilized in place of the methyl palmitate.
Example IV In accordance with this example, the same ingredients re employed as in Example 1, except that the fatty materials comprise palmitic acid alone, in place of a mixture of stearic and palmitic acids.
Example V In accordance with this example, the same ingredients are used as in Example I, except that the fatty materials comprise about 12 percent of methyl palmitate, about 62 percent palmitic acid and about 26 percent stearic acid.
In using the composition of the invention, the composition is discharged from the aerosol container through the usual nozzle on to a surface which is to be decorated. This is in accord with the well known practice for effecting decorations with these artificial snows.
As before indicated, a principal feature of this invention is in the utilization of a particular mixture of fatty materials, the mixture comprising fatty acids in combination with esters having hydrophilic and oleophilic groups. Such ester not only provides improved dispersion and distribution of the fatty acid product, but, in addition, provides fluidity to the product at a much lower temperature than is provided by the artifical snow products presently available.
It will be apparent from the foregoing that various modifications in the composition may be made, within the scope of this invention, which are within the skill of the art as contemplated.
The various features of this invention which are believed to be new are set forth in the following claims.
We claim:
1. An improved artificial snow composition comprising, in combination, a flocking agent comprising between about 1 percent and about 20 percent of said composition, said flocking agent including a long chain fatty acid having from between 12 and 22 carbon atoms, a fluidizing agent in an amount of between about 1 percent and 20 percent of said flocking agent, said fluidizing agent being an ester of a short chain polyol having from 1 to 4 carbon atoms and a long chain fatty acid having from 12 to 22 carbon atoms, a propellant comprising polyhalogenated lower alkanes in an amount of about 60 percent and percent of said composition, a binding agent comprising synthetic resin polymer in an amount of about between .25 percent and 2 percent of said composition, and a solvent for said binding agent which is miscible with said flocking agent.
2. An improved artificial snow composition comprising, in combination, a flocking agent comprising between about 1 percent and about 20 percent of said composition, said flocking agent comprising a mixture of pahnitic acid and stearic acid, a fluidizing agent in an amount of between about 1 percent and 20 percent of said flocking agent, said fluidizing agent being methyl palmitate, a polyhalogenated lower alkane refrigerant propellant in an amount of about 60 percent and 90 percent of said composition, polyvinylacetate in an amount of about between .25 percent and 2 percent of said composition, and a solvent for said binding agent which is miscible with said flocking agent.
3. An improved artificial snow composition compris- 6 ing, in combination, a mixture of palmitic acid and stearic m HIIt f a ut 1 Percent Of d mp i i and t acid, the palmitic acid comprising about 70 percent and ylene chloride in an amount of about 2 percent of said the stearic acid comprising about 30 percent of said mixcomposition for dissolving said polyvinyl acetate. tu-re, said mixture comprising about 12 percent of said composition, a fluidizing agent in an amount of about 5 7 References Cited in the file of this Patent 10 percent of said mixture of fatty acids, said fiuidizing UNITED STATES PATENTS agent being methyl palnntate, a propellant COmPllSlIlg polyhalogenated lower alkanes in an amount of about 85 2,659,704 Kerr, Nov. 17, 1953 percent of said composition, polyvinyl acetate in an

Claims (1)

1. AN IMPROVEMENT ARTIFICAL COMPOSITION COMPRISING, IN COMBINATION, A FLOCKING AGENT COMPRISING BETWEEN ABOUT 1 PERCENT AND ABOUT 20 PERCENT OF SAID COMPOSITION, SAID FLOCKING AGENT INCLUDING A LONG CHAIN FATTY ACID HAVING FROM BETWEEN 12 TO 22 CARBON ATOMS, A FLUIDIZING AGENT IN AN AMOUNT OF BETWEEN ABOUT 1 PERCENT AND 20 PERCENT OF SAID FLOCKING AGENT, SAID FLUIDIZING AGENT BEING AN ESTER OF A SHORT CHAIN POLYOL HAVING FROM 1 TO 4 CARBON ATOMS AND A LONG CHAIN FATTY ACID HAVING FROM 12 TO 22 CARBON ATOMS, A PROPELLENT COMPRISING POLYHALOGENATED LOWER ALKANES IN AN AMOUNT OF ABOUT 60 PERCENT AND 90 PERCENT OF SAID COMPOSITION, A BINDING AGENT COMPRISING SYNETHETIC RESIN POLYMER IN AN AMOUNT OF BETWEEN .25 PERCENT AND 2 PERCENT OF SAID COMPOSITION, AND A SOLVENT FOR SUCH BINDING AGENT WHICH IS MISCIBLE WITH SAID FLOCKING AGENT.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3265650A (en) * 1963-05-20 1966-08-09 Robert J Kerr Inc Artificial snow compositions comprising polyvinyl acetate and water
WO1986002936A1 (en) * 1984-11-06 1986-05-22 Permasnow Limited Method for making artificial snow
US4793142A (en) * 1985-06-04 1988-12-27 Permasnow (Australasia) Limited Method for making artificial snow
DE102013227157A1 (en) * 2013-12-24 2015-06-25 Organic Protection GmbH Use of fatty acid esters as snow substitute

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2659704A (en) * 1953-08-31 1953-11-17 Protective Coatings Corp Self-spraying artificial snow composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2659704A (en) * 1953-08-31 1953-11-17 Protective Coatings Corp Self-spraying artificial snow composition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3265650A (en) * 1963-05-20 1966-08-09 Robert J Kerr Inc Artificial snow compositions comprising polyvinyl acetate and water
WO1986002936A1 (en) * 1984-11-06 1986-05-22 Permasnow Limited Method for making artificial snow
GB2191570A (en) * 1984-11-06 1987-12-16 Permasnow Ltd Method for making artificial snow
US4742958A (en) * 1984-11-06 1988-05-10 Permasnow (Australasia) Limited Method for making artificial snow
US4793142A (en) * 1985-06-04 1988-12-27 Permasnow (Australasia) Limited Method for making artificial snow
DE102013227157A1 (en) * 2013-12-24 2015-06-25 Organic Protection GmbH Use of fatty acid esters as snow substitute

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