US2659704A - Self-spraying artificial snow composition - Google Patents

Description

Patented Nov. 17, 1953 UNED STATES PATENT OFFIC SELF- SPRAYHVG ARTIFICIAL SNOW COMPOSITION No Drawing. Application August 31, 1953, Serial No. 377,681

30 Claims.

My invention relates to an improved decorative composition, and more particularly, to an improved self-spraying artificial snow formulation.

For some time spray snow," or self-spraying artificial snow has been available commercially, particularly as a Christmas season item. In essence, the spray snow is a packaged product which contains a suitable flocking agent or material suspended, dispersed or dissolved in a pressurized normally gaseous propellant, and the snow is sprayed from this package, as desired, through a suitably restricted aperture to obtain a spraying effect from the release of the pressurized gaseous propellant. As the material is thus sprayed, the flocking agent takes the form of flocculent snow-like particles which fall upon and generally adhere to the article or object being sprayed. Certain synthetic resins have been employed as flocking agents, and the most commonly employed propellant has been a Freon gas propellant.

Freons are recognized in the art as a class of polyhalogenated lower alkanes used generally as refrigerants. Such alkanes have not more than two carbon atoms (i. e., methane and ethane) and are at least trihalogenated with the lower molecular weight halogens (i. e., fluorine and chlorine), there being at least one fluorine (F) atom and at least one chlorine (Cl) atom in the molecule; and these compounds have the formula:

CDCIFXYQn-i) wherein n is an integer from 1 to 2, X is C1 or F, and Y is Cl, F or H. Examples: trichloromonofiuoromethane, dichlorodifluoromethane, chlorotrifluoromethane, dichloromonofluoro methane, difluoromonochloromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, monochloropentafluoroethane, and chlorodifluoromethyl methane, which have boiling points ranging from about 30 C. to 50 C.

A gas propellant is, of course, a gas under the conditions of use; in order to perform its function, it is stored under pressure (as a liquid) and released through an orifice to obtain the propellant effect (as a gas). The Freon gas propellants are thus gases at room temperature.

It will, of course, be appreciated that the spray snow packaged formulation requires a rather substantial quantity of the Freon gas propellant, in order to have an effective spraying or propelling action. On the other hand, the amount of the flocking agent used is a comparatively smaller amount, ranging from the minimum amount that may be used for practical purposes in order to obtain an appreciable quantity of snow from a given packaged unit to the maximum amount which may be used without obtaining a concentration so great that the flocking process during spraying is impeded or effectively destroyed. Heretofore, the most suitable commercially available spray snow formulations contained about 7% acrylic resins and about 93% Freon gas propellant (comprising a mixture of three Freons) As will be appreciated, both the acrylic resins andthe Freon gases are relatively expensive. An attempt has been made to reduce the cost of the aforementioned formulation, by substituting phenolic resin for about one-half of the'acrylic resin, but it has beenfound that this formulation has a tendency to undergo bubbling instead of flocking when sprayed at a close range. In fact, it has generally been necessary heretofore to carry out the spraying operation from a distance of at least 36 inches in order to effectively avoid bubbling. This, also, leaves much to be desired in connection with self-spraying snow formulations. The ingredients used in these commercially available snow sprays also have a very distinct odor which is noticeable during the spraying operation and which is undesirable for many purposes.

It is, therefore, an important object of the instant invention to provide an improved selfspraying artificial snow formulation.

It is a further object of the instant invention to provide a spray snow which flocs without bubbling at very close spraying ranges, which has a substantially increased quantity of active or solid ingredients per packaged unit, and/or which permits the use of ingredients aflording better odor control than that heretofore obtainable.

It is a further object of the instant invention to provide an improved self-spraying artificial snow-forming composition comprising a higher fatty acid as a bulking material, a synthetic resin polymer as a flocking agent, a suitable solvent therefor, and a volatile polyhalogenated lower molecular weight alkane refrigerant as the gas propellant. I

, formulation permits the use of a higher solids content. This is a very great advantage in most i Stilla further objector the instant invention I I is to provide i an improved composition compris- I wherein one of the radicals R and R. is an alkenyl radical and the other is an alkyl radical, Rhas 1 not more than 3 carbon atoms, R has notmore I than 4 carbonatoms, an ester wherein R is un-' saturated has a total of 4 carbon atoms, and an important aspect or advantage'is thatthe instant cases, whereiniit is more desirable to use low or mini- I mum solids content; Whatever thesolids con-f tent, the unique synergistic effect obtained by i I the use of the fatty acid and resin in combinationembodies the various advantages just mentioned, and it permits the use of high solids when i desired (wherein abcut.5-15% fatty acid is used). In high solids formulations, the preferred ,range forthe fatty acid is about 843%, and.

the most preferred amount is about 11%. In low solids formulations, the preferred range is about to 8-'-10%,'and the'mostpreferred'amount is about The overlapping proportion of -.8-% between the two preferred proportions ester whereinR is'unsaturated hasa totalof 4-8 carbon atoms.

be sprayed by gas propulsion to form such coating, which consistsessentially' of the ingredients of said coating intimately dispersed in 1 -6 parts ofasuitable solvent.

Other and further objects, advantages, and

features of myinvention will become apparent to those skilled in the artifrom the following detaileddisclosure of preferred embodiments there- I 'My invention consists in an improved selfspraying artificial snow-forming composition" comprising a higher fatty acid as .abulking mate- I rial, a'synthetic resin polymer as a flocking agent, a suitable solvent therefor, and a volatile polyhalogenated low molecular weight alkane refrigerant as the propellant, said resin being a polymer of an ester having the formula:

wherein one of the radicals R and R is an alkenyl radical and the other is an alkyl radical, R has not more than 3 carbon atoms, R has not more than 4 carbon atoms, an ester wherein R is unsaturated has a total of 4 carbon atoms, and an ester wherein R is unsaturated has a total of 4-8 carbon atoms.

As a bulking agent or material for my composition I have found the higher fatty acids (1. e., 012-018) to be uniquely superior. Such acids include lauric, myristic, palmitic, stearic, oleic, etc., and the most preferred of these is stearic, which gives definitely superior results. The bulking agent is used, as its function indicates, to replace or supplement a portion of the resin content and for this purpose, it may be used in amounts ranging from about 2% to about 15% of the composition. (As used herein, the term "per cent and "parts mean percent and parts by weight unless otherwise specifled.) Actually, there are a number of distinct advantages provided by the instant formulation and these include improved spraying performance (particularly by resistance to bubbling at close ranges), a whiter snow product, a "fluffler" snow product, and an improved odor during spraying (particularly by the masking eflect of the stearic acid upon the somewhat acrid acrylic acid odor). Another particularly A more specific obiectof-the instant invention v is to provide an improved flocculent sprayed coat- ,ing of artificial snow consisting essentially of2-15. parts of stearic acid and IVs-8V2 parts of polyc :methylmeth acrylate resin or poiyvinylacetate ,resin; and an improved composition adapted to represents the most preferred proportion in coma positions. wherein neither extreme of the solids I contents is desired, although it is still appreciably- ,above the solids contents heretofore used.

: 'Asthe resin component, or flockingagent, I

have found certain synthetic resin polymers to p be particularly'suitable,whereas others are sub I bstantially or whollyinoperative. 'There'sins of the; invention are olymers of an ester having the formula:

' wherein one of the radicals'R and R is an 'al-" p kenyl radical and the other. is analkyl radical, R has not more than -3 carbon atoms, R has not more than 4 carbonatoms, an'ester wherein R is'unsaturated has a total of 4 carbon atoms, and r an ester wherein-R is unsaturated has a; total of i 48 carbon atoms. I

I Referring to the above definition, it will be seen that the ester is vinylacetate, wherein R is unsaturated and the total number of carbon atoms is consequently four. If R. is unsaturated, then the radical o p at may be methacrylyl or acrylyl, and the radical --O-R' may be methoxy, ethoxy, propoxy or butoxy, B. being an alkyl radical having not more than 4 carbon atoms. methylmethacrylate and methylacrylate, ethylmethacrylate and ethylacrylate, propylmethacrylate and so on up to butylmethacrylate. Methylacrylate has a total of four carbon atoms and butylmethacrylate has a total of eight carbon atoms. Of course, mixtures and copolymers may be used. The acrylic polymers just referred to may be defined as polymers of an ester having the following formula:

o x-lLo-x' wherein X is an alkenyl radical having not more than 3 carbon atoms and not more than 2 carbon atoms in a chain, and X is an alkyl radical hav ing not more than 4 carbon atoms. The most preferred of the acrylic polymers is polymethylmethacrylate resin.

The flocking agent or resin is used. as its function indicates, in combination with the bulking agent to effectively cause suitable flocking of the combined ingredients so as to simulate the texture of snow. Again, high, low or medium solids content formulations may be employed. In general, the flocking agent is used in amounts although there are special situations I Such esters include ranging from about 1% to about 8%% of the composition, and in the high solids formulation, it is used in the range 2 /28 /2% and preferably about 5-7%. Using the most preferred resins, such as polymethylmethacrylate and Polyvinylacetate, and the preferred amounts of the bulking agent for the high solids formulation, it has been found that about 6% resin gives superior results.

In the low solids formulation, the preferred amount of resin is about 2-5% and most preferably 3%. In a medium solids formulation, about 4-5% is most preferred.

The solvent is used in the instant sprayable composition so as to obtain an intimate mixture or dispersion of the solid ingredients, namely, the resin and the bulking agent, so that such ingredients may be effectively borne by the gas propellant on to the article to be covered With the resulting snow-like flocculent product. Preferably, the solvent is sufficiently active to effect complete solution of both the solid ingredients, and the solvent is, of course, used in an amount sufficient to accomplish the complete dissolving of such ingredients, so as to provide a single liquid phase which is to be gas-propelled to form the spray. In this single liquid phase, the propellant is, of course, dissolved and the solvent plus the propellant which is miscible therewith should be capable of dissolving entirely the solids content. Such a solvent may be chlorinated hydrocarbon, an ester, an aromatic hydrocarbon, a ketone or even water in some cases. The selection of the most suitable solvent is, in most instances, within the skill of the art, since the solvents for these resins (and fatty acids) are known. Most preferably a volatile solvent, such as acetone, may be used, if no fire hazard is involved, and methylene chloride and/or a non-propellant liquid Freon, such as Freon-11 (trichloromonofiuoromethane) may be preferred otherwise. The amount of solvent used may range from about to about 60% of the composition, and about 10-40% is the range for high solids formulations. The preferred ranges are about 25-30% in a high solids formulation, about 30-45% in a medium solids formulation, and about 40-50% in a low solids formulation.

The instant combination of a bulking agent and a flocking resin, intimately dispersed or dissolved in the solvent, is uniquely adapted to be sprayed by suitable gas propulsion to form a synthetic snow coating, which coating ultimately consists of only the fatty acid bulking agent and the flocking resin, since the solvent will be lost by evaporation. The final coating has distinctly superior fluffy, white snow-like texture, and may be obtained in the substantial absence of imperfections resulting from bubbling, even if spraying is carried out from a very close range.

The gas propellant employed is, of course, a Freon refrigerant of the type hereinbefore described. Most preferably, it is one of the particularly volatile or low boiling Freons, such as dichlorodifiuoromethane (Freon-12) which has a boiling point of -28 C. It will also be noted that a very substantial portion of the spraying composition consists of the bulking material, the flocking agent and the solvent, so that a substantially smaller proportion of the gas propellant need be used in the instant composition. Also, the instant composition contains, if desired, at least about twice as much active material, which will ultimately result in snow-particle formation, as those heretofore used.

An example of a preferred high solids formulation for use in the instant invention is as follows:

11% bulking agent--stearic acid 6% flocking agent polymethylmethacrylate resin 28% solvent-acetone 55% propellantdichlorodifiuoromethan The above formulation was suitably packaged and snow spraying therewith, even a close range of less than 18 inches, resulted in excellent flocking with no bubbling. Substantially, the same results were obtained using polyvinylacetate resin in place of the polymethylmethacrylate resin in the above formulation.

Other formulations which are particularly useful in the practice of the invention include:

Amount Range Low Solids: Percent Percent (A) Stearic acid 5 3-10 Acrylic resin 3 2-5 Fre0nll.... 46 Freon-l2... 46 Rem.

(ll) S'earlc acid 5 3-10 Acrylic resin 1 3 2-5 Methylene chloride. 46 40-50 Freon-l2 46 Rem.

Medium S. llds:

o stearic acid 9 8-10 Acrylic resin 1 4 4-5 Methylene chloride. 31 25-35 Fro on-ll l 6 0-10 Freon-l2 50 Rem.

(D) Stcaric aciL 9 8-10 Acrylic resin 1 4 4-5 Methylene chloride. 37 30-45 Freon-l2 50 Rem.

(E) stearic acid 8 8-10 Paiyvinylacetate resin 5 4-5 Methylene chloride 30 30-45 Freon-l2 57 Ram. High S'ill'lS! (F) Steal-i0 acid 11 843 Acrylic resin 1 6 5-7 Methylene chloride 28 25-30 Freon-l2 55 Rem.

1 Acrylic resin: B-72 Acrylic" (Rohn and Haas) or Lucite 46 (Du Pom)-polymethylmethacrylatc.

Using each of the foregoing formulations, excellent results are obtained in the spraying operation and in the resulting snow product.

It will thus be seen that the instant invention permits the use of as much as two and onehalf times more active ingredients than were used heretofore in snow sprays, and the instant invention permits the use of approximately onehalf as much Freon than was used heretofore in commercial formulations. In addition, a very substantial amount of the active ingredients consists of a relatively inexpensive fatty acid, stearic acid, which is substantially less expensive than the acrylic resin. The instant bulking agent, unlike phenolic resins heretofore suggested, materially assists in the flocking operation by suitable cooperation with the fiocking resin, and in no way impairs the flocking process or causes bubbling or other undesirable phenomenon. Also, the presence of a substantial amount of a solvent which may be selected on the basis of its characteristic odor, or lack thereof, is present in the instant formulation so as to reduce appreciably the odor ordinarily accompanying snow spraying operations.

It will be understood that modifications and variations may be effected without departing from the scope of the novel concepts of the present invention.

This is a continuation-in-part of my application Serial No. 318,953, filed November 5, 1952, entitled Self-Spraying Coating."

I claim as my invention:

1. A composition comprising 5-15% of a C12-C1s fatty acid, 2%;-8 of a synthetic resin polymer, 10-40% of a solvent for the acid and the resin, and the balance consisting essentially of a polyhalogenated lower alkane refrigerant propellant, said resin being a polymer of an ester selected from the group consisting of vinyl acetate and an ester having the formula:

x-g-o-x' wherein x is a 01-03 alkenyl radical having not more than 2 carbon atoms in a chain and X is a C1-C4 alkyl radical.

2. A composition comprising 8-13 of a C111-C1a fatty acid, 5-7% of a synthetic resin polymer. of a solvent for the acid and the resin, and the balance consisting essentially of a polyhalogenated lower alkane refrigerant propellant, said resin being a polymer of an ester selected from the group consisting of vinyl acetate and an ester having the formula:

0 x-A-dwherein X is a C2-C3 alkenyl radical having not more than 2 carbon atoms in a chain and X is a C1-C4 alkyl radical.

4. A composition comprising 5-15% of a 012-018 fatty acid, 2 /2-8 /2% of polyvinylacetate resin as a flocking agent, -40% of a solvent for the acid and the resin, and the balance consisting essentially of a polyhologenated lower alkane refrigerant propellant.

5. A composition comprising 5-15% of a 012-018 fatty acid, 2 -8 of polymethylmethacrylate resin as a flocking agent, 10-40% of a solvent for the acidand the resin, and the balance consisting essentially of a polyhalogenated lower alkane refrigerant propellant.

6. A composition comprising 5-15% of stearic acid as a bulking agent, 2 /2-8V2% of a synthetic resin polymer, 10-40% of a solvent for the acid and the resin, and the balance consisting essentially of a polyhalogenated lower alkane refrigerant propellant, said resin being a polymer of an ester selected from the group consisting of vinyl acetate and an ester having the formula:

wherein X is a C2C3 alkenyl radical having not more than 2 carbon atoms in a chain and X is a C1-C4 alkyl radical.

7. A composition comprising 5-15% of stearic acid as a bulking agent, /z-8V2% of polymethylmethacrylate resin as a flocking agent, 10-40% of a solvent therefor, and the balance consisting essentially of the dichlorodifluoromethane propellant, the solvent being a solvent for the wherein X is a C2-C3 alkenyl radical having not more than 2 carbon atoms in a chain and X is a C1-C4 alkyl radical, the solvent being a solvent for the acid and the resin, and forming a one-phase liquid system with the propellant in the composition.

9. A composition as claimed in claim 8 wherein the bulking agent is stearic acid, the flocking agent is polymethylmethacrylate resin and the propellant is dichlorodifluoromethane.

10. A composition as claimed in claim 8 wherein the bulking agent is stearic acid, the flocking agent is polyvinylacetate resin and the propellant is dichlorodifluoromethane.

11. A composition as claimed in claim 8 wherein the bulking agent is stearic acid, the flocking agent is polymethylmethacrylate resin, the solvent is acetone, and the propellant is dichlorodifluoromethanc.

12. A composition as claimed in claim 8 wherein the bulking agent is stearic acid, the flocking agent is polymethylmethacrylate resin, the solvent is methylene chloride, and the propellant is dichlorodifluoromethane.

13. A self-spraying artificial snow-forming composition having the following formulation: 11% stearic acid, 6% polymethylmethacrylate resin, 28% acetone, and 55% dichlorodifluoromethane.

14. A self-spraying artificial snow-forming composition having the following formulation: 11% stearic acid, 6% polymethylmethacrylate resin, 28% methylene chloride, and 55% dichlorodifluoromethane.

15. A self-spraying artificial snow-forming composition having the following formulation: 5% stearic acid, 3% polymethylmethacrylate resin; 46% trichloromonofluoromethane, and 46% dichlorodifluoromethane.

16. A self-spraying artificial snow-forming composition having the following formulation: 9% stearic acid, 4% polymethylmethacrylate resin, 31% methylene chloride, 6% trichloromonofluoromethane, and 50% dichlorodifluoromethane.

17. A composition comprising 2-15% of a Cir-C18 acid, 1 /g8 /2% of a synthetic resin polymer. 10-60% of a solvent for the acid and the resin, and the balance consisting essentially of a polyhalogenated lower alkane refrigerant propellant, said resin being a polymer of an ester selected from the group consisting of vinyl acetate and an ester having the formula:

wherein X is a C2-C3 alkenyl radical having not more than 2 carbon atoms in a chain and X is a C1-C4 alkyl radical.

18. A composition comprising 3-10% of a CIT-C18 fatty acid, 2-5% of a synthetic resin polymer, 40-50% of a solvent for the acid and the resin, and the balance consisting essentially of a polyhalogenatcd lower alkane refrigerant propellant, said resin being a polymer of an ester selected from the group consisting of vinyl acetate and an ester having the formula:

xJLo-x' wherein X is a C2-C3 alkenyl radical having not more than 2 carbon atoms in a chain and X is a C1-C4 alkyl radical.

19. A composition comprising of a Crz-Cza fatty acid, 3% of a synthetic resin polymer, 40-50% of a solvent for the acid and the resin, and the balance consisting essentially of a polyhalogenated lower alkane refrigerant propellant. said resin being a polymer of an ester selected from the group consisting of vinyl acetate and an ester having the formula:

0 lat-OJ wherein X is a C2-C3 alkenyl radical having not more than 2 carbon atoms in a chain and X is a C1-C4 alkyl radical.

20. A composition comprising 13-10% of a (312-018 fatty acid, 2-5% of a polymethylmethacrylate resin as a flocking agent, 40-50% of a solvent for the acid and the resin, and the balance consisting essentially of a polyhalogenated lower alkane refrigerant propellant.

21. A composition comprising 8'-10% of a C12- Cm fatty acid, 4-5% of polymethylmethacrylate resin as a flocking agent, 30-45% of a solvent for the acid and the resin, and the balance consisting essentially of a polyhalogenated lower alkane refrigerant propellant.

22. A composition comprising 12-15% of stearic acid as a bulking agent, lV -8 /2% of a synthetic resin polymer, 10-60% of a solvent for the acid and the resin. and the balance consisting essentially of a polyhalogenated lower alkane refrigerant, said resin being a polymer of an ester 4 selected from the group consisting of vinyl acetate and an ester having the formula:

wherein X is a C2-C3 alkenyl radical having not 5 more than 2 carbon atoms in a chain and X is a C1-C4 alkyl radical.

23. A composition comprising 2-15% of stearic acid as a bulking agent, 1 /2-8 /275 of polymethacrylate resin as a flocking agent, 10-60% of a 24. A self-spraying artificial snow-forming composition comprising 340% of Cm-Cia fatty acid as a bulking agent, 2-5% of synthetic resin polymer as a flocking agent. a suitable volatile solvent therefor, and a volatile polyhalogenated low molecular weight alkane refrigerant as a propellant, said resin being a polymer of an ester selected from the group consisting of vinyl acetate and an ester having the formula:

. wherein X is a C2-C3 alkenyl radical having not more than 2 carbon atoms in a chain and X isa C1-C4. alkyl radical, the solvent being a solvent for the acid and the resin, and forming a onephase liquid system with the propellant in the composition.

25. A composition as claimed in claim 24 wherein the bulking agent is stearic acid, the flocking agent is polymethylmethacrylate resin and the propellant is dichlorodifluoromethane.

26. A composition as claimed in claim 24 wherein the bulking agent is stearic acid, the flocking agent is polyvinylacetate resin and the propellant is dichlorodifluoromethane.

27. A composition as claimed in claim 24 wherein the bulking agent is stearic acid, the flocking agent is polymethylmethacrylate resin, the solvent is trichloromonofluoromethane, and the propellant is dichlorodifiuoromethane.

28. A self-spraying artificial snow-forming composition comprising 8-10% of a Cia-Cu fatty acid as a bulking agent, 4-5% of a synthetic resin polymer as a flocking agent, a suitable volatile solvent therefor, and a volatile polyhalogenated low molecular weight alkane refrigerant as a propellant, said resin being a polymer of an ester selected from the group consisting of vinyl acetate and an ester having the formula:

x- -o-x' wherein X is a C2-C3 alkenyl radical having not more than 2 carbon atoms in a chain and X is a C1-C4 alkyl radical. the solvent being a solvent for the acid and the resin, and forming a onephase liquid system with the propellant in the composition.

29. A composition as claimed in claim 28 wherein the bulking agent is stearic acid the flocking agent is polymethylmethacrylate resin and the propellant is dichlorodifluoromethane.

30. A composition as claimed in claim 28 wherein the bulking agent is stearic acid, the flocking agent is polymethylmethacrylate resin, the solvent is methylene chloride, and the propellant is dichlorodifluoromethane.

ROBERT J. KERR.

No references cited.

Claims (1)

1. A COMPOSITION COMPRISING 5-15% OF A C12-C18 FATTY ACID, 21/2-81/2% OF A SYNTHETIC RESIN POLYMER, 10-40% OF A SOLVENT FOR THE ACID AND THE RESIN, AND THE BALANCE CONSISTING ESSENTIALLY OF A POLYHALOGENATED LOWER ALKANE REFRIGERANT PROPELLANT, SAID RESIN BEING A POLYMER OF AN ESTER SELECTED FROM THE GROUP CONSISTING OF VINYL ACETATE AND AN ESTER HAVING THE FORMULA: