US3812043A - Package for dispensing an ice-removing composition - Google Patents

Package for dispensing an ice-removing composition Download PDF

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US3812043A
US3812043A US00318504A US31850472A US3812043A US 3812043 A US3812043 A US 3812043A US 00318504 A US00318504 A US 00318504A US 31850472 A US31850472 A US 31850472A US 3812043 A US3812043 A US 3812043A
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valve
package
group
outlet
composition
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US00318504A
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Der Linde W Van
C Weslager
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D83/00Containers or packages with special means for dispensing contents
    • B65D83/14Containers or packages with special means for dispensing contents for delivery of liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant for a product delivered by a propellant
    • B65D83/44Valves specially adapted therefor; Regulating devices
    • B65D83/46Tilt valves
    • 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
    • C09K3/18Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • C09K3/185Thawing materials

Definitions

  • a package adapted for preparing and dispensing a heated de-icer composition comprising a container having an outlet and a valve adapted to control the dispensing of said composition therefrom, and containing (A) at least one water-soluble ice-melting substance selected from the group consisting of monohydric C -C saturated aliphatic alcohols, ethylene glycol, propylene glycol, diethylene glycol, acetone, methylethyl ketone or mixtures of the foregoing,
  • R R and R can be the same as each other or different from each other and are selected from the group consisting of: H, CH C H C H- C H CZHQOH, C3H5OH, 0r C4H8OH,
  • R3, R4, R5, R6 and R3, R9, R10, R11 can be the same as each other or different from each other and are selected from the group consisting of H, CH or C2H5 m can be 0 through 5, n can be 1 through 6 provided that n and m are selected so that m+n is no greater than about 6,
  • (E) means to provide intimate contact between materials (A), (B) and (C) while (A) is being conveyed toward said outlet.
  • This invention relates to an aerosol-type package for preparing and dispensing a composition capable of melting and removing a deposit of ice, frost or the like from ice a surface, for example, from an automobile windshield.
  • a composition is some times referred to in the art as a de-icer composition.
  • a package adapted for preparing and dispensing a heated de-icer composition comprising a container having an outlet and a valve adapted to control the dispensing of said composition therefrom, and containing (A) at least one water-soluble ice-melting substance selected from the group consisting of monohydric C -C saturated aliphatic alcohols, ethylene glycol, propylene glycol, diethylene glycol, acetone, methylethyl ketone or mixtures of the foregoing,
  • R R and R can be the same as each other or different from each other and are selected from the group consisting of: H, CH C H C3H7, C4H9, C2H4OH, C3H6OH, OI C4H8OH,
  • R3, R4, R5, R6 and R3, R9 R10 can be the Same as each other or different from each other and are selected from the group consisting of H, CH O1 C2H5,
  • n can be 1 through 6 provided that n and m are selected so that m+n is no greater than about 6,
  • (E) means to provide intimate contact between materials (A), (B) and (C) while (A) is being conveyed toward said outlet.
  • FIG. 1 shows an embodiment of the novel package in central vertical section and partially broken away; a portion of the valve stem is shown partially broken away; a portion of the valve stem is shown in front view.
  • the dispensing valve is in the closed position.
  • FIG. 2 shows a portion of the package of FIG. 1 in which the dispensing valve is in the open position.
  • FIG. 3 shows an enlarged perspective view of the lower face of the valve head of FIG. 1. The drawing is described in further detail in Example 1.
  • the water-soluble ice-melting substance is preferably made up of about 60-100% by weight of a C -C saturated aliphatic monohydric alcohol and up to about 40% by weight of a polyhydric alcohol, particularly when the package is to be used for removing ice or frost from automobile Windshields and the like.
  • a polyhydric alcohol particularly when the package is to be used for removing ice or frost from automobile Windshields and the like.
  • the monohydric alcohol is 50-100% by weight of isopropanol and up to 50% of methanol, ethanol, propanol or blends thereof.
  • Component (A) can be entirely monohydric alcohol or it can be made up entirely or partially of other water-soluble substances which are capable of melting ice when dispensed from the package and which are not harmfully reactive with the surfaces of the article to which the de-icer composition is to be applied; for example, (1) a polyhydric alcohol such as ethylene glycol, propylene glycol or diethylene glycol, (2) a ketone such as acetone or methyl ethyl ketone, (3) salts such as sodium chloride and calcium chloride. When a salt is used it is preferably present as a solution in water or alcohol. When a polyhydric alcohol is present, the amount used is adjusted to give the composition the desired evaporation rate and anticorrosion characteristics. In some of the most useful embodiments of the invention, about 60-85% of component (A) is present based on the combined weight of components (A), (B), (C) and (D) in the package.
  • a polyhydric alcohol such as ethylene glycol, propylene glycol or di
  • Hydrogen peroxide is usually preferred as component (B) of the package of this invention.
  • useful component (B) compounds are barium peroxide, calcium peroxide, urea hydrogen peroxide, and various hydroperoxidates.
  • the latter which contain hydrogen peroxide of crystallization, include sodium borate hydroperoxidate, magnesium carbonate hydroperoxidate and sodium pyrophosphate hydroperoxidate.
  • component (B) can be admixed with an inert carrier such as water.
  • Component (C) must be capable of initiating the heatgenerating reaction of component (B) at the storage temperature of the package.
  • the storage temperature of the package may be well below freezing as is often the case in an unheated automobile or garage, or it may be the temperature of a heated automobile or home; for example, the storage temperature is likely to be a temperature within the range of about minus 29 C. to plus 27 C. (about minus 23 F. to plus 80 F.).
  • Compounds suitable for use as component (C) include sulfite salts of alcohol amines.
  • Suitable alcohol amines from which sulfite salts can be formed include those having the following structure:
  • R R and R can be the same as each other or different from each other and are selected from the group con- Sisting Of: H, CH3, C2H5, C3H7, C4Hg, C2H4OH, C H OH, or C H OH,
  • R R R R R and R R 10 R can be the same as each other or different from each other and are selected from the group consisting of H, CH or C H m can be 0 through 5, n can be 1 through 6 provided that n and m are selected so that m+n is no greater than about 6.
  • Suitable alcohol amines from which sulfite salts can be formed include the following:
  • Sulfite salts of alcohol amines can be formed by any suitable method including passing S0 through the alcohol amine.
  • Sulfite salts of alcohol amines are preferred because of their compatibility and solubility with the ice melting substance and because they have little or no tendency to form a deposit which will unduly reduce visibility when the composition is applied to a windshield. Furthermore, sulfite salts of alcohol amines are desirable because unlike many reducing agents, relatively small amounts of such salts will produce suitable heat generation with a 12% or less weight percent solution of hydrogen peroxide in water. It is desirable to use a concentration of hydrogen peroxide of 12% or less, and preferably less than 10%, since at greater concentrations, hydrogen peroxide can cause permanent eye damage. This is believed to be an important consideration because if for some reason the aerosol can failed and only the hydrogen peroxide was expelled from the can, if its concentration was greater than 12%, permanent eye damage could be caused if it contacted the eye.
  • the reducing agent is mixed with component (A), and the resulting mixture is stored within a chamber adapted to prevent said mixture from coming in contact with component (B) while the valve means that controls the dispensing of the de-icer composition is closed.
  • component (D) of the novel package is a propellent capable of providing fluid pressure sufficlent to dispense the ice-melting substance when the dlspensing valve is open.
  • the useful propellents include those known to be operable in an aerosol-type package, for example, a compressed gas such as nitrogen, nitrous oxide or carbon dioxide, or a volatile organic material such as isobutane, straight-chain aliphatic hydrocarbons, and water-insoluble chlorine and fluorine substituted hydrocarbons having suitable vapor pressure.
  • About 325% of propellent is usually preferred based on the combined weight of propellent and other fluids within the package.
  • Component (E) of the package of this invention consists of means to provide contact between components (A), (B) and (C) while the charge of ice-melting substance is being conveyed to the container outlet.
  • a preferred form of component (E) comprises a common duct 26 located downstream from the opening of the open valve as shown in the attached drawing, and means to feed components (A), (*B) and (C) into said duct from the isolated storage chambers formed by can 34 and tube 33. It can be seen in FIG. 2 that gap 37 is the opening of the open valve.
  • Another preferred form of component (E) comprises a common duct located upstream from the opening of the open valve. This is shown in FIG. 1 of U.S.
  • duct 20 is located upstream from the central portion of valve 17 (near point 47) where the valve opens, and the components of a de-icer composition can flow into said duct from the isolated storage chambers formed by can 24 and tube 26 when the valve is opened.
  • additives can also be present in the package and dispensed as a component of the heated de-icer composition, for example, water, odor-controlling agents, surfactants, anticorrosive agents and viscosity controlling agents.
  • the package of the present invention is useful for preparing and dispensing a heated de-icer composition.
  • the package Prior to use, the package can be stored at ordinary room temperature or at the ice-forming temperatures commonly encountered in an unheated automobile standing outdoors in cold winter weather.
  • the invention makes it possible to remove deposits of ice, frost and the like from automobile windshields and other surfaces with surprising speed and efficiency.
  • a heated charge of ice-melting composition can be prepared and applied instantaneously by simply opening the valve and allowing the heated composition to flow from the outlet onto the ice-covered surface.
  • the ice-removing procedure can include, if desired, the operation of automobile windshield wipers.
  • the package can be entirely free of any awkward attachments and there is no need for a source of electricity, steam or hot water.
  • outer container 34 which is adapted for storing a liquid under pressure, is a can of the type commonly used in aerosol dispensers.
  • the upper portion of can 34 is rounded and tapered to form a circular opening surrounded by a rolled bead 1'8 spun from the metal of the can.
  • the rolled edge of bowl-shaped cover 19 tightly engages bead 18, and after the contents of the can are inserted, it is crimped therewith to form a pressure-proof seal.
  • Top wall 20' of can 34 has an aperture which is outwardly flanged about axis a perpendicular to wall 20; in this aperture is lockingly and sealingly fitted a tilt-opening self-closing dispensing valve.
  • the dispensing valve comprises a tubular seal 17 made of a resilient elastic rubber composition fitted sealingly in aperture 27; the valve also comprises a tubular stem 14 made of a relatively rigid plastic composition fitted coaxially (on axis a) and sealingly in seal 17.
  • the rigid stem has relatively little elastic deformation under load compared with that of resilient seal 17.
  • Stem '14 terminates inside of can 34 in disc-shaped valve head 25 and terminates outside of can 34 in dispenser outlet 10.
  • the exterior portion (above aperture 27) of stem 14 has (a) a laterally extending shoulder 16 which abuts against the upper end face 13 of seal 17 at a level remote from that of wall 20 and (b) a laterally extending ring 15 in locking contact with a matching groove in the inner wall of seal 17.
  • Collapsible inner container 33 is a flexible plastic tube which is smaller than can 34 and has a beaded upper end 23 sealingly fitted in annular groove 31 in the side wall of valve head 25-.
  • Lower face 32 of valve head 25 forms the top wall of collapsible container 33.
  • end face 21 also forms part of the top wall of container 33 since it serves as a closure for channels 24 when the valve is closed.
  • the heat-sealed lower end 35 of tube 33 almost touches bottom wall 36 of can 34.
  • Tubular seal 17 has an enlarged lower portion 28 which has a large washer-like sealing surface in contact with the inner side of wall 20 adjacent aperture 27, and which terminates inside of can 34 in an annular end face 21 at a level remote from the level of top wall 20; and valve head 25 has a laterally extending annular shoulder 22 in sealing contact with end face 21, thereby forming a breachable seal.
  • the resilient material of seal 17 is slightly compressed at end face 21.
  • annular gap or chamber 30 (counterbore recess) which is in communication with dispenser outlet 10 through lateral port 29 and central passage 26 of stem '14.
  • Port 29 is provided by drilling a hole diametrically through the valve stem just above shoulder 22.
  • Annular chamber 30 is partitioned by the breachable seal from the chamber containing liquid 38.
  • valve head 25 is perforated with 8 channels 24; each channel has a diameter of 32 mils. These channels provide communication between the interior of collapsible tube 33 and (at) end face 21 of tubular seal 17 when the valve is closed, and (b) gap 30 when the valve is open. It can be seen in FIG. 2 that the interior of the chamber containing liquid 38 and the interior of tube 33 are in communication with annular chamber 30 (and therefore port 29, passage 26 and outlet 10) only when stem 14 is tilted enough to breach the seal and thereby provide a gap 37 between end face 21 of the seal and annular shoulder 22 of the valve head.
  • Cap 11 has internal threads to match external threads 12 of the upper portion of stem 14. When the cap is in place, its lower edge abuts upon head 18; thus stem 14 is locked in the erect position.
  • the dispenser shown in FIG. 1 is adapted for storing liquid 38 (including a propellent) in can 34 and a dilTerent liquid 39 in tube 33, and for dispensing these two liquids simultaneously and intermittently through outlet 10.
  • cap 11 is removed and the dispenser is inverted so that the upper portion of can 34 is filled with liquid; stem 14 is tilted to open the valve, and liquids 38 and 39 become mixed as they flow into gap 30 through gap 37 en route to outlet 10.
  • the flow of both liquids into gap 30 stops the instant the valve stem is permitted to return to the erect positoin and starts again the instant the valve stem is tilted.
  • a Formula 1.1 reducing agent composition is prepared by (a) mixing 55.6 parts of tetra-Z-hydroxypropyl-ethylene-diamine with 30.5 parts of methanol and 1.5 part water, (b) cooling the resulting mixture to 0 C., and (c) passing sulfur dioxide into the cooled mixture until 12.4 parts of sulfur dioxide is reacted with the diamine.
  • the resulting Formula 1.1 composition is a solution of 69.5 parts of tetra-Z-hydroxypropyletylenediamine-dihydrosulfite in 30.5 parts of methanol.
  • a Formula 1.2 composition is prepared by mixing 30 parts of the Formula 1.1 composition with 70 parts of a 50/50 blend of methanol and isopropanol.
  • the package shown in FIG. 1 is prepared for use by (1) placing 200 grams of the Formula 1.2 composition into can 34 (a 12 ounce can), (2) displacing the air in the can with isobutane, (3) assembling valve stem 14, tubular seal 17 and cover 19 as described above and shown in FIG. 1, (4) placing 20 ml.
  • Cap 11 is removed, the package is held in an inverted position (bottom side up), the valve is opened by tilting the valve stem, a quantity of heated de-icer composition is dispensed from outlet 10 onto an ice-coated windshield, and the valve is allowed to close.
  • the dispensed de-icer has a tempedature of 63 C., and it rapidly removes the coating of ice from the windshield.
  • the valve is rapidly opened and closed to dispense numerous small amounts of heated de-icer composition onto ice-coated areas of Windshields and other objects, thereby quickly removing the layer of ice.
  • the separately stored liquid materials within can 34 and tube 33 flow through gap 37 into gap 30; and as the resulting composition entering gap 30 flows through port 29, duct 26 and outlet 10, it becomes mixed and heated substantially instantaneously as the result of a rapid exothermic reaction between the tetra-Z-hydroxypropylethylenediamine-dihydrosulfite and the hydrogen peroxide.
  • the de-icer composition flowing into duct 26 contains about 6 parts of Formula 1.2 for each part of the 11.5% hydrogen peroxide solution.
  • Example 1 When the performance of the package prepared in Example 1 is compared with that of a package prepared in the same manner except for the omission of the hydrogen peroxide in tube 33, it is found that a 5 gram portion of the heated composition dispensed from the package of Example 1 is capable of removing 60-70% more ice in 15 seconds than the same amount of the non-heated composition dispensed from the peroxide-free package.
  • EXAMPLE 2 A package having beneficial utility for the rapid removal of ice or frost from Windshields and the like is prepared as described in Example 1 except the propellent carbon dioxide is used instead of isobutane in steps (2) and (7); in step (7), enough carbon dioxide is introduced into the can so that the pressure within the package is about 80 p.s.i.g. When the resulting package is stored at 0 C. for several hours prior to use, it is still very useful for the rapid removal of ice or frost from Windshields, the dispersed heated de-icer having a temperature of 50 C.
  • a package adapted for preparing and dispensing a heated de-icer composition comprising a container having an outlet and a valve adapted to control the dispensing of said composition therefrom, and containing (A) at least one water-soluble ice-melting substance selected from the group consisting of monohydric C -C saturated aliphatic alcohols, ethylene glycol, propylene glycol, diethylene glycol, acetone, methylethyl ketone or mixtures of the foregoing,
  • R R and R can be the same as each other or different from each other and are selected from the group consisting of: H, CH C H C H C4H9, C2H4OH, C3H6OH, Or C4H3OH,
  • R R R R R and R R R R R can be the same as each other or different from each other and are selected from the group consisting of H, CH3, OI C2H5,
  • n can be 1 through 6 pro vided that n and m are selected so that m-l-n is no greater than about 6,
  • (E) means to provide intimate contact between materials (A), (B) and (C) while (A) is being conveyed toward said outlet.
  • component (C) is selected from the group consisting of sulfite salts of the following alcohol amines and mixtures of sulfite salts of the following alcohol amines:
  • a heated de-icer composition obtained by intimately 9.
  • a process for removing a deposit of ice or the like from a surface which comprises applying to said deposit a heated de-icer composition as defined in claim 8 in an amount sufiicient to melt the deposit.

Abstract

A PACKAGE ADAPTED FOR PREPARING AND DISPENSING A HEAT DI-ICER COMPOSITION COMPRISING A CONTAINER HAVING AN OUTLET AND A VALVE ADAPT4ED TO CONTROL THE DISPENSING OF SAID COMPOSITION THEREFROM, AND CONTAINING (A) AT LEAST ONE WATER-SOLUBLE ICE-MELTING SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF MONOHYDRIC C1-C3 SATURATED ALIPPATIC ALCOHOLS, ETHYLENE GLYCOL, PROPYLENE GLYCOL, DIETHYLENE GLYCOL, ACETONE, METHYLETHYL KETONE OR MIXTURES OF THE FOREGOING, (B) A PEROXIDE CONTAINING COMPOUND CAPABLE OF REACTING WITH RAPID GENERATION OF HEAT WHEN CONTACTED WITH AN INITIATOR, (C) AT LEAST ONE INITIATOR CAPABLE OF INITIATING, AT THE STORAGE TEMPERATURE OF THE PACKAGE, THE HEAT-GENERATING REACTION OF SAID PEROXIDE CONTAINING COMPOUND, SAID INITIATOR SELECTED FROM THE GROUP CONSISTING OF SULFITE SALTS OF ALCOHOL AMINES HAVING THE STRUCTURE

R1-(N(-R2)-C(-R3)(-R4)-C(-R5)(-R6))N-(N(-R7)-C(-R8)(-R9)-

C(-R10)(-R11))M-OH

WHEREIN: R1, R2 AND R7 CAN BE THE SAME AS EACH OTHER HOR DIFFERENT FROM EACH OTHER AND ARE SELECTED FROM THE GROUP CONSISTING OF: H, CH3, C2H5, C3H7, C4H9, C2H4OH, C3H6OH, OR C4H8OH, R3, R4, R5, R6 AND R8, R9, R10, R11 CAN BE THE SAME AS EACH OTHER OR DIFFERENT FROM EACH OTHER SELECTED FROM THE GROUP CONSISTING OF H, CH3, OR C2H5, M CAN BE 0 THROUGH 5, N CAN BE 1 THROUGH 6 PROVIDED THAT N AND M ARE SELECTED SO THAT M+N IS NO GREATER THAN ABOUT 6. AT LEAST ONE OF THE MATERIALS (B) AD (C) BEING ISOLATED WHEN SAID VALVE IS CLOSED, (D) A PROPELLENT CAPABLE OF PROVIDING SUFFICIENT FLUID PRESSURE TO DISPENSE SUBSTANCE (A) FROM SAID OUTLET WHEN SAI VALVE IS OPEN, AND (E) MEANS TO PROVIDED INTIMATE CONTACT BETWEEN MATERIALS (A), (B) AND (C) WHILE (A) IS BEING CONVEYED TOWARD SAID OUTLET.

Description

May 21, 1974 w. B. VAN DER LINDE ETA!- PACKAGE FOR DISPENSING AN ICE-REMOVING COMPOSITION Filed Dec. 26, 1972 v INVENTORS NILLEH B. VAN DER LINDE CLINTON A. WESLAGER AGENT US. Cl. 252-70 United States Patent 3,812,043 PACKAGE FOR DISPENSING AN ICE-REMOVING COMPOSITION Willem B. van der Linde, Cherry Hill, N.J., and Clinton A. Weslager, Hockessin, Del., assignors to E. I. du Pont de Nemours and Company, Wilmington, Del. Continuation-impart of application Ser. No. 85,808, Oct. 30, 1970, which is a continuation-in-part of application Ser. No. 660,346, Aug. 14, 1967, both now abandoned. This application Dec. 26, 1972, Ser. No. 318,504 Int. Cl. C09k 3/18 10 Claims ABSTRACT OF THE DISCLOSURE A package adapted for preparing and dispensing a heated de-icer composition comprising a container having an outlet and a valve adapted to control the dispensing of said composition therefrom, and containing (A) at least one water-soluble ice-melting substance selected from the group consisting of monohydric C -C saturated aliphatic alcohols, ethylene glycol, propylene glycol, diethylene glycol, acetone, methylethyl ketone or mixtures of the foregoing,
(B) a peroxide containing compound capable of-reacting with rapid generation of heat when contacted with an initiator,
(C) at least one initiator capable of initiating, at the storage temperature of the package, the heat-generating re action of said peroxide containing compound, said initiator selected from the group consisting of sulfite salts of alcohol amines having the structure I I R4 Re 11 R0 Rn m wherein:
R R and R, can be the same as each other or different from each other and are selected from the group consisting of: H, CH C H C H- C H CZHQOH, C3H5OH, 0r C4H8OH,
' R3, R4, R5, R6 and R3, R9, R10, R11 can be the same as each other or different from each other and are selected from the group consisting of H, CH or C2H5 m can be 0 through 5, n can be 1 through 6 provided that n and m are selected so that m+n is no greater than about 6,
at least one of the materials (B) ad (C) being isolated when said valve is closed,
(D) a propellent capable of providing suflicient fluid pressure to dispense substance (A) from said outlet when said valve is open, and
(E) means to provide intimate contact between materials (A), (B) and (C) while (A) is being conveyed toward said outlet.
CROSS REFERENCE TO RELATED APPLICATIONS This is a continuation-in-part of pending application Ser. No. 85,808, filed Oct. 30, 1970, and now abandoned, which application is a continuation-in-part of application Ser. No. 660,346, filed Aug. 14, 1967, and now abandoned.
BACKGROUND OF THE INVENTION This invention relates to an aerosol-type package for preparing and dispensing a composition capable of melting and removing a deposit of ice, frost or the like from ice a surface, for example, from an automobile windshield. Such a composition is some times referred to in the art as a de-icer composition.
There is a need in the art for an aerosol-type package l) which can be stored not only at ordinary room temperatures but also at outdoor winter ice-forming temperatures, and (2) which is ready for immediate use at these temperatures for rapidly and efliciently removing ice or frost from a windshield or the like by opening a dispenser valve and allowing the de-icer composition to flow from the package outlet directly onto the ice-covered windshield.
SUMMARY OF THE INVENTION According to the present invention, there is provided:
A package adapted for preparing and dispensing a heated de-icer composition comprising a container having an outlet and a valve adapted to control the dispensing of said composition therefrom, and containing (A) at least one water-soluble ice-melting substance selected from the group consisting of monohydric C -C saturated aliphatic alcohols, ethylene glycol, propylene glycol, diethylene glycol, acetone, methylethyl ketone or mixtures of the foregoing,
(B) a peroxide containing compound capable of reacting with rapid generation of heat when contacted with an initiator,
(C) at least one initiator capable of initiating, at the storage temperature of the package, the heat-generating reaction of said peroxide containing compound, said initiator selected from the group consisting of sulfite salts of alcohol amines having the structure JEZELEMELZZEKLOH wherein:
R R and R, can be the same as each other or different from each other and are selected from the group consisting of: H, CH C H C3H7, C4H9, C2H4OH, C3H6OH, OI C4H8OH,
R3, R4, R5, R6 and R3, R9 R10, can be the Same as each other or different from each other and are selected from the group consisting of H, CH O1 C2H5,
m can be 0 through 5, n can be 1 through 6 provided that n and m are selected so that m+n is no greater than about 6,
at least one of the materials (B) and (C) being isolated when said valve is closed,
(D) a propellant capable of providing sufiicient fluid pressure to dispense substance (A) from said outlet when said valve is open, and
(E) means to provide intimate contact between materials (A), (B) and (C) while (A) is being conveyed toward said outlet.
BRIEF DESCRIPTION OF THE DRAWING In the attached drawing, FIG. 1 shows an embodiment of the novel package in central vertical section and partially broken away; a portion of the valve stem is shown partially broken away; a portion of the valve stem is shown in front view. The dispensing valve is in the closed position. FIG. 2 shows a portion of the package of FIG. 1 in which the dispensing valve is in the open position. FIG. 3 shows an enlarged perspective view of the lower face of the valve head of FIG. 1. The drawing is described in further detail in Example 1.
3 DESCRIPTION OF THE PREFERRED EMBODIMENTS With reference to component (A) of the novel package, the water-soluble ice-melting substance is preferably made up of about 60-100% by weight of a C -C saturated aliphatic monohydric alcohol and up to about 40% by weight of a polyhydric alcohol, particularly when the package is to be used for removing ice or frost from automobile Windshields and the like. Especially preferred as the monohydric alcohol is 50-100% by weight of isopropanol and up to 50% of methanol, ethanol, propanol or blends thereof. Component (A) can be entirely monohydric alcohol or it can be made up entirely or partially of other water-soluble substances which are capable of melting ice when dispensed from the package and which are not harmfully reactive with the surfaces of the article to which the de-icer composition is to be applied; for example, (1) a polyhydric alcohol such as ethylene glycol, propylene glycol or diethylene glycol, (2) a ketone such as acetone or methyl ethyl ketone, (3) salts such as sodium chloride and calcium chloride. When a salt is used it is preferably present as a solution in water or alcohol. When a polyhydric alcohol is present, the amount used is adjusted to give the composition the desired evaporation rate and anticorrosion characteristics. In some of the most useful embodiments of the invention, about 60-85% of component (A) is present based on the combined weight of components (A), (B), (C) and (D) in the package.
Hydrogen peroxide is usually preferred as component (B) of the package of this invention. Also included among the useful component (B) compounds are barium peroxide, calcium peroxide, urea hydrogen peroxide, and various hydroperoxidates. The latter, which contain hydrogen peroxide of crystallization, include sodium borate hydroperoxidate, magnesium carbonate hydroperoxidate and sodium pyrophosphate hydroperoxidate. If desired, component (B) can be admixed with an inert carrier such as water.
Component (C) must be capable of initiating the heatgenerating reaction of component (B) at the storage temperature of the package. The storage temperature of the package may be well below freezing as is often the case in an unheated automobile or garage, or it may be the temperature of a heated automobile or home; for example, the storage temperature is likely to be a temperature within the range of about minus 29 C. to plus 27 C. (about minus 23 F. to plus 80 F.).
. Compounds suitable for use as component (C) include sulfite salts of alcohol amines. Suitable alcohol amines from which sulfite salts can be formed include those having the following structure:
R R and R, can be the same as each other or different from each other and are selected from the group con- Sisting Of: H, CH3, C2H5, C3H7, C4Hg, C2H4OH, C H OH, or C H OH,
R R R R and R R 10 R can be the same as each other or different from each other and are selected from the group consisting of H, CH or C H m can be 0 through 5, n can be 1 through 6 provided that n and m are selected so that m+n is no greater than about 6.
Examples of suitable alcohol amines from which sulfite salts can be formed include the following:
diethylhydroxyethyl amine* methyldihydroxyethyl amine* tetrahydroxyethyldiaminoethylene* trihydroxyethyl amine* 4 dimethyl-Z-hydroxypropyl amine* dimethyl-3-hydroxypropyl amine* diethyl-Z-hydroxypropyl amine diethyl-S-hydroxypropyl amine* methyl-Z-dihydroxypropyl amine* methyl-3-dihydroxypropyl amine dimethyl-Z-hydroxybutyl amine dimethyl-3-hydroxybutyl amine diethyl-Z-hydroxybutyl amine diethyl-3-hydroxybutyl amine dimethylethanol amine* methyl-Z-dihydroxybutyl amine methyl-3-dihydroxybutyl amine N,N,N'-trimethyl-N'-hydroxyethyldiaminoethylene* N,N,N'-triethyl-N'-hydroxyethyldiaminoethylene* N,N-diethyl-N,N'-dihydroxyethyldiaminoethylene* N,N-dimethyl-N',N'-dihydroxyethyldiaminoethylene* N-ethyl-N,N',N'-trihydroxyethyldiaminoethylene* N-methyl-N,N',N-trihydroxyethyldiaminoethylene* N,N,N',N",N"-pentahydroxyethyl diethylene triamine N,N,N',N",N-penta-2-hydroxypropyl diethylene triamine N,N,N',N'-tetrahydroxyethyl ethylene diamine N,N,N',N-tetra-2-hydroxypropyl ethylene diamine N-hydroxyethyl-N,N,N'-tri-2-hydroxypropyl ethylene diamine.
Sulfite salts of alcohol amines can be formed by any suitable method including passing S0 through the alcohol amine.
Preferred are sulfite salts of the above mentioned alcohol amines that are followed by an asterik (i.e.
Sulfite salts of alcohol amines are preferred because of their compatibility and solubility with the ice melting substance and because they have little or no tendency to form a deposit which will unduly reduce visibility when the composition is applied to a windshield. Furthermore, sulfite salts of alcohol amines are desirable because unlike many reducing agents, relatively small amounts of such salts will produce suitable heat generation with a 12% or less weight percent solution of hydrogen peroxide in water. It is desirable to use a concentration of hydrogen peroxide of 12% or less, and preferably less than 10%, since at greater concentrations, hydrogen peroxide can cause permanent eye damage. This is believed to be an important consideration because if for some reason the aerosol can failed and only the hydrogen peroxide was expelled from the can, if its concentration was greater than 12%, permanent eye damage could be caused if it contacted the eye.
In a preferred embodiment of the novel package, the reducing agent is mixed with component (A), and the resulting mixture is stored within a chamber adapted to prevent said mixture from coming in contact with component (B) while the valve means that controls the dispensing of the de-icer composition is closed.
As indicated above, component (D) of the novel package is a propellent capable of providing fluid pressure sufficlent to dispense the ice-melting substance when the dlspensing valve is open. The useful propellents include those known to be operable in an aerosol-type package, for example, a compressed gas such as nitrogen, nitrous oxide or carbon dioxide, or a volatile organic material such as isobutane, straight-chain aliphatic hydrocarbons, and water-insoluble chlorine and fluorine substituted hydrocarbons having suitable vapor pressure. About 325% of propellent is usually preferred based on the combined weight of propellent and other fluids within the package.
Component (E) of the package of this invention consists of means to provide contact between components (A), (B) and (C) while the charge of ice-melting substance is being conveyed to the container outlet. A preferred form of component (E) comprises a common duct 26 located downstream from the opening of the open valve as shown in the attached drawing, and means to feed components (A), (*B) and (C) into said duct from the isolated storage chambers formed by can 34 and tube 33. It can be seen in FIG. 2 that gap 37 is the opening of the open valve. Another preferred form of component (E) comprises a common duct located upstream from the opening of the open valve. This is shown in FIG. 1 of U.S. 3,325,056, which is hereby incorporated by reference, where it can be seen that duct 20 is located upstream from the central portion of valve 17 (near point 47) where the valve opens, and the components of a de-icer composition can flow into said duct from the isolated storage chambers formed by can 24 and tube 26 when the valve is opened.
Various known additives can also be present in the package and dispensed as a component of the heated de-icer composition, for example, water, odor-controlling agents, surfactants, anticorrosive agents and viscosity controlling agents.
The package of the present invention is useful for preparing and dispensing a heated de-icer composition. Prior to use, the package can be stored at ordinary room temperature or at the ice-forming temperatures commonly encountered in an unheated automobile standing outdoors in cold winter weather. The invention makes it possible to remove deposits of ice, frost and the like from automobile windshields and other surfaces with surprising speed and efficiency. A heated charge of ice-melting composition can be prepared and applied instantaneously by simply opening the valve and allowing the heated composition to flow from the outlet onto the ice-covered surface. The ice-removing procedure can include, if desired, the operation of automobile windshield wipers. The package can be entirely free of any awkward attachments and there is no need for a source of electricity, steam or hot water.
The examples which follow are given for the purpose of illustrating the invention. All quantities shown are on a weight basis unless otherwise indicated.
EXAMPLE 1 With reference to FIG. l of the attached drawing, outer container 34, which is adapted for storing a liquid under pressure, is a can of the type commonly used in aerosol dispensers. The upper portion of can 34 is rounded and tapered to form a circular opening surrounded by a rolled bead 1'8 spun from the metal of the can. The rolled edge of bowl-shaped cover 19 tightly engages bead 18, and after the contents of the can are inserted, it is crimped therewith to form a pressure-proof seal. Top wall 20' of can 34 has an aperture which is outwardly flanged about axis a perpendicular to wall 20; in this aperture is lockingly and sealingly fitted a tilt-opening self-closing dispensing valve. The dispensing valve comprises a tubular seal 17 made of a resilient elastic rubber composition fitted sealingly in aperture 27; the valve also comprises a tubular stem 14 made of a relatively rigid plastic composition fitted coaxially (on axis a) and sealingly in seal 17. The rigid stem has relatively little elastic deformation under load compared with that of resilient seal 17. Stem '14 terminates inside of can 34 in disc-shaped valve head 25 and terminates outside of can 34 in dispenser outlet 10. By gently pressing the side of stem 14 near the outlet, the stem can be tilted above a pivot point located between its two ends (near the bottom of ring 15); as the stem is tilted, its lower portion moves laterally within annular gap 30. When the tilting pressure is removed from the valve stem, the stem is returned to the erect, closed position by the resilient elastic rubber seal.
The exterior portion (above aperture 27) of stem 14 has (a) a laterally extending shoulder 16 which abuts against the upper end face 13 of seal 17 at a level remote from that of wall 20 and (b) a laterally extending ring 15 in locking contact with a matching groove in the inner wall of seal 17.
Collapsible inner container 33 is a flexible plastic tube which is smaller than can 34 and has a beaded upper end 23 sealingly fitted in annular groove 31 in the side wall of valve head 25-. Thus, there is a chamber outside of tube 33 and within can 34 in which liquid 38 can be stored in isolation from the liquid in the tube. Lower face 32 of valve head 25 forms the top wall of collapsible container 33. In a sense, end face 21 also forms part of the top wall of container 33 since it serves as a closure for channels 24 when the valve is closed. The heat-sealed lower end 35 of tube 33 almost touches bottom wall 36 of can 34.
Tubular seal 17 has an enlarged lower portion 28 which has a large washer-like sealing surface in contact with the inner side of wall 20 adjacent aperture 27, and which terminates inside of can 34 in an annular end face 21 at a level remote from the level of top wall 20; and valve head 25 has a laterally extending annular shoulder 22 in sealing contact with end face 21, thereby forming a breachable seal. When the valve is closed, the resilient material of seal 17 is slightly compressed at end face 21. The inside diameter (inner wall) of the lower portion 28 of tubular seal 17 in a region adjacent end face 21 is enlarged so that this portion of the seal is separated from the lower portion of stem 14 by an annular gap or chamber 30 (counterbore recess) which is in communication with dispenser outlet 10 through lateral port 29 and central passage 26 of stem '14. Port 29 is provided by drilling a hole diametrically through the valve stem just above shoulder 22. Annular chamber 30 is partitioned by the breachable seal from the chamber containing liquid 38.
As shown in FIG. 3, valve head 25 is perforated with 8 channels 24; each channel has a diameter of 32 mils. These channels provide communication between the interior of collapsible tube 33 and (at) end face 21 of tubular seal 17 when the valve is closed, and (b) gap 30 when the valve is open. It can be seen in FIG. 2 that the interior of the chamber containing liquid 38 and the interior of tube 33 are in communication with annular chamber 30 (and therefore port 29, passage 26 and outlet 10) only when stem 14 is tilted enough to breach the seal and thereby provide a gap 37 between end face 21 of the seal and annular shoulder 22 of the valve head.
Cap 11 has internal threads to match external threads 12 of the upper portion of stem 14. When the cap is in place, its lower edge abuts upon head 18; thus stem 14 is locked in the erect position.
The dispenser shown in FIG. 1 is adapted for storing liquid 38 (including a propellent) in can 34 and a dilTerent liquid 39 in tube 33, and for dispensing these two liquids simultaneously and intermittently through outlet 10. When using the dispenser, cap 11 is removed and the dispenser is inverted so that the upper portion of can 34 is filled with liquid; stem 14 is tilted to open the valve, and liquids 38 and 39 become mixed as they flow into gap 30 through gap 37 en route to outlet 10. The flow of both liquids into gap 30 stops the instant the valve stem is permitted to return to the erect positoin and starts again the instant the valve stem is tilted.
A Formula 1.1 reducing agent composition is prepared by (a) mixing 55.6 parts of tetra-Z-hydroxypropyl-ethylene-diamine with 30.5 parts of methanol and 1.5 part water, (b) cooling the resulting mixture to 0 C., and (c) passing sulfur dioxide into the cooled mixture until 12.4 parts of sulfur dioxide is reacted with the diamine. The resulting Formula 1.1 composition is a solution of 69.5 parts of tetra-Z-hydroxypropyletylenediamine-dihydrosulfite in 30.5 parts of methanol.
A Formula 1.2 composition is prepared by mixing 30 parts of the Formula 1.1 composition with 70 parts of a 50/50 blend of methanol and isopropanol.
The package shown in FIG. 1 is prepared for use by (1) placing 200 grams of the Formula 1.2 composition into can 34 (a 12 ounce can), (2) displacing the air in the can with isobutane, (3) assembling valve stem 14, tubular seal 17 and cover 19 as described above and shown in FIG. 1, (4) placing 20 ml. of 11.5% hydrogen peroxide (88.5% water) into tube 33, (5) attaching tube 33 to the lower end of the valve stem (valve head 25) so that the beaded top 23 of tube 33 is engaged with groove 31 of the valve head, (6) placing the valve, cover and tube assembly resulting from steps (3)-(5) in position with the cover fitted on the can and crimping the rolled edge of cover 19 with can bead 18 to form a pressure-proof seal, (7) introducing grams of isobutane into the can by means of a conventional under-the-valve .filler apparatus, thereby providing sufiicient propellent so that the pressure within the package is about 30 p.s.i.g. at 24 C., (8) screwing on the dispenser cap 11 so that its lower end tightly abuts upon the top of cover 19, said cap providing a means to insure that the valve will not be inadvertently oened during storage and shipment of the package, and (9) with the package at 24 C., shaking the package for a few seconds so that the Formula 1.2 composition and propellent in can 34 are adequately blended with one another. None of the liquid in can 34 or tube 33 can escape into duct 26 or gap 30 during the shaking because of the sealing contact between end face 21 of the tubular seal and annular shoulder 22 of the valve head.
Cap 11 is removed, the package is held in an inverted position (bottom side up), the valve is opened by tilting the valve stem, a quantity of heated de-icer composition is dispensed from outlet 10 onto an ice-coated windshield, and the valve is allowed to close. The dispensed de-icer has a tempedature of 63 C., and it rapidly removes the coating of ice from the windshield. The valve is rapidly opened and closed to dispense numerous small amounts of heated de-icer composition onto ice-coated areas of Windshields and other objects, thereby quickly removing the layer of ice.
While the valve is held open by tilting the valve stem, the separately stored liquid materials within can 34 and tube 33 flow through gap 37 into gap 30; and as the resulting composition entering gap 30 flows through port 29, duct 26 and outlet 10, it becomes mixed and heated substantially instantaneously as the result of a rapid exothermic reaction between the tetra-Z-hydroxypropylethylenediamine-dihydrosulfite and the hydrogen peroxide. The de-icer composition flowing into duct 26 contains about 6 parts of Formula 1.2 for each part of the 11.5% hydrogen peroxide solution.
When the performance of the package prepared in Example 1 is compared with that of a package prepared in the same manner except for the omission of the hydrogen peroxide in tube 33, it is found that a 5 gram portion of the heated composition dispensed from the package of Example 1 is capable of removing 60-70% more ice in 15 seconds than the same amount of the non-heated composition dispensed from the peroxide-free package.
EXAMPLE 2 A package having beneficial utility for the rapid removal of ice or frost from Windshields and the like is prepared as described in Example 1 except the propellent carbon dioxide is used instead of isobutane in steps (2) and (7); in step (7), enough carbon dioxide is introduced into the can so that the pressure within the package is about 80 p.s.i.g. When the resulting package is stored at 0 C. for several hours prior to use, it is still very useful for the rapid removal of ice or frost from Windshields, the dispersed heated de-icer having a temperature of 50 C.
What is claimed is:
1. A package adapted for preparing and dispensing a heated de-icer composition comprising a container having an outlet and a valve adapted to control the dispensing of said composition therefrom, and containing (A) at least one water-soluble ice-melting substance selected from the group consisting of monohydric C -C saturated aliphatic alcohols, ethylene glycol, propylene glycol, diethylene glycol, acetone, methylethyl ketone or mixtures of the foregoing,
(B) a peroxide containing compound capable of reacting with rapid generation of heat when contacted with an initiator,
(C) at least one initiator capable of initiating, at the storage temperature of the package, the heat-generating reaction of said peroxide containing compound, said initiator selected from the group consisting of sulfite salts of alcohol amines having the structure desert 1.
wherein:
R R and R; can be the same as each other or different from each other and are selected from the group consisting of: H, CH C H C H C4H9, C2H4OH, C3H6OH, Or C4H3OH,
R R R R and R R R R can be the same as each other or different from each other and are selected from the group consisting of H, CH3, OI C2H5,
m can be 0 through 5, n can be 1 through 6 pro vided that n and m are selected so that m-l-n is no greater than about 6,
at least one of the materials (B) and (C) being isolated when said valve is closed,
(D) a propellant capable of providing sufficient fluid pressure to dispense substance (A) from said outlet when said valve is open, and
(E) means to provide intimate contact between materials (A), (B) and (C) while (A) is being conveyed toward said outlet.
2. A package according to claim 1 wherein about 60 by weight of substance (A) is a C -C saturated aliphatic monohydric alcohol.
3. A package according to claim 1 wherein compound (B) is hydrogen peroxide.
4. The package according to claim 1 wherein initiator (C) is mixed with substance (A).
5. The package of claim 1 wherein component (C) is selected from the group consisting of sulfite salts of the following alcohol amines and mixtures of sulfite salts of the following alcohol amines:
diethylhydroxyethyl amine methyldihydroxyethyl amine tetrahydroxyethyldiaminoethylene trihydroxyethyl amine dimethyl-Z-hydroxypropyl amine dimethyl-3-hydroxypropyl amine diethyl-Z-hydroxypropyl amine diethyl-S-hydroyxpropyl amine methyl-Z-dihydroxypropyl amine methyl-3-dihydroxypropyl amine dimethyl-Z-hydroxybutyl amine dimethy1-3-hydroxybutyl amine diethyl-2-hydroxybutyl amine diethyl-3-hydroxybutyl amine dirnethylethanol amine methyl-Z-dihydroxybutyl amine rnethyl-3-dihydroxybutyl amine N,N,N'-trimethyl-N'-hydroxyethyldiaminoethylene N,N,N-triethyl-N-hydroxyethyldiaminoethylene N,N-diethyl-N',N-dihydroxyethyldiaminoethylene N,N-dimethyl-N,N'-dihydroxyethyldiaminoethylene N-ethyl-N,N,N-trihydroxyethyldiaminoethylene N-methyl-N,N',N-trihydroxyethyldiaminoethylene N,N,N',N",N"-pentahydroxyethyl diethylene triamine N,N,N',N",N"-penta-2-hydroxypropyl diethylene triamine contacting the following in the presence of a volatile propellent material:
9 N,N,N', -tetrahydroxyethyl ethylene diamine 'N,N,N,N'-tetra-2-hydroxypropyl ethylene diamine N-hydroxyethyl-N,N,N'-tri-2-hydroxypropyl ethylene diamine. 6. The package of claim wherein compound (B) is 5 hydrogen peroxide.
7. The package of claim 6 wherein initiator (C) is mixed with substance (A).
8. A heated de-icer composition obtained by intimately 9. A composition according to claim 8 wherein about -100% of substance (A) is a C -C saturated aliphatic monohydric alcohol.
10. A process for removing a deposit of ice or the like from a surface which comprises applying to said deposit a heated de-icer composition as defined in claim 8 in an amount sufiicient to melt the deposit.
References Cited UNITED STATES PATENTS 2,342,759 2/1944 Schechter et al 62-1 3,079,340 2/1963 Reamer 252188 3,096,290 7/1963 Duane et al 252- 3,167,515 1/1965- Hinckley et a1. 252-188 3,341,418 9/1967 Moses et al 167-85 3,503,885 3/1970 Wedell 252188 3,557,004 1/ 1971 Yolles 42470 LEON D. ROSDOL, Primary Examiner H. A. PITLICK, Assistant Examiner US. Cl. X.R.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060162344A1 (en) * 2004-03-15 2006-07-27 Ontech Delaware Inc. Container with module for heating or cooling the contents
US20080248162A1 (en) * 2007-03-27 2008-10-09 Cryovac, Inc. On-demand meat tenderizing package
US20100062130A1 (en) * 2008-09-10 2010-03-11 Cryovac, Inc. Package assembly for on-demand marination and method for providing the same
US20140048568A1 (en) * 2011-02-10 2014-02-20 Jordi Demey Dispensing aerosol valve for pressurized container, dispensing adapter therefor, and assembly of a pressurized container with an adapter

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060162344A1 (en) * 2004-03-15 2006-07-27 Ontech Delaware Inc. Container with module for heating or cooling the contents
US20080248162A1 (en) * 2007-03-27 2008-10-09 Cryovac, Inc. On-demand meat tenderizing package
US20100062130A1 (en) * 2008-09-10 2010-03-11 Cryovac, Inc. Package assembly for on-demand marination and method for providing the same
US7993692B2 (en) 2008-09-10 2011-08-09 Cryovac, Inc. Package assembly for on-demand marination and method for providing the same
US20140048568A1 (en) * 2011-02-10 2014-02-20 Jordi Demey Dispensing aerosol valve for pressurized container, dispensing adapter therefor, and assembly of a pressurized container with an adapter

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