DE2436327A1 - LIQUID DEFROSTING AGENT AND METHOD TO PREVENT THE COLLECTION OF SNOW AND / OR ICE ON OUTDOOR SURFACES - Google Patents

Description

PATENT ADVOCATE

. BERNHARD RICHTER

85 NUREMBERG
Beethovenstrasse 10 - Telephone (0911) 695015

July 26, 1974

Anthony J. Bonnanzi ", Westport" oad,
Fairfield, Con., <. c tu cut / UoV:

"Liquid defrosting agent and process?! -, to the '.'cri ^ l
the accumulation of jchnee and / odor ice on
in the open air <_; ~ .ien surfaces "

The invention relates to e ^ .i. ; ^s lüsoi {jos En-ioj .un, ⁿ ; s- bzv. Defrosting agents and in particular oi.i Aotaunitt: -. ,.: «Au 'im
Open areas ai; ->t> racht werJ -r ^ ΐιί., ι then the accumulation of ice unc / iacr tendon ·? ■ j. . ν = '.';. c -.1, as well as a method for preventing the AnsoiMlun, '; ν- ι
Snow and / or ice on nil.-hui in the open air.
(Open air area) by applying an .Ibtaumi; tc 's.

Ice and snow accumulations or anhsiufur.gen on walking
p-er \, streets and other open-air areas must be removed in the ro-v, el. Removal is usually done
by physical or mechanical removal of the ice or snow from the open-air area covered with it by shoveling, plowing or the like. There have been already made attempts to do provide means which RuII-

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prevent ice and / or snow accumulation from the outset let, however, these preliminary searches were up to Jai.zt not very successful.

Thus, the traditional method of removing ice and snow, which is a tedious and labor intensive removal process, is usually still used rather than successfully preventing the accumulation of ice and snow. This particularly applies to ordinary Geh.- and roads and the like, normally encountered in d c s iclitbeVölker areas to homes or Einzelh.ariL.elsgoschäften *

It is true that for some time now Nacriuriici.iorid t : ~ il calcium chloride containing agents ei'häxtlicä, aio angel / -! . avf a surface applied uer'ion can to .. '; ... ^ accumulation of liis and snow on it c ~. prevent _O e.och they find only limited use and most homeowners and shopkeepers go the problem wide ri:. _; .n by removing after the accumulation, rather than by preventing the accumulation or accumulation of jus and snow. The reason that the currently known agents for preventing the formation of ice and snow accumulations have not met with desensitizing approval and achieved success is presumably to be seen in several factors which are related to certain disadvantages common to all such prophylactically applicable known agents more or less strongly attached.

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Sodium chloride preparations, commonly referred to as "rock salt", are used for melting from ice or snow associated with serious disadvantages, since they produce a chalky-white residue, which is usually dragged into houses, shops or other indoor spaces, causing unsustainable pollution leads. Another notable factor in the use of such defrosting agents is their cost. Since these defrosting agents have to be applied in large quantities to cover fairly large areas, prevent too high costs their economic success and their applicability. Rock salt has the serious disadvantage of leaving behind a dirty residue, however, it is so inexpensive that, despite its drawbacks, it is considered useful to a limited extent will. Other defrosting agents that solve the problem of the formation of a dirty when using rock salt Attempt to remove residue, but must be made available at a relatively low cost to be economically acceptable to be, which would be a prerequisite for their widespread use. That rock salt substitute do not provide effective prevention of snow accumulation at acceptably low costs, has been found to be the main reason for these defrosting agents to be widely adopted.

It is therefore obvious that a defrosting agent for

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prevention of ice and snow accumulation that as general can be considered successful and useful, should cost little without other intolerable disadvantages how to produce a dirty residue. Of course there would be a remedy that would have these properties in a defrosting agent that actually effectively prevents the accumulation of ice and snow, in combination would exhibit a significant technical advance.

Another aspect that must be taken into account with such prophylactically applicable defrosting agents must is the fact that the application of these funds must be repeated at intervals. In the case of long-term j ..- j'arn Snowfall will have the effect of such a Ab.:.arr, - .. ctels namely eventually disappear, whereupon 3ine zvuito or, further application is required. However, it is difficult or even difficult with the currently known defrosting agents impossible to tell when further application is required. This need is usually first then to recognize when a considerable accumulation or accumulation of snow has already taken place and up has evolved to a degree that reapplication of the defrosting agent is less effective or even completely useless power. It would therefore be advantageous if a path could be opened up which would make it possible for the Need for a second or further use of a prophylactically applicable defrosting agent during or briefly after. the entangler. the effect of a first or

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related defrosting agent application, so in good time recognize that no further treatment preventive build-up of snow masses can take place before the need a renewed application of the defrosting agent is recognized.

The invention is therefore based on the object of creating a new defrosting agent which prevents the accumulation of ice and snow and which avoids the disadvantages of the previously known cleaning agents and, in particular, does not tear dirty residues behind at a low price -n-, enables the necessity of a renewed treatment to be recognized in good time without special aids.

- ' ^{: it} has now been found that a 30 to ■' -! ^r i vol. .on ;, ¹ C. r. : one -.- ..: ir.ylene glycol, preferably eir.L .. ^; - AA <.yL - i. ^ L :: ol with 2 ti :. 6 carbon r.toir .-.! N · ιηϋ insb-jsoraer: ic ■ _s :. An aqueous solution containing cn- or propylene glycol and cine I-an amount, gev ^ oilir-l "■■ 1, of the order of about C ^ ₁ % of an organic dye, if it is a surface exposed to the weather, for example a Go odvr-r Fahrwep; or the like, which effectively prevents the accumulation of ice or snow on this surface without leaving an unsightly or dirty residue.

The subject of the invention is thus a liquid defrost

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medium, consisting essentially of 30 to 45 percent by volume at least one alkylene glycol with 2 to 6 carbon atoms, dissolved in water and a compatible organic acid group containing at least one sulfonic acid group Dye in an amount sufficient to give the defrosting agent a color that is visually recognizable is when it is in contact with a surface.

The defrosting means of the invention can be proportionate to a low price, thereby increasing the prospect of their economic -: /! Success, and that they are widely accepted and widely used. The special one Selection of the ingredients and the range of proportions in which, the ingredients in the Ab i: aumit means The existence of the earth leads to the combination favorable properties or features that the inventive Defrosting means distinguish, among other things, the possibility of preventing the accumulation of ice and / or snow at low cost and without creating undesirable To be able to prevent soiling.

The use of glycols as opposed to other polyhydric alcohols such as glycerin is an important feature of the invention, since a replacement of the glycols with glycerine results in a cleansing agent mixture with a different viscosity would result in the ease of use of the

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Would affect the defrosting agent. Also, the use of glycerin yields what is perhaps more important is, a defrosting agent whose coefficient of friction, jeringer is as that of a defrosting agent with a glycol .. One covered with a defrosting agent based on glycerin Open-air areas are therefore slightly more slippery than an open-air area covered with a defrosting agent according to the invention be.

The dye present in the defrosting agents according to the invention makes it possible to identify the presence of the defrosting agent on a surface. If snow or ar ^T :: Ls hit the treated open-air area, melt and flow away, the effect of the applied glycol defrosting agent is reduced, as part of the defrosting agent is whitened by the melt that runs off. The occurrence dies.cs process can on the basis of staining, as o. The Abtaumittel and dar.iit b ^ hanualten existing area by öen in Abtaumittel. Dye bestowed: ¹ wivi, sr know and be followed. The coloration caused by the dye can be seen on the treated open air tube and ensures that, through its fading as a result of the runoff caused by the melting of ice or snow, it indicates the need to use defrosting agent again, without an accumulation or - accumulation of ice and / or snow needs to be allowed to a prohibitive extent.

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It has been found that an addition of only i / iO percent by volume of an organic dye is sufficient to provide a reasonable indication that reapplication of the Defrosting agent is required. Of course it can be dependent of the desired color also in car or less Dye can be added. Wicht j g is scrnit only, that the dye is added in an amount sufficient to give the defrosting agent a visible color.

Suitable dyes are suitable for the purposes of the invention organic dyes containing sulfonic acid groups (-SCIl) contain. Dyes that do not contain sulfonic acid groups, leave strong residual stains on the treated open-air area. As a result, it is difficult to ivtiin not even impossible to determine whether the area in question "still has adequate antifreeze protection or a there is sufficient defrosting effect. That is, when using no sulfonic acid groups Dyes still have a considerable residual color even when the anti-freeze effect is complete disappeared.

Dyes from the following groups are particularly suitable:

Aromatic sulfonic acids, e.g. Acid Yellow 1 (acid yellow l), C.I. IO316 and bromamic acid;

Nitrososulfonic acids, e.g. acid green 1,

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C.I. 10020;

Monoazosulfonic acids, e.g. acid orange 7 (acid orange 7), C.I. 15510 and acid blue 92, C.I. 13390;

Diazo sulfonic acids, e.g. 97 (acid red 97), C.I. 20890;

and

Anthraquinone sulfonic acids, e.g. Acid Blue 78 (acid blue 78), C.I. 62105, acid blue 25, C.I. 62055 and acid green 25, C.I. 6155O.

Optionally, depending on the color you want, you can too other dyes from the above groups can be used if they contain sulfonic acid groups.

The discovery that by adding only about 0.1 percent by volume of such a dye to a 30 to 45 volume percent aqueous glycol solution is effective Recognition possibility for the necessity of a Again on defrosting agent application is created allows it to have this feature available with minimal cost too which increases the chances that the invention will be economical borrowed success and is generally well received, can be increased further.

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Although ethylene and propylene glycols have long been known to be effective antifreeze agents, particularly for traction vehicle engine cooling systems, their use as snow accumulation preventive agents by applying and treating open spaces on a commercial scale has never been successful. The ^ rfIt.! Surrounds a greatly simplified glycol mixture i.ur available, which due to its simplicity can be made available at minirria.Yiij · costs. An important feature of the invention, however, is to be seen in the fact that, according to the invention, a defrosting means is available which, despite its great simplicity; riJ .-. 0.1.1 ; .- jLoic. At a low price not only sufficient to prevent ice and snow samples, but also clean and unproblematic. -sr: ', τ ... - iiciiidbar, since there are no dirty backs.: s car :.' 3 ■ ... ^T leaves behind. The core, dar Erf ir. Iai ..; i. .. ί. 1 cer discovery to see that the advance.ierj.cl ur ^ ur-'jd: .ί · ο combination of features b: '. W. Features on * ,, loh ·. uird, .wer., one ethylene or propylene glycol v.xide of a dye in el + ien within the mentioned critical threshold values of the mixture ratio with water xisrut.

The Dcreicheru achieved according to the invention. ;;;; uor * "ohw κ VJ .-- Ü continue untc: Consideration of the Tatsadis vei-utu ·.-licht that, r, .ar.; even after de '-and of the Tecünilc numerous different tie types of j: ..; ..ii> ^NISC: s were proposed, these Geuii ^ che However ζώ .. 'fiche supply.

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contained kits which, while providing many of the characteristics and properties desirable to the performance and manageability of the mixture, increased the cost and the intricate composition of the mixtures. These additional Koston w: x \ increased complexity of the composition can Although the effectiveness exneibestimmten glycol solution for certain specific Am ·, ending purposes increase, but decrease equal to ^ oi cig also:. Sized market opportunities than ordinary Μί ^, ο-u / ar Verhinaor ing of Snow accumulations,

The defrosting mixes of the invention can, on the other hand, be converted into an LC ^ ^>: \ .aiva by their specialized composition and their low cost. Price bought and on sidewalks ociox 'F aar weighed «- be applied, whereby the aafKuvu'idenden i.:/'"'M. Rubs then, veriii large Frciluf ti' laugh b (: vt; c;: t (V .ior h \ - Iianaeli must not become proiiibitiv high, when carrying out the method of the invention -carui the defrosting agent according to the invention on a free air surface essentially free of snow and / or ice accumulation by "any suitable method, preferably simply by spraying it out of a container, for example, a c-r gc. - where. ' \ who are treated according to defrosting agents, confess to an open-air pavement made of beguiling, aaprr. 1r or the like.

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Compliance with the specified limit values in the range from 30 to 45 percent by volume of glycol in water was considered critical for several reasons. Since the J ^T au;> tzwock the invention effectively prevent the accumulation of snow and / or ice rait minimum cost J ..- 3t, -was found that the use of ethylene ocer propylene glycol to a veitostgohenden Kostenvcirrirgorung while maintaining eir : .r vol lausroich. ■ -iri -ji; Effect leads. Ethylene and propylene glycol are \ x: \ ~ for the purposes of the invention, however, koruian preferred glycols, other AlkylenglykoIe and / or Polyalkylenglykoie ,, for example, polyethylene glycol or poly u cpylenglykol, i ;; i τ.. ^ a ^; : .- m used to succeed. It is J "but it hiu ^ av / iron that in view of the planned: - \ INTENDED USE;, ύ-τ ..oglichst low cost presupposes the use of such other glycols requires a selection, <i *... not "to a reduction in the economic attractiveness of the invention or of it." i / Klur.-.- sgenia .'-. .; n Ab .-. aumeans through excessive cost struc- ture.

It has been found that the effectiveness of the Abtaumittel when exceeding the limit values of the _n orfindur jsgemäß einzuhgJtenden content range of 30 to h ~) Volupienprozent Clykol reduced and zwnr both under and boi HBOR spine critical region lying Prozentsä'zen the Clykolkonzentration ,, If the glyco concentration is increased above 45 percent by volume, it decreases, as in f:?; tg; the effectiveness of the defrosting

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means for preventing ice and / or snow accumulation, therefore exceeding the upper limit value should be avoided, since it also increases the cost of the defrosting means because of the higher cost of the added glycol. A reduction dor concentration below 30 volume percent impaired, as stated, the performance of the Abtaumitte'is, ·. · Hen this wira applied to a treated area as _t Jie ability cxior snow is reduced to prevent the accumulation of ice unci /.

The mechanism by which the critical limits of the glycol content according to the invention are determined in percent by volume, is, as far as it can be seen, probably related to the freezing properties that the defrosting agent does. .> · ^ Rändelten outdoor area gives, sov.ie mi ε üor _t on ... · inhergehenden effect on incident ice or snow incident. It is believed that the freezer; unk i: a. cte to a erf indungsgernäßen Abtaurni], O <n-.iöl · te outdoor area impinging ice or snow reduced v ^r ill, causing the ice or the snow is usually at the question populated areas prevailing temperatures is brought to melt. An increase in the glycol concentration above 45 percent by volume or a decrease in the glycol concentration below 30 percent by volume apparently guessed a higher percentage of ice and / '! - aru ^ or ·. Ci ' end up as snow

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a mixture of defrosting agents, the composition of which lies within the stated limit values, thereby reducing its effectiveness of the defrosting agent is reduced. It should be noted that the above statement is given with the intent will facilitate understanding of the invention and serve as a likely basis for the determination the specified critical limit values. SU is but not as a limitation or definition of Uinfar.g and understand the scope of the invention.

. A preferred, specific embodiment of the Z. "invention is a Abtaumittel from about 37 percent by volume -: '. ■ hy, .en- and / or propylene glycol in water, about 0,' \ Voi'iiaen -" - rcent Fuchsin contains. This defrosting agent was found to be used up to a screeching fall of. - »about; 5 ^ m with regard to the prevention of snow and / or 1; ί -xx, .- collection effective. When the defrost with Cc-1 airolct on. <. The area to be treated is applied by pouring, spraying or soaking the area to be treated, the treated area is tinted or tinted by the dye added to the inventive photographic agent. This coloring can be determined visually by a user and enables; This means that the presence of the prophylactic defrosting agent on the treated surface is to be determined brought and flows wof _: - The abf lic · .. "sndo melt washes

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the defrosting agent applied to the surface. Continued Snowfall will therefore bring-on the coloring or turning of the treated surface to disappearance. There, as already mentioned, a single application of the defrosting agent according to the invention up to a snowfall height of About 15 cm is effective when the amount of snow falls As this value approaches, the color or tint of the treated area fades or disappears. Can be recognized that ο a second treatment with the ab - De-icing agent is required. The need for more subsequent treatments with the Abtaumitxol for strong or prolonged snowfall is of course the same Way to recognize.

The stripping agents of the invention are first sprayed onto the surface in a pressurized storage tank sprühondon Spi'ühdüijc- applied. By means of a single spray nozzle on the Sn.de of a flexible hose, the user can maintain or fix the area to be covered. The area to be covered is sprayed until it is visibly moistened or wetted. Usually k , h liters of defrosting agent to cover an area of

2
about 9 »3 ni to coat.

The Beisjii -: "· xe a -." Clarify the invention.

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Sealed concrete blocks with an area of around 9.3 dm each were _{cooled to -6 t} 7 ° C in a chamber. After cooling, hi ml of a mixture of 37 percent by volume; Äthylonglykol, Cj volume percent water and 0.1 percent by weight of a .Warbst egg.> R Ji, the table below listed of Ce gl Giciinrir-iiJig · sprayed with oir for each Blorx Abtauni. ί: ο1 was used with a different dye each time.

After the de-icing agent had been sprayed on, 100 ml of freshly fallen snow, which had a temperature of -6> 7 ° C. and was allowed to roll at -0.7 ° C., were sprinkled on each of the blocks. If after trying a; Eastern staining was present strong enough to be visually detected. Dust ^ n a ioitcrfiii 'Lei "ienge of 100 ml of snow in each case as long or c'." Repeated until either only one versoJra. ^1. ! ■ Jp .- 'i ■ reading color present or no further ibsclii .-' rlzsn. of the snow. Each of the examined. Abtautr.ittol was then determined with respect to the snow mea ^ o of ι OO λ! ; - / wiri valued the number of amounts of snow that could be carried to £.! before the melting ceased.

All color r u . ? ■? ::. were carried out by a single observer, namely rc-- 'visually, that is to say without aids, in order to , can actually use the defrosting agent ... ε-iler. /sdingur.jjen to simulate. Ie that

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since a user of the product in question, e.g. a homeowner, If no quantitative measuring devices were available, naturally observe and determine this visually as well would have to determine whether there is sufficient residual color on the surface to determine whether it is already it is necessary to use the defrosting agent again.

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Tabel

Time required to melt the snow (minutes)

dye Color
indox
CI S c hne dusting ^
First second Third 40 60 Remain
de spots
or Fürbunp; 3 group 1 40 "60 Acid yellow 1
(Acid Yellow 1) IO316 20th 40 60 no Acid green 25
(Acid Green 25) 6155Ο 20th 4C 60 weak Acid green 1
(Acid Green 1) 10020 20th 40 60 very weak 3 acid red 97
(Acid Red 97) 2Ο89Ο 20th 40 do very weak Acid Orange J
{ Ac id Orange 7) I55IO 20th 4o SChVitC; Sävreblau 25
(Ai ... ^ri lue 25) 62055 20th '-: 0 6 ' r CUTVcL..χ Sourublau 78
(Acid Llue 78) 02105 20th 40 60 Sarah 92
{Sorry Blue 92) I339O 20th s c Ii awake Tlrnmaitii η «Η 11T" ft 20th Ic ei ine

3-i'Uppe 2

B:; 3iscl:, - Violet c 2 'Basic Violet 2) 42520

Basic violet 1 (Sasic Violet 1) 42535

ßasisch-Violetc 4 (Basic Viole-c k) 42000

BasiscIi-.Blue Z'o (3asic: 31ue 26) l> -k0 '' -.

Basic blue? (Basic Glue 7) - '' '' Basic cli green 4 (Basic Green 4) ■ '-

20th 40 60 weak 20th 4o 60 ' considerable 20th 40 60 considerable 20th ', 0 60 strong 20th 40 60 considerable 20th 40 6o moderate , / 087 5 BATH ORIGINAL

As can be seen from the test results shown in the table above, the dyes of group 1 disappeared consistently and proportionally to the loss of antifreeze or thawing effect. So the defrosting agents with dyes were missing
of this group, all of which contained sulfonic acid groups, determined that the defrosting agent had to be terminated again if the color was essentially defective.

With the dyes of group 2, on the other hand, was not riur
no one timmung respect to achieve color of ~ / ~ rbleil ·> nd η '^ · j'cken or but these dyes
With one exception, all of them left strong stains or colouration in the form of the ornate. on you, j-osk, although the antifreeze or defrosting effect bere ..; -; had completely disappeared.

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Claims (7)

Patent claims: 1.JLiquid defrosting agent, consisting essentially of ¹ ^ - / 30 to 45 percent by volume of at least one alkylene glycol with 2 to 6 carbon atoms, dissolved in water and a compatible organic dye containing at least one sulfonic acid group in an amount sufficient to make the defrosting agent to impart a color that is visually recognizable when it is in contact with a surface. 2. defrosting means according to claim 1, characterized in that that it, based on its total volume, is about 0. 's volume percent Contains dye (s). 3. defrosting agent according to claim 1 or 2, characterized in that it is a dye from the group of aromatic sulfonic acids, nitro, monoazo, diazx> and Contains anthraquinonesulphonic acids. 4. defrosting agent according to claim 3 _t, characterized in that it is as Farbscoff acid yellow 1 (acid yellow i), Ercmaminsäura, acid green 1 (acid green 1), acid orange 7 (acid orange 1 '\ _Λ acid blue 92 (acid blue 92) Acid red 97, Acid blue 78, Acid blue 7B, Acid blue 25 or Acid green 25. 509845/0875 5. defrosting agent according to one of claims 1 to k, characterized in that it contains ethylene and / or propylene glycol as alkylene glycol. 6. Procedure for preventing the accumulation of snow and / or ice on open-air areas by applying a. Defrosting means, characterized in that on the free of snow and / or ice a defrosting agent according to one of claims 1 to 5 is applied to the open-air area. 7. The method according to claim 6, characterized in that one the defrosting agent by Druocspritzen directly on di Applying open-air area, while this is essentially is free of snow and ice. 509845/0875