DE1569467A1 - Process for the production of plastic bodies inflated with gas - Google Patents

Description

: PATtNTANWXLTE 1 5 6 8Λ 6 7

PROF. DR. DR. J. REITSTÖTTER DR.-ING. WOLFRAM BUNTE

8 MUNICH IB, HAYDNSTRASSE 8. PERNRUF (0811) 83 4712, "

Dr. Expl.

Munich, the I3. March 1965 M / 774?

YERFAHREH FOR THE MANUFACTURING OF PULLED UP WITH OAS KMSTS'JOFFBODIES.

The invention relates to plastic inflated with gas - Shaped bodies, their manufacture and their application · Im in particular, it relates to the manufacture of plastic microspheres and other plastic moldings that are inflated can, if so desired, and on the application of this body to boiling liquids or solids such as, for example cosmetic tonics or creams, edibles or nutritional substitutes, To supply or pressurize coatings or the like with entrapped gases, thereby creating desirable changes in the volume of the same, in the insulating properties etc. can be caused

A particular embodiment of the invention relates to it special attention to the use of such inflated bodies as pressure

■ 90983371274 ""

BATH ORIGINAL "

Means in eelbsttreibenden Sohaumzubereitungen that la dealing manchaal unriohtlg as "aerosols" beseiohnet "earth vie Basiersohaum, edible Sohlagsahne, fire Lösohsohaum, actual sprays rom aerosol type vie schweißrerhütende coat, insecticidal Spraye, hair sprays and even vie in solids edible, non-nutritive substances or low-calorie waffles, which are useful to combat feelings of hunger, and the like

Ub to avoid unnecessary repetition aims to be perfect Description of the US patent 5 12-262 should be noted, however, their basic characteristics, which are also those of the goal-lying Invention are peculiar to summed up here for a better understanding should be. This invention basically describes the Sinsohluß or the encapsulation of a tight, thermally stable "generator" into a plastic body or into particles and the puffing or puffing up the latter by a "gas filling" at a preselected time · This happens because the plastic containing the generator a "diffusion agent" is exposed that penetrates into the plastic can diffuse and there with the enclosed generator with evolution of gas reacted. So there are the basic requirements for the producer apart from his ability to react to the gas devolatilizing Diffusing agent in its thermal stability, i.e. in its ability to contribute without decomposition, evaporation or gas evolution

909833/1274

BATH ORIGINAL

the processing temperature used in the manufacture of the producer containing plastic body is applied to withstand. In the additional application are a number of effective combinations of plastic, suction agents and lubricants described, these as well as others alike in the present invention can be used and their special selection of course something depends on the intended use.

Sometimes it is desirable to loosen up products in order to More extensibility or the need to improve or change it, to increase its volume, or to improve its insulating properties to improve, or to create a propellant for dispersing, etc .. Up to now, however, this was associated with technical difficulties, which were either caused by the premature consumption of the gas from the product through the atmosphere or the use of expensive, gas-generating chemicals and processes are required or complicated pressure-release systems are required, whereby also a combination of these various difficulties could arise. . _. ■; ■■■ /. ■

The present invention relates to gas insulators

such as gas-inflated plastic microspheres that for the inclusion of a number of products instead of τοη gas in liquid

90 98 33/127 4

Tiger shape are suitable. The present invention relates to also "air-containing" or gas-laden creams and other preparations, di · contain gas in enclosed or semi-enclosed form, and also a process for the production and packaging of these preparations. Microspheres made of plastic or casings are very special Subject of the invention to contain gas in latent form and to be inflated if so after attachment in the appropriate Environment becomes necessary. These and other features as well as the operation, uses, and advantages of the present invention can be found in more detail in the following description and the illustrative examples · All amounts and ratios of substances are parts by weight unless otherwise stated

It has now been found that new and improved gas-puffed ones Plastic bodies as pearls or microspheres or in other Shape can be made suitable for inclusion in a product or molded article that is pressurized or loosened should be »The plastic beads or microspheres or others Bodies are created by encapsulating or otherwise enclosing a highly gas-evolving substance or mixture ("generator") such as Sodium bicarbonate or a mixture of the same with dry citric acid or the like made in a suitable plastic of appropriate size and shape such as polyvinyl alcohol. Of the

909833/1274

BATH ORIGINAL

resulting bodies containing the producer can then be used in the preparation or the mass to be loosened or put under pressure can be incorporated, the desired effect being achieved by expanding the Plastic body by exposing it to a suitable one Diffusion agents such as moisture or an aqueous one Acid can be achieved through the special plastic used can penetrate and in it a Sas duroh implementation with the included Creators set free · We prefer to be producers and diffusion agents chosen so that their reaction results in a gas, which diffuses out of the inflated plastic body at a much slower rate than the diffusion agent in can diffuse into the body.

Any suitable method for producing the bloated Plastic body can be used. For example, if microbeads be prepared according to a preferred embodiment of the invention, this can be done with advantage by dissolving a water-soluble Plastics such as polyvinyl alcohol in water along with a appropriate amount of sodium bicarbonate or other gas generator achieved that does not react with water

In preparing such an aqueous solution of Plastic and pottery it is preferable to use enough water

809833/1274; _BATH

to allow the formation of a clear solution. The education maximum concentration suitable for such a solution will vary somewhat depending on the choice of plastic and producer used, however, suitable concentrations are borrowed from the preceding Experiments can be determined · In general, are solutions with about 2 - 10 # plastic, e.g. about 3 - 7 # polyvinyl alcohol, plus the desired amount of producer, e.g. about 2 to 100 parts Producers per 100 parts of plastic, when performing the present Invention suitable · The resulting solution is with vigorous stirring in a large amount of a hot, essentially with Water non-miscible liquid, e.g. a hydrocarbon such as xylene or toluene, which is preferably kept at or near the boiling point are dispersed in droplet form, being a water-in-oil emulsion with small Teilohen arises, which a Teilohendurohmesser between about 0.1 to 100 microns, and preferably between about 1 to about 10 microns, and form the disperse phase. It can be minor Amounts of an Eaulgator such as lanolin or lanolin alcohols, non-ionic Substances, monoglyceryl stearate or other known emulsifying agents can be added to support the formation of the dispersion. When this dispersion is boiled, the water present becomes an azeotrope Geaieoh removed with the hydrocarbon, and dispersed watery droplets are converted into plastic microspheres, which contain the producer like sodium bicarbonate.

909833/1274

SAD ORIG / NAL

Similar microspheres can also be obtained by spray drying or Atomizing the original solution, which contains the generator in the plastic, by hot milling the generator with the molten polymer on rollers or in a Banbury mixer below the decomposition temperature of the generator and by mechanical milling or other comminution the resulting mixture is made into a small rope size after cooling and hardening; such a solid mixture can also be used in a non-reactive medium such as Xylene in the case of polyvinyl alcohol are dispersed from which the microspheres can be recovered by centrifugation or filtration

Another method is to use suitable pearls Melt extrusion of the plastic can be obtained in which the previously finely powdered producer has been dispersed, then being chopsticks or threads of the desired diameter are formed and the then divided into particles or grains of suitable length.

When mechanical grinding or crushing to form these producer-containing plastic beads are used, it is often advantageous, this by heating to a higher than the melting temperature of the plastic and below the decomposition temperature of the Producer located temperature for finishing while

90983 3/127 4 _BATH

They are dispersed in a liquid that contains the plastic does not solve easily. This fuses the sharp corners and ensures maximum containment or encapsulation of the generator within each bead.

Another method of making inflated plastic bodies consists in the application of the generator to the plastic as an ink-like dispersion in a liquid such as xylene, Toluene or benzene, i.e. in a liquid that is not a solvent for the plastic used. In these cases the Generic "ink" on a fabric or film of the plastic by means of a flexographic offset printing machine or the like applied, the solvent evaporated and another film or fabric over the printed area by any conventional Heifisiegelungsteohnik is layered. Depending on the type and the manner in which the generator-containing ink is transferred to the plastic various shapes of inflated bodies can be obtained in this way. For example, small pearls can appear on it this type can be produced by applying fine dots of the ink and then punching them out of the coated film Ss can also be formed with indentations or corrugations when the coated film is expanded if the ink is applied in a dot pattern or in suitable stripes. Egg

909833/1274

^ß AD Origi _Nal

Cardboard-like structures that are used to pack eggs, or other zer-. used for common objects can be made in this way when the ink is applied in the required manner »

Regardless of the method used, the amount of the generator enclosed in the plastic should usually be dimensioned in such a way that because they expand about 25-350 times the volume of the plastic body cause *, e.g. in the case of the essentially spherical pearls, a 5 to 7-fold or greater expansion of the holiday diameter. For this purpose, the producer is usually made of plastic in one Concentration from about 1 to 100 parts and preferably from about 1 to 75 parts of the producer per 100 parts of plastic included.

When the generator is enclosed between sheets or fabrics made of plastic or the concentration in a plastic body is such that the particles of the generator are relatively duroh each other If thin plastic membranes are separated, full bloating easily occurs when the diffusion agent penetrates into the generator a * When the producer is surrounded by a relatively thick layer of plastic is, the expansion can be accelerated by heating the system, so that the heat of the enclosed plastic when entering the Bloating is facilitated

909833/1274 ^BAD

If more pressure is required than homogeneous penetration of the product is required, a suitable pressure generator can be used Body in Torah of a substantially flat double-walled plastic container or envelope are made, in which a appropriate amount of the producer in a single or in several tasers is included. For example, a producer such as sodium bicarbonate plus anhydrous acid, e.g. citric acid, can be placed between two sheets of polyvinyl alcohol of suitable shape which then heat sealed to form a container or envelope They are then placed in a pressure vessel before the product is packaged to be inserted in the same · If, for example, a round, disk-like Sheath or a container of this type on the bottom of a pressure vessel Clay put about the same Durohmesser and the container then with a cosmetic preparation such as an aqueous base foam emulsion is filled and immediately closed, the container becomes like an under when the emulsion is exposed and the grass develops afterwards Spring-loaded piston, thereby facilitating the dispersion of the liquid content when the dispersion valve or mechanism is opened

Regardless of whether the invention is applied to the microspheres, which are dispersed in the basic liquid and then dispersed or whether it is applied to the lining continuously

909833/1274 bad or «« «.

remains in the container, the gaseous propellant remains, which may in the plastic body or the sheath according to the present invention is developed, essentially indefinitely enclosed in the plastic. This is a great advantage in pressure packaging, in which it facilitates the initial stage of packaging the product because im In contrast to the use of volatile propellants, this is a loss of propellant can not easily enter · When moreover the bloated Plastic remains permanently in the container, either in In the form of a lining or in the form of pearls, which are located in the container settle rather than disperse in the liquid product remain, will pressurize a more permanent one according to the invention all obtained with a volatile propellant included as such in the liquid product.

The plastics particularly suitable for the present invention are those that are permeable to moisture " Water-soluble plastics such as polyvinyl alcohol are very special suitable if it is desired to put the inflatable plastic body in To produce the finest Kügelohea shape. In the same way, however, are water-permeable, although water-insoluble thermoplastics such as homopolymer «or copolymers of vinyl acetate», of vinyl chloride, Vinyl acetate copolymers, ethylene vinyl acetate copolymers (im Commercially available under the name Elvax) ®d @ r hydrolyzed derivatives

909833/1274

BATH

ISb

Act of "the same, homopolymer" or copolymer "of styrene, the polyethylene, Cellulose esters such as cellulose acetate, propionate or butyrate ■ Can be used with or without the addition of small amounts of suitable plasticizers. For example, in the case of polyvinyl alcohol it is often advantageous » about 5 to 10 percent by weight of an alcoholic plasticizer such as glycerin, propylene glycol, ethylene glycol, sorbitol, etc. to be added, as these "plasticizers" make it easier for the polymers to dissolve in water. In addition, this is done by the small pearls that are created more pliable, which is an advantage if these are "pearls for inclusion." to be used in cosmetic «creams, etc.» · The other mentioned thermoplastic plastic «can in a similar way with the usual ester-like Weiohmaohern such as dibutyl phthalate, dibutyl sebaoate etc * to be softened.

It is also possible to use resinous polymers of the aoryl or methacrylic acid, e.g. copolymers of acrylic acid with methyl methacrylate or to use with acrylonitrile, in which case the polymerized Organic acid can serve as the source of the acid required to react with the producer in the diffusion of water into the same is required. It is also possible to replace the previously mentioned ones individual plastic "this" to be used as mixtures with one another * Even non-polymeric substances like aoetylated ulycerol mono-

90 9833/1274

BATH

Any plastic medium containing the producer can be used will.

If it is desired to make small beads for use in an aqueous medium, medium to high viscosity polyvinyl alcohol which is at least 98% hydrolyzed is preferably used because it is practically insoluble in cold but fairly soluble in hot water. However, if the inflatable beads or bodies are to be used in a substantially non-aqueous system or in a single use product, less fully hydrolyzed polyvinyl acetate polymers, e.g., acetate polymers which are about 85-90% hydrolyzed, can also be used. If the remaining acetate groups are between about 35 and 5 ⁰ , the hydrolyzed polyvinyl alcohol dissolves in cold water, but precipitates when heated. Only when the hydrolysis is essentially complete, so that the acetate content of the polymer is not more than about 2 ^, does the alcohol become soluble in hot water and only swell in cold water. The commercially available types of vinyl alcohol are white powders with a density of 1.3 and a tensile strength

^1/2/2

«Between around 63O kg / om and 1190 kg / om or even nooh higher ·

If required in some cases, inflatable pearls or manufacture products of this invention from polyvinyl alcohol and

909833/1274 _bp

To have them available in an essentially completely water-insoluble shade, this can be done by treating the pearls in another known manner with glyoxal or with chromium salts such as chromium sulfate or chromium filtrate. This treatment disrupts the usual diffusion of moisture because the polymer does not increase it jedooh the resistance to the action to be developed of the solvent liquid water and the ability to gases such as GO _2, rome producers to hold back.

When working with water-insoluble plastics such as polyvinyl acetate or cellulose esters can be made expandable microspheres by dissolving the plastic in a suitable solvent, e.g. acetone, Methyl ethyl ketone, Ä'thylaoetat, various Cellusolves etc and then dispersing the finely divided producer in the organic Solution to be prepared with vigorous stirring · The producer is advantageously in these lalls of a size that is less than a micron lies. The polymeric solution that contains the generator dispersed is then redispersed in a lioht solvent with vigorous stirring, for example in a relatively high-boiling hydrocarbon such as xylene, toluene or a refined kerosene or an oil fraction, the oxidized solvent is distilled off and agflomeration is prevented using kräfifeia SuhMm *. the

909833/1274

BAD ORlGiNAL

Microbeads can then be recovered by! Filtration. if a high-boiling hydrocarbon oil is used as a dispersion medium every best of the same can be washed out with petroleum ether or the like.

An anhydrous manufacturing process like the one just described enables the production of microbeads using a generator consisting of 2 components »e.g. a carbonate component and an acid component, as will be explained later, "which generate gaseous carbon dioxide when these beads are mixed with water come into contact

They are particularly suitable producers in this invention the bicarbonates of the alkali metals, e.g. Natriuabioarbo & at, Kaliuabioarbonat, Lithium bicarbonate and the corresponding carbonates or earth " alkali carbonates such as calcium or magnesium carbonate. Dependent on Sound of the intended use, however, can be any other, In the U8-Fatentsohrift 5 128 262 described generation system also rer » be turned. With producers such as Caloium- or Aluminiuacarbi *, who react with steam, water can either be in the liquid or in the Vapor phase can be used as a diffusion agent when the plastic in which the producer is immersed, there is sufficient compared to water is permeable. If a producer who is sensitive to water

909033/1274 bath

of course, an anhydrous inclusion method is required be applied·

Is the producer used a compound like a carbonate or a bio-carbonate or a powdered metal like zinc or Aluminum, the presence of an acid sur release the desired Requires gas filling and if the presence of the required acid in the environment in which the inflated plastic body of the invention is used, such as in a Cream or a liquid preparation cannot be approved, as these may require a neutral or alkaline pH value Acid required for gas development in the plastic at the beginning be incorporated, provided that the acid component selected in this way is compared to the bio-carbonate or another gas-generating producer until suitable triggering, for example by diffusion foreign moisture does not react

For example, a powdered mixture containing a solid acid, an acid anhydride or an acid salt and a producer such as sodium bicarbonate in substantially equivalent amounts contains, are enclosed in the plastic before it is converted into microbeads, whereby the desired gas development occurs, when these pearls are enclosed in an aqueous medium or

909 8 3 3/1274 ^BAD oriqi _Nal

otherwise exposed to moisture, causing water to enter the plastic beads diffused, and there a reaction between producer and Acid component with the formation of gas causes · To contain Acidic substances suitable for use in the microbeads are solid organic ones Acids, a «B. Citric acid, lactic acid, tartaric acid and oxalic acid} acid anhydrides such as maleic anhydride, succinic anhydride and phthalic anhydride, organic acid salts like acid sodium nitrate as well inorganic, acidic compounds such as sodium bisulfite, sodium pyrosulfite, Sodium pyrosulfate or, in general, water-soluble pyrosulfites, pyrosulfates, Bisulfites, bisulfates and acid phosphates of sodium or others Alkali metals and the like. Maleic anhydride is one of them advantageous acidic component for the purposes of the present Invention due to the high acid number, for example 49 parts (Ϋ2 mol) of this anhydride are sufficient to with 84 parts (1 mol) of sodium bioarb onate to react with the evolution of one mole of carbon dioxide

On the other hand, the acidic component required for the gas generation reaction can also be obtained in that as plastic one of the known! copolymers is used, which itself is acidic Component such as a copolymer of an acrylic acid ester such as ithylaorylate or methyl methaorylate or the like with a small amount of aoryl or methacrylic acid, or the corresponding

909833/1274

the copolymers of acrylonitrile or dergletohen old such eC, ü ~ unsaturated organic acids, which have carboxyl groups in the presence of water, which bits of the included producer can react.

The invention will now be illustrated by a few examples

example 1
Part 1

Inflatable microspheres made of polyvinyl alcohol are formed made of an aqueous solution of the following components!

5 parts polyvinyl alcohol, granular, solid hydrolyzed, high viscosity (Elvanol 72 .60)

2.5 parts of sodium carbonate
0.5 parts glycerin
92.0 parts of water

These ingredients are heated to 95 G with stirring, with moderate stirring for about 30 minutes at this temperature until sur Formation of a clear solution continues.

9 0 9833/127 A bad original

The resulting clear PVA-NaHCO_ solution is slowly, drop by drop from a drip funnel into a closed vessel with 1,000 parts Vigorously stirred, boiling xylene was added to the 0.25 part of lanolin had been added to facilitate the suckling. · The vessel. is ait a HüokflusskÜhler, a high speed stirrer and a Dean-Stark-Waseerfall · provided · The stirring becomes sufficiently strong maintained, including a Moaogenization of the PVA «NaHCO_ solution as Produce water-is-oil dispersion. Pie will boil kept so large, including the removal of the water as an azeotropic mixture Ensure of xylene-H ^ Q as quickly as the PVA solution is added will. After adding the solution and draining it, the resulting Xylene suspension of PVA-NaHCO, -Kugeloheß filtered or centrifuged and put the balls in a yakuua oven at -100 ° C for a few hours dried·

The particle size of the resulting microbeads containing bio-carbonate generally ranges from about 0.1 to about 5 microns and mainly depends Sound the stirring speed, the speed of the addition the aqueous solution sub-oil bath and the speed of boiling. The use of these microbeads to put under Druok a cosmetic Cream is described in Part 2 below.

909833/12 7.4

Part 2

A common erea-type anti-alcoholic drug will be like follows producedι

52 i “ Water

18 56 Acid-stabilized Glyeerylaonostearat («Tegaoid Begular ^N )

5 1 » propylene glycol

20 " Aqueous, basic aluminum chloride complex and 50 " basic aluminum chloride

5 + whale advice

100 parts of this emulsion are then added at Bauateaperatur with 2 parts lactic acid and with 10 parts PYA-M * HCO_-Mlkroperlen with a part size swisohen about O ₉ 2 to about 2 microns τβτ- ■ ieoht, which as in part 1 of this example were manufactured. The resulting Misohung is immediately given at ataosphere pressure and building temperature in a steel Sruokdose, which contains a dispensing valve and a Einauohrohr τοη of the kind that are used for the distribution of Sohaua ύφχ ^ , ie in a container that is usually used as an aerosol boabe then the vessel is re-closed in the usual way. The expansion of the microbeads and the submergence of the contents of the container occurs after a few hours of standing, with the contents

909 8-3 3/1274 BAD original

on request, any show under Sruok »can be handed in.

Example 2

The microbeads (5 parts) prepared as in Example 1 were made into wafers using edible gelatin (1 part) as a binder. deadttel pressed. When ingested, these waffles got through in the stomach the effect of the stomach acid is bloated and thus counteract the feeling of hunger. They can be used as a diet aid or as a food substitute Can be used.

Example V

Inflatable polyvinyl alcohol microspheres were prepared in the same manner as in Example 1 except that the following

■■ "'- ■
• parts were used!

10 parts polyvinyl alcohol

5 parts caloiuao carbonate

0.5 parts glycerin

84.5 TeUe waeeer

90 98 3 3/127 U

example A.

In. The sea example is the manufacture of inflatable microbeads described in a non-aqueous system. 10 parts polystyrene and 1 part fine aluminum carbide powder (0.044 mm masonry width) are ground on hot rollers until the aluminum carbide is evenly distributed in the polystyrene. After cooling, the dispersion becomes mechanically at low temperature under anhydrous conditions grind to a fine PulVera. The resulting powder (10 parts) is then stirred into 500 parts of boiling anhydrous butanol, the there is no solvent for the plastic, so the small particles melt into spheres, whereby maximum inclusion of the generator in the plastic is achieved »The resulting butanol dispersion is finally cooled and the solid substances filtered off and dried for a few hours in a vacuum oven at 60 ° C

The resulting microbeads expand slightly when they come into contact with steam or hot water.

Example 5

Polystyrene inflatable beads containing a two component generator can be prepared similarly to Example 4 in which 10 parts of polystyrene with a mixture of

909833/1274

1 part hatriuabiocarbonate and 1 part sodium metabisulphite are bound »- -" ... '- :: --'- "■.

For this purpose the sodium bicarbonate and the sodium metabieulfite were used «First of all in a ball mill in a troubled atmosphere Briielung a uniform mixture of the acidic and the alkaline SaI * Teraahlen. The mixed salipulrer was then hot Wftlatn is dispersed in the polyatyrene resin and the resulting Misohung naoh the method described in example 4 converted into microbeads,

You can look at these finely preserved pearls in a similar way wi · the obtained in example 1 are used because they are jβdooh contain an acidic component as well as the actual Irseuger, Their action does not depend on the tone of the diffusion of feeader acid. she can therefore in neutral or in alkaline aqueous media as well be used in humid gaseous environments.

The inflatable pearls of discovery are valuable in this Manufacture τοη Übersüg «with isolating ligatures», uad they slad suitable for use by spraying, dipping, brushing etc.

For example, a preparation suitable for this purpose can be used by dissolving τοη 2 ropes of polyrinyl alcohol in 100 ropes Water and then dispersing τοη JO parts of the aluminum carbide containing polystyrene from Example 4 in this solution in of the cold

The resulting dispersion can then be applied to insulating objects such as, for example, steel pipes are sprayed on and allowed to dry, with rorsugweise radiant heat τοη an infrared lamp or the like to increase the permeability of moisture of the polymer is applied · The water vapor penetrating the polymer reacts with the aluminum carbide with Sr diffraction τοη methane as a gas phase in polystyrene, creating a heat-insulating cover ring is formed around the pipe

The dispersion just described can be applied in a similar manner to masonry or other building materials as acoustic insulation will.

By dispersing the polyethylene-aluminum carbide beads in of the aqueous polyrineal alcohol solution, on the other hand, it is while the latter is hot, it is possible to inflate the pearls in the upper eye or to expose them, bcTor this is applied to the su insulating surface

909833/1274

SAD ORJGijsi _AL

Example 7

Another »to produce τοη inflatable microbeads based on a water reactive generator Method is to use an inert organic solvent as shown in this example.

10 parts of polyvinyl alcohol resin (Elvanol 72-6θ) are dissolved in 100 parts of diethylenetriamine, whereupon the mixture is stirred and heated to about 50 ° C. As soon as a clear solution is obtained, 0.2 parts of Al G- (0.044 mm mesh width) are added Continuing the charging admitted. The resulting dispersion was then added slowly and with vigorous stirring a hoohsiedenkn inert hydrocarbon oil, which was kept boiling and an initial boiling point -of greater than about had 23O ⁰ C, was added, that is an inert liquid which boils above the boiling point of the original organic solvent . This addition takes place in a vessel which is provided with a mechanical mixer and a cooler for the distillation and which enables the solvent to be recovered. The addition is carried out at such a rate that the diethylenetriamine is distilled over as soon as the solution is added to the hydrocarbon.

After the addition and stripping of the amine is complete, the hydrocarbon dispersion of the PVA-Al Cj system was cooled

909833/127 A

15694F7

and filtered or centrifuged · the · solid · were old one washed low-boiling inert liquid that removes the heavy oils, without essentially affecting the plastic bed parts of the beads For example, solvent naphtha can act for this purpose or petroleum ether, benaol, ethyl ether, aoeton, etc. can be used. The solids were eventually circulating at 100 ° C Air dried or in a vacuum oven.

In case of contact with water or water vapor - e.g. air relatir high humidity, the pearls produced in this way expand using methane, whereas polyvinyl alcohol is relatively impermeable. These Pearls can be mixed with any of the binders commonly used in the coating industry and then by spraying either from a cold aqueous system or as a dispersion in an anhydrous one Liquid can be applied. In this way, highly effective sprayed-on thermal or acoustic insulation can be produced. As previously described, when this insulation is applied from aqueous systems, the expansion can be in either the Dispersion occur before or after spraying, depending on on the delay that can occur between the preparation of the dispersion and its application. When used in an anhydrous System, the expansion occurs after application to the treated upper

909833/1274 bad

-.27 -

Fläoht and near evaporation of the volatile carrier and exposure of the perium-containing coating to moisture. This expansion takes place rapidly on contact with steam or poor air of high relative humidity, although a satisfactory expansion also takes place on contact with atmospheric air of low relative humidity for a long period of time. If a non-volatile carrier having a relatively high resistance to water penetration is used in the preparation of the insulating coating, previously expanded beads are used in advance. --'- ^: - ^: ■ ": '■■■■.'"". /

Obviously, numerous modifications and variations, not all of which are intended to be listed here, are possible for those skilled in the art. ■ '.- ■, ..

909333/1274

Claims (1)

Patent sprrtioha 1 /) Method of lere division -of gas inflatable arts toffteilohen, characterized in that a solution of a normally solid plastic and a dense, thermally stable one gas-generating agent is produced in a solvent that is essentially opposite to the »plastic and the gas-generating agent Agent is inert, this solution being converted into a large number of plastic particles without decomposition of the gas-generating agent containing the dense, thermally stable, gas generating agent dispersed therein, with a partial ohmic diameter τοη about 0.1 to 100 microns 2. Method according to claim 1, characterized in that a cellulose ester is used as the plastic. 3 · Method according to claim 1, characterized in that as plastic an essentially water vapor permeable plastic and i-luminiumoarbide is used as a gas generating agent. 909833/127 A 4. Method according to claim 1, characterized in that (a) ale Plastic polyvinyl alcohol is used, (b) the gas generating By means of a SaIa from the group of alkali metal or alkaline earth metal carbonates or bicarbonates or mixtures thereof, and (o) the solvent used is water, the Weight ratio between gas-generating agent on plastic between about 1 ι 50 and 1 s 1 is. 5 »Method according to claim 4, characterized in that the solution by spray drying below the decomposition temperature of the gas generating agent in those containing the gas generating agent Kunststoffkugelohen is transferred. 6. The method imoh claim 4, characterized in that the solution by dispersing them in a normally liquid hydrocarbon solvent, Removing the water from the resulting dispersion and separating the plastic balls into the gas-generating ones Plastic balls containing means is transferred, the carbonate erasugende means τοη of the hydrocarbon solution contain. ■ -: ■ - ■ - ■■ -bad 9098 3 3/1274 7 Process * for the production of self-propelled, pressurized, Liquid preparations which are intended for delivery from pressure vessels are characterized by the fact that a liquid, supplying substance is used Preparation is enclosed in a dispensing container, wherein the preparation (a) At least one plastic body with a gas generant included therein; and (b) a diffusion agent which diffuses through the plastic and into it can develop a gas during the reaction with the enclosed gas-generating agent, the container immediately re-closed while Druok is being created in it, and where the plastic, the gas generating agent and the diffusion agent are selected in such a way that that the rate of diffusion of the gas generated through the Plastic significantly lower than the diffusion rate of the diffusion agent is through it 8. Method according to Auspruoh 7, daduroh gekennseiehnet that a plurality Wipe the small pearls of the water-permeable plastic containing the gas-generating agent with the size of a portion about 0.2 and about 2 microns is used, which is the gas-sucking Agent-containing pearls are used in an amount sufficient to give a pressure of at least 1.05 kg / om in the Manufacture distribution container. 909833/1274 sad original 9. The method according to claim 8, characterized in that the small Plastic beads are essentially made from cellulose ester "earth. 10. The method according to claim 8, characterized in that the small Plastic beads are made from polyvinyl alcohol .; - «earth. - '";" ". ■"' '■ -': ■. 11. The method according to claim Θ, characterized in that the gas generating agent contains a salt from the group of alkali metal carbonates or bicarbonates or alkaline earth metal carbonates, while the diffusion agent contains water and a Saus® during the leaction of the gas generating agent alt the Sif £ & sl @ nsaittel 12. The method according to claim 10, daduroh gekennselohnet that the gas-generating The agent contains aluminum carbide and the diffusion agent contains water. 13 · Method according to claim 8, characterized in that the liquid to be dispersed is a fiaulsion which contains an aqueous and an organic phase · . ~ 90 9833/1274 . 32 - 14 · Method according to Claim 13, characterized in that old gas-generating Means a substance is used which is a (Jas duroh implementation “it sets an acid free, while an emulsion is used as a liquid, which is a continuous one aqueous phase and a pH between about 4 and 6.5 15 · Method according to claim 13, characterized in that the liquid represents an emulsion with an aqueous and an organic bubble and a pH value between about 7 and 9, wherein the small pearls as a gas generating agent an essentially anhydrous mixture of (a) an acidic component from the group of organic acids, organic acid anhydrides and pyrosulphite, pyrosulphates, bisulphites, bisulphates and acidic ones Phosphates of the alkali metals and (b) a carbonate component the group of alkali metal carbonates and bicarbonates and the Contains alkaline earth metal carbonates. 9 0 9 8 3 3/1274 ^8AD original