Laminated sheet.

The invention concerns a composite sheet based on at least two layers, in which at least one outer cover layer, normally insoluble in water, is joined with a water-soluble reactive layer, which in turn constitutes at least by a layer, which contains a dissolution inducer for the cover poop, and therefore, the sealing layer is structured free of pores by extruding a sheet from a thermoplastic synthetic material. ·· .. ·.

In the German publication specification 2,703,005 of the Applicant, a relevant sheet is described for one-time use, as a hygienic top layer for a toilet seat. This sheet, in one embodiment / 1 may be structured as a composite sheet, having * · a water-soluble layer, which is oriented towards the sheet, and on its side away from the user a layer of cover or seal insoluble in water . This cover layer can be dissolved in an acidic or basic medium. For this, the water-soluble layer has a corresponding basic or acid addition, so that the sheet, in the case of a total immersion in water, is soluble as a whole, but it is not soluble when the water comes into contact only with water. your cover layer.

In the European patent application 80 108 243.9 of the applicant (publication number 32,244), which has not yet been published in advance, an improvement of this hygienic top layer for toilet seat is described, and it is also mentioned that this sheet It is suitable as a packaging material and for the manufacture of handbags, sauces and the like.

It has been found that a sheet of the type described by llojn no.

in the European publication specification 32 244 is appropriate, not only in a flexible form but also in a self-supporting form, especially in the form of sheet or plate from semi-rigid to rigid, for many purposes of use, especially as packaging material. Such mechanical holding capacity or such stiffness can be achieved by rigidly formulating the polymers of the re-active layer and / or the actual covering layer, or by providing the reactive layer and / or the cover layer of the product. cargo rails, especially mining materials », them and / or fibrous material. Thus, the reactive layer of the composite sheet can be structured as paper, cardboard, cardboard or corrugated cardboard, being the binder eoipble in water or being able to be dissolved by the inductor? The dissolution contained in the reactive layer, which we preferred, is also at the same time also dissolution inducer for the cover layer. In addition, the reactive layer can also be prepared correspondingly to papermaking by suspending the components from an aqueous solution in an alkaline or acidic medium. The composite sheet can be in the form of cut-out template pieces for packaging material and pre-punched, and may have raised lines for subsequent folding. It may also have been previously shaped to the shape of boxes, possibly with a lid. It is especially suitable as a container for cigarettes and other articles,

po

In an embodiment of the invention, the composite sheet is printed, especially printed in a multi-color manner, which also does not result in any load or pollution to the environment, when the packaging material is simply discarded by the consumer, since containers are rapidly decomposed p.X. <penetration of moisture. If the reactive layer is produced separately from the cover layer, preferably the reactive layer is preferred, and the ability to print can be enhanced by the use of suitable filler materials.^! i

It was also found that for the manufacturing process; The composite sheet according to the invention are colloquially annealed * * - · ·.

and other components which, when decomposed la'lá-;

The mine or the container produced from it have a positive impact on the environment. Thus, components of the sheet or the entire sheet may possess soil-thinning properties and, depending on the choice of the dissolution inducer, may also possess fertilizing properties, when the packages produced from them after use are normally subjected to a putrefaction or compostation (conversion into fertilizer) intentional or are simply discarded. If the containers, after their use, are normally mixed as liquids or are swept by them, components with properties as flocculation aids have been shown to be especially advantageous, about which we will discuss still further on. In a particularly advantageous manner,

Hojh no.

From it, they consist exclusively of those materials that decompose on the side of the reactive layer when they penetrate moisture or liquid, or dissolve by reciprocal induction of dissolution.

The cover layer and / or the reactive layer can also have on its free surfaces a textile covering based on individual fibers, which are anchored therein. upper side of the sheet or are stuck with it. In such a case the length of the fibers, which are felted together and entangled with each other to a limited extent, may be found in the range of about 0.01 to 2 mm or more. The fibers provide a mechanical reinforcement of the sheet and an adhesion of some sheets with others as a result of possible electrostatic charging. Despite e-ΙΐΓσ.,

The sheet, after its use, can be completely dissolved, since the fibers are certainly felted and entangled with each other to a certain degree, but they are not permanently attached to one another. Cellulose fibers, especially cotton fibers, are preferably used as fibers. However, other fibrous materials are also suitable.

27072

The cover layer and the immediately following layer and possibly other layers are nested, especially welded, preferably with each other superficially.

However, they can also be glued by initiation of dissolution of one and / or another of the surfaces or with the aid of a glue. The cover layer and the reactive layer are preferably in the same synthetic material, normally insoluble in water, the reactive layer containing additionally dissolution-inducing additives for itself.

27072

Sheet no. p

- same and for the cover layer. In such a case these additives may be evenly distributed in the reaction layer or they may be present in higher concentration in the boundary zone with respect to the cover layer. Seto generally depends on how thick the reactive layer is and how easily insolubility in water can be converted into a solubility with the help of the dissolution inducer / The reactive layer, when it consists of a water-soluble material , such as hydroxypropylcellulose, can also staz. free of dissolution-inducing additives and have in ei.J * 3. An additional intermediate layer, containing the dissolving-inducing additives, is oriented towards the cover layer. for the cover layer.^J, * ^; Since the cover layer does not need to be

-> "> * *" "sustentadora.cuando the reactive layer takes charge of the support *, is generally thinner than the layer rea *

tiva. It can be kept very thin, since it has become clear that because of extrusion production, a layer thickness of 1 5 / am, a thickness of 2 to 3 / am, is sufficient to achieve a watertightness. desired. Sn generally, therefore, the thickness of the cover layer is less than 10 / am. Whether the thickness of the reactive layer depends on how many additional layers the composite film still contains and what mechanical loads it has to withstand. Its layer thickness is at least 10 to 50 / am and can have the thickness of paper, cardboard or cardboard. The thickness of the reactive layer or of the reactive layers can in this case amount up to 0.5 mm or even has; 1 mm, no limit being established for this purpose. Reinforcements may also be inserted in the layers

Sheet no.

27072 or between the layers, preferably making it possible for the reinforcements, on the other hand, to decompose easily during the dissolution process, as occurs, for example, in the case of individual fibers. The reactive layer can also be structured in porous form and even have the corrugated paperboard structure, and can especially have a corrugated cardboard construction with corrugation * (ripple E) and / or double corrugation. Thicknesses of the composite sheet are possible up to 5 mm and larger. When . It deals with the caoacidad of sODortar mechanical load of the caoa of cover, this, nevertheless ,. it can also be maintained with the same thickness or thicker than the reactive layer, that is- «».

When the cover layer is able to withstand a finished abrasion or scratch, it does not threaten the resistance to water. The cover layer can then be structured.

from self-supporting to rigid, the polymer of the reaction layer may correspond, then, essentially, only the mission of serving as a support, vehicle or binder for the dissolution inducer.

At least when the thickness of the cover layer is in the order of magnitude of the thickness of the reactive layer, or the cover layer is even thicker than the ullage, then the reactive layer is preferably structured or profiled. and formulated in such a way that it dissolves relatively slowly, but before that, store as much moisture as possible. With this the dissolution inductor can be started to dissolve in the reactive layer and the solution of this can in turn lead to the dissolution of the cover layer, before the reactive layer is detached and therefore there is the poly llojn no. It is important that the dissolution inducer is removed by washing, before the cover layer has dissolved. For this purpose they are suitable for the reactive layer, as a binder, inflatable substances, which when made the access of water become gelatinous, but decompose only when the cover layer has also decomposed. It is also possible to adjust the polymer of the reactive layer in such a way that it is soluble at a pH that is substantially neutral or at a weakly acidic or weakly basic pH, but not at a strongly acidic or strongly alkaline pH. When the pH, in the case of water absorption, without em •

• • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • Nap

- ...

it has been detached and the dissolution inductor is extracted • • • partially by leaching, it can also be dissolved

reactive layer. '**

The material of the layer of cubí? It is preferably formed elastically, so that the sheet or plate consisting of sheets or a previously embossed or pre-embossed template piece can be bent or curved to form a package, without the cover layer tearing or tearing.

As the material for the cover layer, the extrudable synthetic materials are suitable, which are not soluble neither in water nor in the essentially neutral aqueous solutions, which are usually present, but which can be made soluble by suitable dissolution inductors, especially acids or ba3e3. On the other hand, the reactive layer may consist of a single synthetic material Ρ Sheet no.

27072 in water or delayed water soluble, such as polyvinyl alcohol or hydroxypropylcellulose (Klucel J from Hercules Eowder) or may contain this synthetic material, for example in the form of a binder for fibers and / or for the dissolution inducer .

Preferred materials for a flexible cover or reactive layer are copolymers or terpolymers of unsaturated organic acids such as acrylic acid, cronic acid, cronic acid, maleic anhydride and crotonic acid as au9 components react with the dissolution inducer,

with vinyl ethers or acrylates as a flexibilizing component. In this case, the reactive components and the flexibilizing components3 can be used in each case •

by themselves or in the form of mixtures. Examples of materials • · *. ; , flexible are exposed in the table, especially ltzs nu • · · · • · · numbers 39 and 68. ·· '·

Preferred materials for a rigid shell or reactive layer are copolymers or terpolymers of unsaturated organic acids such as acrylic acid, methacrylic acid, maleic acid anhydride or crotonic acid as a component that reacts with the dissolution inducer, with styrene or vinyl acetate or methyl methacrylate as stiffening components and vinylethers or acrylates as tenacity-inducing components. In this case, the reactive components and the flexibilisadore3 components and tenacity inducers can be used in each case by themselves or as mixtures between them.

Thus, in one embodiment, preferably at least the cover layer consists of a homopolytic acid lox.

!

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A polymeric or water-insoluble thermoplastic copolymer, but soluble in a basic medium, especially one which is obtained using acrylic acid, methacrylic acid, crotonic acid and / or maleic anhydride with styrene and vinylétei * in the molar ratio 1 : 1: 0.3

Suitable extrudable synthetic materials are also solid copolymers based on vinyl acetate and a small part of crotonic acid, which are present as low viscosity limes and are soluble in alkalis. Such polymer is sold, for example, under the designation Vi \ in.a pas C 305 by the trade name Wacker Chemie GmbH, MBnchep.

• · · · ·

Also the individual layers of the composite sheet may consist of mixtures of synthetic materials.

.....

As dissolution inducers for dissolving the cover layer, it can be used for polymers, especially water-soluble carbonates, secondary phosphates, and water-based polymers. and tertiary, silicates, borates, amines and basic amides. Ia joint use of the so-called disintegrating agents, which upon contact with water se. they intensely swell or generate gases, can also be advantageous. One such disintegrating agent is, for example, sodium carboxymethylcellulose (Nymcel ZSB 10 from Nyma). In such a case, all the materials for the composite sheet are preferably intended to be favorable and uncontaminating for the environment as is widely the case with the aforementioned products.

For the manufacture of the composite sheet, all the layers of the sheet made of thermoplastic materials with corresponding and suitable properties are preferably bonded together by extrusion. In ta

27072 llojn no. In each case the individual layers can be extruded as separate sheets and thereafter these can be bonded together. The connection is preferably carried out while the sheets are still hot and sticky, by simply placing one over the other. However, the surfaces, as already mentioned, can be made sticky at a later time. The sheets that come from the extruder and eventually stretched can be. further processed immediately or can be rolled up for intermediate storage, namely individually and preferably also as sheet, composite.

The individual layers can be extruded back; * ··· '· through a joint extrusion nozzle and in this way * · · · / ···; they can be linked together With this you get a union • ·.

• · · especially intimate. In such a case, however, you should pro; · ·, .. · · Cured that the components of both layers are adapted to each other, so that the resulting waste eventually can be used again in one or the other of the extrusion, without adversely affecting the composition of the material of the layers. Thus, waste containing dissolving inducers, can be used again for the preparation, of a reactive poop or an intermediate layer, containing the dissolution inducer.

In general, the individual sheets leave the extruder in a thicker state than that corresponding to the desired thickness in the composite sheet. In this case, the sheets are stretched to the desired thickness, which can be done individually or in the composite material.

For the sheet according to the invention there are no. eleven

25 '

-numerous possibilities of use, which are mainly present in the packaging sector. The elimination of packaging materials that are no longer usable, today constitute a considerable problem. This can be solved by means of the sheet according to the invention, since this, after use, can be dissolved in water or in aqueous solutions, and as to its material constitution it can be composed in such a way that the substances · · "That in such a case they happen to dissolve are innocuous or uncontaminating of the environment. The anhydride cooolymers of · · ...

Maleic acid and acrylic acid provide after.

• · · · · hydrolysis products similar to polymers based on acrylic acid, widely used as an agent?

• · · · Flocculation aids in the treatment of sludge. "Inc • · "-

• .. · rification. Therefore, they are useful products in an agoa • • • • •

3idual.

• · · · · *

The cellulose derivative Klucel must also be estimated from the toxicological point of view, according to the manufacturer's data, just like a purified cellulose.

The carbonates, phosphates, silicates and borates, which can be used as dissolution inducers, are components of washing agents, as well as the disintegrating agent Nymcel, which can also be used as an auxiliary flocculation agent.

Since the composite sheet according to the invention consists, at least in part, of thermoplastic materials, the packages obtained from the sheet can be closed in a sealed manner by welding or sealing. .

In such case all forms of packaging and. packaging

27072 lloj »nrtm. 12 possess the property that, when discarded after use, they dissolve in an aqueous medium or when moisture penetrates, for example in the open air, within an adjustable period of time.

In a preferred embodiment of the invention, the sheet has, for example, the shape of a cardboard box, a can, a box or the like. In such a case the wall can be structured each time in such a way that it has a tent, both on the inside and on the outside. This can be achieved by the fact that for the formation of a wall, two composite sheets are placed one on top of the other in such a way that their water-soluble sides are oriented towards each other.

• • • • other and the cover layers are oriented towards f.uqra.

• · •_φ ·

In this way boxes and similar items are insensible to moisture. On the other hand, if they are torn * mechanically during or after their use, water can reach the space between the water-soluble layers of the sheet, so that the sheets and therefore the boxes and can be dissolved. Similar. However, it is also possible to structure the composite sheet, so that a water-soluble reactive layer is provided with a cover layer on both sides. After mechanical destruction, this sheet is also entirely dissolvable, since water can penetrate the sheet between the cover layers and dissolve the reactive layer and thereafter the cover layer. In this embodiment it is also possible to structure the reactive layer in a porous manner or to provide it with an absorbent insert, which favors the penetration of water into the layer no. 13 reactivates and therefore accelerates the dissolution process. The same applies to containers based on a rigid composite sheet, which, as already mentioned, may have a corrugated structure in the support layer.

The physical properties and also the chemical properties of the individual layers of the composite sheet can be varied so that for these layers formulations of synthetic materials are used. * *. suitable. The dissolution speed of the individual pockets remains.

• · · ..

determined by the ratio of the acid or base portion in the copolymer or terpolymer to the portion of the nomer or thermonomer, as well as additionally to the tipp and the content of the dissolution inducer in the reflective layer. In addition, the rate of dissolution for the placed sheet can be lowered in such a way that the materials are less soluble or are not soluble enough to be incorporated in the dispersed phase or dissolved form in the mateials of the individual layers. If it is desired, in one and / or in another, of the layers, additives that increase the tackiness can also be incorporated.

According to another embodiment of the invention, the dissolution inductor for the cover layer, itself insoluble in water, can also be incorporated in the reactive layer mediating the use of hollow fibers soluble in water or hollow porous fibers, which .they are loaded, filled or impregnated with the dissolution inducer. This can facilitate the incorporation or fixation of a dissolution inducer, which is not miscible without additional measures with the material of the reactive layer. Tambiér.

llojn nfim. 1 4 possible to foresee the dissolution inductor in encapsulated lining in the reactive layer or in the edge layer for the lining. Thus, the dissolution inducer can advantageously be included in the so-called microcapsules, wherein the envelope or wrapping layer consists of a water-soluble material, which does not melt at the production temperature.

Other features of the invention can be deduced from the following description of preferred embodiments /, in conjunction with the drawings and the claims.

In the drawings:

• Figure 1 shows a cross-section through an embodiment of the invention in the form of a container for dry material;

Figure 2 shows the embodiment shown in figure 1 after emptying and penetration of ./.

• · \ water, in each case in schematic representation;

• · Figure 3 shows a cross-section through another embodiment in the form of a container for material containing water.

In the embodiment of the invention, represented in FIGS. 1 and 2, large wall thicknesses of the individual layers of the container are exaggeratedly represented for the best visibility. The wall 1 of the container has a self-supporting reactive layer 2, which is provided, on its outer side, with a thinner cover layer 3. The proportion of the web thicknesses or thicknesses of the reactive layer to the cover layer is approximately 3%. Both the reactive layer 2 and the cover layer 3 consist of a thermoplastic copolymer having free carboxyl groups or forms them under time no. 1 5 action, of water, which is soluble in a basic medium, but not in acid solutions or in neutral essentials. The reactive layer 2 additionally contains in addition very fine particles 4 of a basic substance, which is incorporated as a dissolution inducer. In such a case the amount of solution inductor 4 is dosed, or is present in sufficient excess, to render both the reactive layer and the cover layer soluble. ·

The container shown in figure 1 has a closed shape in cross section and can be produced, for example, by joint extrusion of both layers directly as a rectangular profile through a suitably structured rectangular nozzle. In this case starting • • *.

of the obtained continuous profile can be cut to size tro, * · · * zos corresponding and suitable, and after the filling and packing can be closed by the ends by welding • • • • • • ra. The package serves for a material that is from chopped to powder form, such as for small items for domestic use, such as needles, screws, etc., but also for cigarettes, food, etc.

By means of the cover layer, resistant to water, the container is made stable against the penetration of water. After the opening and emptying of the container, as shown schematically in FIG. 2, water can penetrate the container and gradually dissolve the reactive layer as a consequence of the dissolution inductor, uniformly distributed therein, the moisture penetrates the container. through the softened reactive layer until it reaches the cover layer, and is able to dissolve it as a consequence

Sheet no. 16 of the dissolved alkaline solution inductor and the high pH value obtained thereby. In this way, the container is totally dissolved, and it can be adjusted, by means of suitable formulation of the layers, the time interval within which the container must be decomposed when water penetrates.

It is also possible to manufacture the container by folding from a sheet or plate and joining the edges together by welding or gluing. If there is enough overlap of the. At the edges, the reactive layer can remain unprotected at the cutting edges without any disadvantage, since in • · ·. .

general · the packaging, before the withdrawal of its contents, •

they do not come into direct contact with water, but only protect their contents against moisture penetration.

• · ·

• ζ

It is also possible to form the sheet in accordance with the invention by means of deep-drawing or drawing or forming a container, which is included in a cardboard, on which the material to be packaged is located, and then cover it with a part of transparent synthetic material, shaped in the form of a cap, based on the sheet according to the invention, which with its edges is firmly joined to the cardboard box and therefore encloses within it the object to be packaged. In this case, the cardboard box can also have the constitution of the sheet or plate according to the invention.

In the embodiment of the invention, shown in FIG. 3, the container has, additionally to the outer cover layer 3, an inner cover layer 5, so that the container can be filled with a liquid also in its inside, without the container being dissolved.

IIoJh no. 1 7

The reactive layer 2 is also structured in a double manner, an outer part 6 of the reactive layer 2 being separated from an inner part 7 by a corrugated structure 8, which serves as a spacer. The two reactive layers can also be arranged side by side only loosely. The corrugated structure 8 serves so that, after tearing open the container, the free penetration of water between £ m- »becomes possible. parts 6 and 7 of the reactive layer 2, in order that the process of dissolution ces ···· '· may take place rapidly because the container has been used. The corrugated structure can be made of a fibrous material, which also decomposes after dissolution of the container or during the latter._and • · ·

It is also possible, from one of such sheets..com • • • • •. · Double sets with cover layers on both sides, .fabr_i • ·.

• · · · car bottles or bottles, for example by means of deep-drawing or blowing procedures.

Example

Below are some examples of the preparation of copolymers and acid terpolymers for the cover layer, these polymers can be used, when mixed with basic substances, also as material for the reactive layer. As the monomer that produces the solubility in bases, maleic anhydride is preferred. Comonomers are preferably used, in the case of copolymers, preferably styrene or methacrylate and, in the case of. terpolymers, additionally ethylvinylethers or methyl acrylate as well as butyl acrylate.

Pojimetry is carried out in the usual way using radical-forming agents, for example peroxide.

I fojn núm 1 8 do3, as catalysts at temperatures between room temperature and 200SC. Suitable polymerization processes include the known polymerization processes including bulk polymerization, with one embodiment being preferred, in an extractor with reaction. Some properties of I03 copolymers and terpolymers thus obtained are shown in the following table. For the formation of the reactive layer the polymers can be mixed with up to 50% by weight of basic substance.

In the table the following abbreviations mean:

• · · · ·

MSA = maleic acid anhydride; WAD = water; PHOS = triamonic phosphate; EVE «Ethylvinyl ether; MAC = methyl acrylate; BAC = n-butyl acrylate; SÜB = substance (exempt.

* · · * Of solvent); ACE = acetone; BEN = benzene; LAP = perpxi • A, ··· 'do of laurolyl; CHC = bis (4-tert.-rbu · · »* · A-tylcyclohexyl peroxydicarbonate) (Perkadox 16).

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<td>and 'κ Ρ-</td><td>- Y tlojn no. twenty</td>

<td>one</td><td>_ Examples of rigid copolymers Copolymerization of vinyl acetate / acid anhydride maleic 13 g (0.5 mole) of vinyl acetate, 49 g (0.5 mole)</td>

<td>κ Y</td><td>of maleic acid anhydride and 0.1 g of peroxide of Lauroyl were dissolved in 400 ml of benzene and heated</td>

<td>•</td><td>to 70^s0 for five hours. From the viscous solution</td>

<td></td><td>the copolymer was precipitated with petroleum ether (80 ftas-r • * ·. · ta 1002C). The copolymer is well soluble in soda lye</td>

<td>10 «</td><td>diluted » * · · · · Copolymerization of styrene / maleic anhydride: · · Aa 52 g (0.5 mol) of styrene and 49 g (0.5 mol) of maleic acid anhydride were heated at 80 ^ 0 during • ' · to six hours with 0.1 ^ of lauroyl peroxide. Μη was obtained • ·</td>

<td>fifteen</td><td>• · * polymer, which dissolved very well in diluted soda lye, • · · • · · · • V • · * · · *</td>

<td>twenty «"</td><td>•</td>

<td>• * 25 to</td><td></td>

<td>30</td><td>•</td>

<td>27072</td><td></td>

<img file="ES284841U_D0001.tif" />

&lt;and_;&gt;.

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