DE3233693A1 - Thermoplastic synthetic resin moulding compositions, and the use thereof for the production of oriented films or composite films - Google Patents

Abstract

Thermoplastic synthetic resin moulding compositions based on mixtures of ethylene-vinyl alcohol copolymers and thermoplastic synthetic resins as a mixture component are used to produce oriented films and packaging materials, for example shrink bags.

Description

Heat shrinkable plastic films are widely used

used for packaging meat and other products.-Either the synthetic resin films are sold to the consumer in the form of shrink bags, which are closed after packing and evacuation, e.g. by heat sealing or by means of a metal clamp. Finally, they are heated, e.g. with hot Water to shrink the film.

Shrink bags have to meet numerous requirements, both be required by the manufacturer as well as the consumer. For the consumer stands in the foreground the suitability of the shrink bag, the filling process, To withstand evacuation, sealing and heat shrinkage. The bag must too be strong enough to survive subsequent handling undamaged. It is also desirable that the bag act as a barrier to the entry of gases works from the environment. Of particular importance is the effect as an oxygen barrier, as oxygen spoils many foods, such as meat. In addition, the Bags be see-through.

For the manufacturer, the focus is on a product that is competitive can be sold and meets the requirements of the consumer. The material from which the bags are manufactured should be easy to extrude and orientate. The process should be suitable for large-scale production. When it comes to orientation the film must be tough enough to withstand stretching without damage. The orientation temperature should not be too high, so that the consumer the Can perform shrinkage in an economical manner.

The known shrink bags are generally made from ethylene-vinyl acetate copolymers manufactured. In some cases the bags contain a layer of a vinyl chloride-vinylidene chloride copolymer, e.g. Saran which serves as an oxygen barrier. Ethylene-vinyl alcohol copolymers (EVOH) have also been proposed as a barrier layer. However, EVOH is sensitive to moisture, it is difficult to process into foils and it is particularly brittle when thin Layer thicknesses.

Despite the advantages is the packaging of meat and other products associated with difficulties by means of shrink bags. This is due to the disadvantages the foils or composite foils currently available for this purpose. In particular when the films are stretched and subsequently shrunk, the films are subjected to heavy loads. The foils are particularly sensitive to the relatively high temperatures, to which they are exposed during orientation and shrinkage.

The foils must fit without warping or separating the layers get oriented. The foils must be adequate at the orientation temperature be strong so that there are no holes, streaks or uneven stretching zones when stretched form. When producing blown film, the film must be the inflated tube wear during the orientation process. After all, you want each of the layers the film will withstand orientation without breaking, separating, or forming holes.

When packaging, the film must respond quickly to heat, the extent However, the shrinkage should not be so severe that the film tears or becomes separate the layers. This is particularly dangerous when packing material with sharp edges.

The known foils with a saran layer have several disadvantages. Saran is brown in color, which is undesirable.

When extruding over longer periods of time, carbon particles are formed in the EX-truder, which later emerge through the nozzle and are enclosed in the film. That's why operation must be interrupted from time to time to clean the nozzle. In the end the energy required to extrude saran is relatively high.

Films with an EVOH layer represent a partial improvement Since EVOH does not deposit carbon particles during processing, it can carry out the extrusion for longer periods of time. The energy consumption when extruding is generally lower. The films obtained can be colorless and clear.

The process of extruding and orienting a film with a However, the EVOH layer is very sensitive to the processing parameters. Furthermore, the barrier properties of the EVOH layer vary considerably in the presence of moisture.

The invention is based on the object, synthetic resin films or

To develop composite films in which the first layer consists of a mixture made of at least 40% of an EVOH copolymer and not more than 60% of a thermoplastic Synthetic resin (mixture component) consists, this mixture in oriented State is compatible with each other. Located on the surface of the first layer a second polymer layer.

In some embodiments, the polymer of the second layer extrude together with the polymer of the first layer. The EVOH copolymer contains preferably about 35% ethylene basic building blocks. The first layer preferably has a thickness of about 5 to 50 gauge.

As thermoplastic synthetic resins (component of the mixture for the EVOH copolymer) come ethylene-ethyl acrylate copolymers, xthylene-acrylic acid copolymers, linear Polyethylene low density poly, linear / ethylene copolymers low density, ionomeric polymers, anhydride-modified polypropylene, anhydride-modified xthylene-vinyl acetate copolymers, Anhydride modified low density polyethylene, anhydride modified polyethylene medium density and anhydride modified high density polyethylene are in question.

The thermoplastic synthetic resin (component of the mixture) for the first layer can be radicals of the general formula as a molecular segment contain. R2 is preferably bonded to the carbon atom via an oxygen bond and R1 can be an aliphatic radical. Many thermoplastic resins which are preferred for the purposes of the invention contain carboxyl groups. The preferred proportion of the carboxyl groups is at least 3% of the thermoplastic synthetic resin. The carboxyl groups can be in more than one form. They are preferably in the form of anhydride groups.

The thermoplastic synthetic resin (compound component) has a melt index, compared to low density polyethylene, of no more than about 10.

The polymer for the second layer is preferably an ethylene polymer or a polymer derived from ethylene. Ethylene-vinyl acetate copolymers are preferred, High density polyethylene, low density polyethylene, ethylene-propylene copolymers, linear low density polyethylene and linear ethylene copolymers lower Density.

In a preferred embodiment, the composite film has a third Layer, which is arranged on the other side of the first layer. All three layers can be extruded together.

The preferred film or composite film has a total thickness of 0.038 up to 0.076 mm. The second layer consists of an ethylene-vinyl acetate copolymer, the third layer made of an ethylene-vinyl acetate copolymer, and the thickness of the third layer is at least 50% of the total thickness.

In a preferred embodiment, the composite film becomes too biaxial oriented shrink bags. The composite film itself is in a Blown film line manufactured.

The invention thus initially relates to a thermoplastic synthetic resin molding compound of at least 40% of an EVOH copolymer and not more than 60% of a thermoplastic Synthetic resin as a component of the mixture and an organic compound, the carbon-oxygen double bonds in the form of carbonyl and carboxyl groups, including acids, anhydrides and esters. The total amount of thermoplastic resin and containing carboxyl groups Mass is at most about 60% of the thermoplastic synthetic resin molding compound.

The quantitative ratio of the thermoplastic synthetic resin to the carboxyl groups containing mass is at least 1: 1.

Preferred thermoplastic synthetic resins are ethylene-ethyl acrylate copolymers, Ethylene-acrylic acid copolymers, linear low density polyethylene, linear Ethylene copolymers of low density, ionomeric polymers, anhydride modified Polypropylene, anhydride-modified ethylene-vinyl acetate copolymers, anhydride-modified Low density polyethylene, anhydride modified medium density polyethylene and anhydride modified high density polyethylene.

Figure 1 shows a preferred embodiment of the invention, a three-layer composite film 100 with the top layer 112, the middle layer 116 and the backing layer 114.

The top layer 112 must be tough enough to protect the underlying Layers as well as to protect the product. In blown film production, like them As described below, the toughness of this layer affects its durability of the inflated film tube.

The carrier layer 114 must be compatible with the product to be packaged be. If the packaging material is to be heat-sealable, the carrier layer is especially important for this purpose. Therefore the polymer for this layer has to be specific to be selected.

The middle layer 116 is attached to the. Carrier layer and - the top layer bound by at least moderate bond strengths. The middle layer serves as a gas barrier, especially as an oxygen barrier.

The films described herein are generally thin and pliable. All of the oriented films in the examples are on the order of thickness from about 0.038 to 0.1 mm (150 to 400 gauge; 100 gauge being 0.038 mm).

Of course, the invention is not restricted to these areas.

The films according to the invention can be oriented by customary methods will. The choice of method depends on the structure of the slides, the nature of their various Components and the intended use. Generally done the extrusion of the film and its orientation according to the so-called double bubble method. With this method, the film is extruded through a ring nozzle to form a tube and fed into a cooling tank filled with water. The hose closes one Band together, which is then heated to its orientation temperature. It will guided in the machine direction between two rows of nip rollers, which with run at different speed of rotation. Between the nip rollers the hose is expanded by means of blown air. Prevent the pinch rollers from pulling away an escape of the blown air. When you inflate the film, it is simultaneously in oriented in the transverse direction. After leaving the peeling nip roller the tube usually to a temperature below the orientation temperature cooled down.

For some uses where there is no need for shrinkage properties arrives, the oriented film can be fixed in the heat.

The favorable properties of the mixture of the EVOH copolymer and the thermoplastic synthetic resin are particularly evident in the production of blown filaments, in which the orientation is carried out according to the double bubble method. Foils with layers of an ethylene-vinyl alcohol copolymer could previously only with greatest difficulties produced and oriented by the blown film process because the EVOH copolymer is very sensitive to the processing conditions reacted. In practice, the instability of the bladder causes a significant one Limitation of the thickness of the films to be produced. On the other hand, the invention allows thermoplastic synthetic resin molding compound a considerable broadening of the parameter ranges, where extrusion and orientation can be performed. This makes it easier the technical production of such films quite considerably, independently whether the film is a single layer or a middle layer made of the ethylene-vinyl alcohol copolymer and the thermoplastic synthetic resin and one or two adjacent layers which normally increase toughness and strength and in this way contribute to the stability of the bladder. EVOH copolymers are inherently brittle. It are the other synthetic resin components of the film that add strength to the bladder. These components preferably include those synthetic resins with which EVOH copolymers are mixed. These synthetic resins are also found in composite films in the layers that do not contain any EVOH copolymer. The incorrect selection of synthetic resins or the setting of incorrect processing conditions in training. and maintaining a stable bladder. It was determined, that it is advisable to heat the film to a temperature of at least 980C, the rigidity or brittleness of the layer containing the EVOH copolymer to a minimum. This improves manufacture and maintenance a stable, flawless bladder. Preferably the film is heated to a temperature heated to at least 1000C in order to soften the EVOH copolymer even more and in this way to limit the brittleness of the film to a minimum.

Since the films of the invention are made from a combination of the most diverse Synthetic resins can be made, it is difficult to control those temperature ranges specify or predict within the an orientation for a particular Foil structure is best achieved. This parameter must therefore usually be used for each film can be determined empirically by a few preliminary tests. Just an example Typical orientation temperatures can be said to be in the range of about 80 up to about 1200C. Also the thickness of the layer containing the EVOH copolymer determines to some extent the optimal orientation temperature. Thicker layers require a higher orientation temperature in order to reduce the brittleness of the EVOH copolymer to diminish.

For some film constructions are even higher temperatures expedient. In view of the fact that the Foil tube must be so soft that he. can be stretched and in view of the well-known brittleness of the EVOH copolymer is the setting of a sufficient heating temperature critical. When this temperature. is too low, takes place in the EVOH copolymer containing layer cracking. If the temperature is too high, soften the dit Side walls of the film, in particular the cover layer and the carrier layer, too thick when stretching, so that the bladder can tear open. The heating temperature must therefore for each slide carefully determined and strictly adhered to in order to make it optimal to be able to process.

Another critical factor affecting the workability of a given Foil structure determines the choice of synthetic resins for each layer. It was found that the thermoplastic synthetic resins in the the EVOH copolymer containing layer and in the outer layer of the film tube preferably should have a low effective melt index. Preferably these have synthetic resins a melt index of at most 10. Synthetic resins (mixture components for the EVOH copolymer) with a melt index of at most 4. The effective Melt index provides a relationship between the energy consumption of an extruder that processes a certain synthetic resin molding compound, compared to the energy consumption of the same extruder when extruding low density polyethylene.

The melt index of low density polyethylene is considered to be identical assumed with the melt flow index as determined according to ASTM test standard D1238 will. In most cases there is a direct relationship between enamel index and the melt flow index of the polymer, measured according to the ASTM test standard mentioned. However, in some cases, e.g. linear low density polyethylene, it differs the melt index is different from the ASTM standard. Therefore the enamel index is through defines the actual rheology in the extruder.

For single-layer films made using less viscous thermoplastic Synthetic resins have been made, the orientation can also be in usual Effect in roll groups for stretching and a tenter frame. One more way is the orientation in one direction by press rolls. The respectively applied As already explained above, the methodology depends on the type and composition the synthetic resin components and the structure of the film to be produced.

The compatibility of the thermoplastic synthetic resins in the synthetic resin molding compounds and in particular the oriented films are determined first according to the degree of haze judged in the slide. Significant cloudiness is a sign of intolerance. Another sign of intolerance is shown by banding or other irregularities in the bladder. Usually those are slides that show good clarity and uniformity, made from compatible synthetic resins built up. They are used as barriers against oxygen under the conditions of use viewed. On the other hand, a slide can look as if they are made up of one another Compatible synthetic resin mixture exists. However, it actually contains individual particles in the barrier layer, which can only be seen with a light microscope. This layer therefore allows oxygen to pass through easily. The compatibility is therefore defined by the degree of oxygen tightness. Usually it also shows itself through good Appearance of the slide.

The effective melt index or melt index is important for processability. The compatibility is determined by the presence of molecular segments or basic building blocks with the grouping in the layer containing the EVOH copolymer. Numerous thermoplastic synthetic resin molding compositions of the invention contain carboxylic acid, ester and anhydride groups in the component of the mixture for the EVOH copolymer.

According to the invention, ethylene-vinyl alcohol copolymers are used, which are practically completely hydrolyzed and can be extruded. It can partially saponified EVOH copolymers can also be used. but have this Synthetic resins do not have the required barrier effect against gases. You are therefore less preferred. Preferred EVOH copolymers contain at least about 40 mol percent Ethylene units. Preferred EVOH copolymers come under the trade name EP-E from Kuraray with 45% ethylene units and GL-E from Nippon Gohsei with 40% ethylene units on the market. Are acceptable for some uses also EVOH copolymers with a lower ethylene content, such as GL-D from Nippon Gohsei with 29% ethylene units and EP-F from Kuraray with 35% ethylene units.

The melt flow index of the EVOH copolymers is determined according to the ASTM test standard D-1238 determined at a load of 2160 g.

The copolymers EP-E and EP-F have a value of 5.8 at 1900C or 1.5. The copolymers GL-E and GL-D have a value of 8.0 and 2100C, respectively 7.4.

The thermoplastic synthetic resin, i.e. the mixture component for the EVOH copolymer, as a rule, has certain general properties. Normally it is made up of olefinic basic building blocks or chain segments, such as ethylene or propylene units. It has a low effective melt index of preferably below 4, and it contains functional groups with a carbon-oxygen double bond. This grouping is also known as the carboxyl mass. It should be pointed out that compatible blends of linear low density polyethylene successful can also be processed in the absence of groups with a carbon-oxygen bond, such as carbonyl, anhydride, carboxylic acid and ester groups.

Specific examples of thermoplastic resins made with the EVOH copolymer can be mixed are ethylene-ethyl acrylate copolymers, ethylene-acrylic acid copolymers, linear low density polyethylene, linear ethylene copolymers lower Dense, ionomeric polymers, anhydride-modified polypropylene, anhydride-modified Xthylene-vinyl acetate copolymers, anhydride-modified polyethylene lower Density. Anhydride modified medium density polyethylene and anhydride modified High density polyethylene. Combinations of these synthetic resins and other synthetic resins are also suitable as a mixture component, including partially saponified Ethylene-vinyl acetate copolymer The thermoplastic synthetic resin probably has various interdependent effects. It serves as a dispersant for Dispersing the EVOH copolymer and protecting the moisture-sensitive EVOH copolymer against water.

Thermoplastic synthetic resin mixture components with functional Groups that react chemically with the hydroxyl groups of the EVOH copolymer can also reduce the water sensitivity of the EVOH copolymer.

Finally, the thermoplastic resin also serves as a diluent for the EVOH copolymer and thus improves the oxygen tightness of the film.

The interaction of these properties can be determined in experiments, carried out in the presence of high humidity. An EVOH copolymer, like GL-D, which is high in vinyl alcohol units, should normally have excellent oxygen tightness.

This is also the case in a dry atmosphere. To surprise- the wise however, the experimental results show that it is very difficult to obtain an acceptable one Oxygen tightness e.g.

to be obtained from packaging material in which meat is packed, because the EVOH copolymer is very sensitive to moisture. On the other hand, lets the EVOH copolymer EP-E, which has a low vinyl alcohol content ten has been successful with a wide variety of thermoplastic synthetic resins mix as a component in a wide range of mixing ratios, and it shows excellent oxygen tightness. Thus is the interaction all variables, including the environment, with several of these variables act independently of each other, the cause of whether a certain film structure can be produced and whether this film is a sufficient gas barrier for the packaged Product represents.

The layer 116 with the EVOH copolymer contains about 40 to about 90 mole percent EVOH copolymer and accordingly 10 to 60% thermoplastic Synthetic resin as a component of the mixture. A minimum of 40% EVOH copolymer is required to achieve the required oxygen tightness. 10% of the thermoplastic Resin are at least required to make the thermoplastic resin molding compound to impart the properties necessary for extruding and orienting the film and for which other favorable properties are required.

The synthetic resin molding compound has several effects. Generally has the EVOH copolymer is considerably higher for numerous purposes Oxygen tightness as required for the packaged product. Consequently the cheaper resin blend component contributes to economy. on in this way, part of the EVOH copolymer can be saved.

The resin blend ingredient also appears to decrease those Moisture sensitivity of the EVOH copolymer. Packaging material for meat typically exposed to 92 to 99% relative humidity.

By reducing the EVOH copolymer's sensitivity to moisture the oxygen tightness can be compared to that of 100% EVOH copolymer often improve the existing layer. It is understandable that a 100% EVOH copolymer existing layer does not have a functionally acceptable oxygen barrier in contact with meat because this copolymer is sensitive to moisture. Of the Synthetic resin mixture constituent sets the concentration of the EVOH copolymer down, but increases the effect of the EVOH copolymer in a humid environment, since he shields the EVOH copolymer from this damp environment.

The synthetic resin blend component also allows greater flexibility with regard to the amount of EVOH copolymer used and with regard to the thickness the middle layer in the blown film process. It was found that the thickness a layer consisting of 100% EVOH copolymer in the blown film process is limited to a maximum thickness. For synthetic resin mixtures with considerable quantities of thermoplastic synthetic resin as a component of the mixture, there will be no such Restrictions observed.

In addition to a minimum thickness for the production of the layer, the EVOH copolymer is containing layer is generally not limited in terms of its thickness. the Thickness depends solely on economic factors and on the characteristics of the desired product.

For applications where high humidity does not occur, the second advantage described above does not have to be taken into account. the however, other advantages apply. In this rall, however, you have greater flexibility activity with regard to the type of EVOH copolymer used, since in this case the different moisture sensitivity of the different EVOH copolymers doesn't matter. The carrier layer 114 is the layer that is the inner Represents the surface of the extruded tube in the Dopo pelblasenverfahren. Provided the film can be used as a shrink film for the production of shrink bags is intended, the carrier layer 114 serves as an adhesive layer.

The gluing can be done either by applying heat during shrinking the film or by the direct application of heat during heat sealing. A typical method of self-sealing a packaged product is in U.S. Reissue PS 30,098. It can be seen that this procedure is only the effect of the carrier layer 114 is explained by way of example.

Another favorable property of the carrier layer 114 is directly related along with their arrangement between the moist packaging product and the moisture-sensitive middle layer 116. To the extent that the backing layer 114 acts as a moisture barrier acts, it also reduces the water concentration in the middle layer 116.

As a result of the low water concentration in this layer, the The oxygen tightness of the middle layer 116 is improved over a layer 116, which is connected to a layer 114, which has a lower moisture-tightness having.

The carrier layer 114 was admittedly in connection with its heat sealability described, but it can vary considerably in its composition, depending on the intended use of the film.

For producing a film for a heat-sealable shrink film it is desirable that the thickness of the support layer 114 be a significant percentage the total thickness of the composite film. In preferred carrier layers the thickness is at least 50% of the total thickness. There are the most varied of them Heat-sealable resins are acceptable, but synthetic resins are made from an ethylene-vinyl acetate copolymer preferred, which contains about 8% vinyl acetate units.

The cover layer 112 is the layer that forms the outer surface of the tube in the double-bubble process. During the production of the foil and especially when stretching the film in the form of a bubble, the top layer imparts 112 the bladder has sufficient tear strength.

It has been found experimentally that it does the double bubble process very difficult to maintain a stable bladder when combined with the Layers 112 and 116 the synthetic resin of layer 112 significant amounts of EVOH copolymer and the synthetic resin of layer 116 contains, for example, an ethylene vinyl acetate copolymer with 8% vinyl acetate units.

If the composition of the layers is reversed, i.e. the top layer 112 no significant amounts of EVOH copolymer and the carrier layer 116 EVOH copolymer contains, however, a stable bladder can be easily produced.

The thickness of the cover layer 112 is not critical. The below Experimental results reported show successful operation at one thickness from only 40 gauge and up to 120 gauge.

It has been found experimentally that when using synthetic resins for the layers 112 and 114, which are suitable for shrink films, the layers 112 and 114 control the ability of the film to act as a shrink film. The kind the thermoplastic resins for the middle layer 116 is generally not critical for the shrink function.

A conventional blown film line for the double-bubble process is used in the examples used. The obtained film is biaxially oriented at a stretching ratio ton about 3: 1 each in the machine direction and the cross direction. The workability becomes subjective due to the observed difficulties in making one sta bilen bubble rated. The resulting films are subjective for clarity and Rated uniformity. Finally, the foils are checked for oxygen permeability examined at 230C and 100% relative humidity. Usually these will Attempts carried out only once. The results of several tests are separate specified.

Embodiments of three-layer film tubes are according to the processes described above. Example 1.154 serves as an illustration. An ethylene-vinyl acetate copolymer is used for the carrier layer and the top layer used with 8% vinyl acetate basic building blocks. The middle shift will be 80 Parts by weight of the EVOH copolymer EP-E as granules, dry mixed with 20 Parts by weight of ethylene-acrylic acid copolymer XDR-4E as granules. The synthetic resins are extruded through three extruders and in an annular nozzle to form a three-layer Hose united. The hose is cooled on the outside, laid flat and then put back on 10,000 heated. The heated, flattened tube is then passed through a pair of squeeze rollers led and inflated into a bubble that is both in the machine direction and oriented biaxially in the transverse direction at a draw ratio of about 3: 1 will. The bladder is then cooled from the outside by means of cooling air. Then will the bladder laid flat, cut open and wound up.

The composite film obtained is based on layer structure and oxygen permeability examined. The results are summarized in Table I. the end It can be seen from Table I that the backing layer is 222 gauge. the middle layer has a thickness of 29 gauge while the top layer has a thickness of 92 gauge. The oxygen permeability is 194 cm3 / m2 / 24 h at 230C and 100% relative humidity.

All the films given in the examples are similar Way using the same synthetic resins for the top layer and the backing layer manufactured. Only the composition of the middle layer is given in the table.

From Table II the chemical composition is that in the examples polymers used.

Table I Thermoplastic Molding Compound O2 Permeability Layer Example EVOH-Co- Mixture- Mixture per 0.0254 mm profile No. polymeri stock- Abso- EVOH copolybate part nis,% 1> 'lut2) merisate 1,154 EP-E XDR-4E 80/20 222/29/92 194 45 2,148 EP-E XDR-4E 60/40 169/40/83 329 79 3,155 EP-E XDR-4F 80/20 126/17/77 163 22 4.149 EPE XDR-4F 60/40 117/32/92 479 92 5.131 EP-E 452 90/10 172/16/70 129 19 6,109 EP-E 452 80/20 130/15/59 214 26 7,108 EP-E 452 70/30 121/17/49 189 22 8,107 EP-E 452 60/40 147/30/70 211 38 9,129 EP-E 2045 90/10 130/14/49 267. 34 10,103 EP-E 2045 80/20 139/22/76 149 26 11.102 EP-E 2045 70/30 139/32/63. 199 45.

12,101 EP-E 2045 60/40 169/41/120 169 42 13,089 EP-E 2045 50/50 109/21/45. 259 27 14,089 EP-E 2045 50/50 174/34/64 209 36 15,088 EP-E Sclair 11P 50/50 161/33/49 264 44 16,132 EP-E PL-1 90/10 126/10/40 217 20 17,095 EP-E PL-l 67/33 144/25/52 169 28 18.094 EP-E PL-l 50/50 122/30/62 284 43 19.133 EP-E PL-2197 90/10 223/18/101 109 18 20,133 EP-E PL-2197 90/10 184/23/75 125 26 21,155 EP-E PL-2197 85/15 140/21/78 276 49 22,166 EP-E PL-2197 80/20 129/16/64 209- 27 23,167 EP-E PL-2197 75/25 126/17/77 219 28 24,168 EP-E PL-2l97 70/30 114/25/60 182 32 25,093 EP-E PL-2197 50/50 133/23/64 309 35 26,000 EP-E PL-2109 90/10 175/16/59 184 26 Table I - continued 27,000 EP-E PL-2109 80/20 164/16/71 234 30 28,000 EP-E PL-2109 70/30 1 »1/10/68 519 36 29,130 EP-E QF-500 90/10 164/20/55 169 30 30,106 EP-E QF-500 80/20 133/24/60 153 29 31,105 EP-E QF-500 70/30 126/21/62 154 23 32,104 EP-E QF-500 o0 / 40 146/14/61 254 22 33.092 EP-E QF-500 50 / 50- 133/14/62 538 38 34.090 EP-E LF-500 50/50 175/28/71 243 34 35.091 EP-E NF-500 50/50 1n1 / 22/51 558 61 36.152 GL-E XDR-4E 80/20 117/20/87 314 50 37.146 GL-E XDR-4E 60/40 167/38/124 319 73 38.153 GL-E XDR-4F 80/20 126/18/84 334 48 39.147 GL-E XDR-4F 60/40 136/34/76 299 61 40.128 GL-E 452 90/10 152/12/76 219 24 41.124 GL-E 452 80/20 133/16/61 339 43 42.012 GL-E »52 75/25 116/06/53 579 26 43.012 GL-E -452 75/25 99/07/48 599 31 44.012 GL-E 452 75/25 115/06/67 599 27 45.012 GL-E -452 75/25 110/06/59 608 27 46.012 GL-E -4o2 75/25 129/20/58 254 38 47.120 GL-E 452 70/30 117/21/69 559 82 48.116 GL-E 452 60/40 138/30/76 499 90 49.027 GL-E 452 50/50 162/40/71 279 56 50.126 GL-E 2045 90/10 186/17/11 204 31 51.122 GL-E 2045 80/20 166/30/116 324 78 52.118 GL-E 2045 70/30 237/32/158 418 94 53.Q86 GL-E 2045 50/50 84/15/51 1500+ 120t 54,000 GL-E 8231 50/50 108/54/62 519 140 55,000 GL-E 8231 50/50 151/90/92 327 147 Table I - continued 56,000 GL-E 657 75/25 156/42/84 216 68 57,000 GL-E 657 75/25 102/30/54 309 70 58,125 GL-E PL-1 90/10 190/23/118 194 40 59.121 GL-E PL-1 80/20 136/17/80 254 35 60.117 GL-E PL-1 70/30 143/28/55 339 66 61.113 GL-E PL-1 60/40 158/29/72 269 47 62.081 GL-E PL-1 50/50 182/10/92 609 30 63.127 GL-E PL-2197 90/10 201/22/102 209 41 64.123 GL-E PL-2197 80/20 182/20/90 232 37 65.119 GL-E PL-2197 70/30 189/29/102 229 46 66.115 GL-E PL-2197 60/40 175/23/95 389 54 67,000 GL-E PL-2109 90/10 178/9/56 339 27 68,085 GL-E QF-500 50/50 147/25/21 538 67 69.083 GL-E LF-500 50/50 117/22/68 879 97 70.084 GL-E NF-500 50/50 126/23/70 619 71 71.161 GL-ET XDR-4E 80/20 124/16/63 294 38 72.160 GL-ET 2045 80/20 167/18/97 229 33 73,159 GL-ET PL-2197 80/20 125/14/88 254 28 74,156 EP-F. XDR-4E 80/20 144/22/71 459 81 75,150 EP-F XDR-4E 60/40 136/20/85 538 77 76,157 EP-F XDR-4F 80/20 152/26/101 388 81 77.151 EP-F XDR-4F 60/40 143/18/60 999 108 78.052 EP-F 2045 50/50 137/30/71 329 49 79.056 EP-F QF-500 50/50 134/09/62 279 13 80.056 EP-F QF-500 50/50 150/13/67 272 18 81,057 EP-F NF-500 50/50 102/20/60 353 35 82,054 EP-F PL-2 50/50 116/18/64 334 30 1) Thickness (gauge) of the carrier layer / middle layer / top layer 2) cm3 / m2 / 24 h at 230C and 100% relative humidity Tabel II Synthetic resin mixture component in the middle containing EVOH copolymer Layer Mixture Chemical Composition Melt Index Component ASTM-D1238 XDR-4E EAA, 5.1% AA 0.5 XDR-4F EAA, 8.2% AA 1.1 452 EAA, 6.5% AA 2.0 2045 LLDPE 1.0 Sclair 11P LLDPE copolymer 0.7 8231 Monomer es Polymer 5.0 657 EVA 0.5 PL-1 Anhydride modified EVA 1.0.

PL-2197 anhydride modified PP 2.0 PL-2109 anhydride modified PP 1.2 QF-500 anhydride-modified PP 4.7 LF-500 anhydride-modified LDPE 1.2 NF-500 anhydride-modified MDPE 2.0 PL-2 anhydride-modified HDPE 0.9 EP-E .EVOH - 45% ethylene building blocks 5.8 at 1900c GL-E EVOH - 40% ethylene building blocks 8.0 at 2100C GL-ET EVOH - 40% * - Ethylene basic components 3.5 at 2100C EP-F EVOH - 35% ethylene building blocks 1.5 for i900C GL-D EVOH - 29% ethylene building blocks 7.4 at 210 ° C EAA = ethylene-acrylic acid copolymer LLDPE = linear polyethylene low density EVA = ethylene-vinyl acetate copolymer PP = polypropylene LDPE = Low density polyethylene MDPE = medium density polyethylene HDPE = polyethylene high @icht The effect of the EVOH copolymer as an oxygen barrier in a film with a MoCon oxygen analyzer at 230C and 0% relative Humidity determined. The examination of packaged products has shown that that this test does not necessarily determine the ability of a film to inhibit oxygen transmission reproduces under conditions that occur when packaging moist food, such as Meat, predominate. Typical conditions here are generally 3.30C and 99 % relative humidity on the inside of the package and 92% relative humidity on the outside of the packaging. The EVOH copolymer is under these conditions generally very sensitive to high relative humidity. The extent of the Sensitivity cannot be predicted by testing at low humidity.

In tests on packaged meat it was found that the oxygen barrier function the film can be predicted with some accuracy by determining the oxygen permeability with a MoCon oxygen analyzer at 230C and 100% relative humidity. A value of 100% relative humidity is obtained by clicking on the Slide a damp cloth during the experiment. It was found that the foil can adequately protect meat against oxygen diffusion if the absolute oxygen permeability under these conditions equal to or less than 350 cm3 / m2 / 24 h. The majority of the test results were among these Conditions received. Some foils with oxygen permeabilities from above 350 under these conditions also provide sufficient protection. Additional However, research is needed to confirm this statement for each slide. The experiments can be carried out according to the information described above.

Several of the examples listed do not satisfy the 350 cm3 parameter, however, because of their structure, they show that minor structural changes are likely will give the desired value. Examples 42.012 are typical for this up to 45.012, where the foils have a very thin middle layer. That Example 46.012 shows a similar structure of the film with a thicker middle one Layer and a fully adequate barrier function.

So the examples themselves show modifications, the desired foils for certain packaging conditions.

A single reading under the meat packaging conditions is given in Example 83 in Table III.

This measured value was when the films were again examined Examples 19.133 and 20.133 were obtained. The measured values for example 9.t33 are in Table III for. Comparison given. Thus, Table III shows the relationship between the oxygen permeability at 230C and 100% relative humidity and oxygen permeability in the presence of meat. The moisture on both sides of the film are measured separately, as shown in Table III. From Table III and Example 83 it can be seen that the film with the EVOH copolymer containing middle layer much less sensitive to changes in the relative humidity is at high values than a film with a medium Layer that consists only of EVOH copolymer.

Table III Oxygen permeability in the presence of meat test conditions middle layer temperature- relative humidity control ex. 83 temperature, top-carrier-OC layer layer 100% EP-E 100% GL-E 90% EP-E, 108 2197 23 100 100 - - 109 3.3 92 99 20 11 10 3.3 100 100 38 73 13 The 350 cm3 parameters are important. Films with significantly higher oxygen permeability 100% relative humidity may however be used for other products suitable.

These films rely on their low oxygen permeability investigate relative humidity.

The films according to the invention are therefore not set to a value of 350 cm3 oxygen permeability restricted.

What is more important is the processability of the films and their compatibility the thermoplastic synthetic resin molding compound containing EVOH copolymer in combination with acceptable oxygen tightness in applications as they normally would occur in practice. For example, the thermoplastic according to the invention Synthetic resin molding compounds based on EVOH copolymers are used in dry environment, e.g. for packaging dry food such as baked goods. In this case, moisture sensitivity does not matter. Thermoplastic Synthetic resin molding compounds and films produced from these molding compounds, which are not acceptable Oxygen permeability at relatively high humidity can be among these Conditions are excellent. For example, film structures are where Mixtures with the EVOH copolymer GL-D are used, generally too sensitive to moisture at Use in a high humidity atmosphere. they are however, excellently suited due to their high content of vinyl alcohol units as packaging material for dry products.

The invention has been explained above on the basis of three-layer films . However, it is obvious that the invention also films with more or less Shifts concerns.

L e r s e i t e

Claims (76)

Thermoplastic synthetic resin molding compounds and their use for the production of oriented foils or composite foils P a t e n t a n s p r ü c h e 1. Oriented Synthetic resin film, which is a mixture of at least 40% of an ethylene-vinyl alcohol copolymer and at most 60% of a thermoplastic synthetic resin as a blend component contains, wherein the film contains a compatible mixture in the oriented state. 2. Oriented synthetic resin film according to claim 1, which has a second polymer Contains layer in contact with the first layer, the first layer comprising the synthetic resin mixture is. 3. Oriented synthetic resin film according to claim 2, characterized in that that the polymer for the second layer can be coextruded with the first Layer. 4. Oriented synthetic resin film according to claim 2, characterized in that that the ethylene-vinyl alcohol copolymer at least about 3 '% ethylene building blocks contains. 5. Oriented film according to claim 1 or 2, characterized in that that the thermoplastic synthetic resin (component of the mixture) is an ethylene-ethyl acrylate copolymer, an ethylene-acrylic acid copolymer, linear low density polyethylene linear ethylene copolymer of low density, an ionomeric polymer, an anhydride-modified one Polypropylene, an anhydride-modified ethylene-vinyl acetate copolymer Anhydride modified low density polyethylene, an anhydride modified polyethylene medium density, an anhydride modified high density polyethylene, or a partial is saponified ethylene-vinyl acetate copolymer. 6. Oriented synthetic resin film according to claim 2, characterized in that that the first layer has a thickness of about 5 to about 50 Gauge. 7. Oriented synthetic resin film according to claim 1, 2, 3, 4 or 6, characterized. characterized in that the thermoplastic synthetic resin (mixture component) has carboxyl groups contains. 8. Oriented synthetic resin film according to claim 7, characterized in that that the carboxyl group content of the thermoplastic synthetic resin is at least 0.5% amounts to. 9. Oriented synthetic resin film according to claim 1, 2, 3, 4 or 6, characterized characterized in that the thermoplastic resin has a melt index in comparison to low density polyethylene of no more than about 10. 10. Oriented synthetic resin film according to claim 7, characterized in that that the thermoplastic resin has a melt index, compared to polyethylene low density, of no more than about 10. 11. Oriented synthetic resin film according to claim 2, 3, 4 or 6, characterized characterized in that the polymer for the second layer is an ethylene-vinyl acetate copolymer, High density polyethylene, low density polyethylene, an ethylene-propylene copolymer, a linear low density polyethylene or a linear ethylene copolymer low density is. 12. Oriented synthetic resin film according to claim 2, 3, 4 or 6, characterized characterized in that the thermoplastic synthetic resin (mixture component) has carboxyl groups and the polymer for the second layer contains an ethylene-vinyl acetate copolymer, Polypropylene, high-density polyethylene, low-density polyethylene, an ethylene-propylene copolymer, a linear low density polyethylene or a linear ethylene copolymer low density is. 13. Oriented synthetic resin film according to claim 2, 3, 4 or 6, characterized characterized in that the thermoplastic synthetic resin (mixture component) is a Melt index, compared to low density polyethylene, of no more than about 4 and the polymer for the second layer is an ethylene-vinyl acetate copolymer, Polypropylene, high density polyethylene, low density polyethylene, an ethylene-propylene copolymer, linear low density polyethylene or a linear ethylene copolymer lower Density is. 14. Oriented synthetic resin film according to claim 2, 3, 4 or 6, characterized characterized in that the thermoplastic synthetic resin (mixture component) has a melt index, as compared to low density polyethylene, of no more than about 4 and the polymer for the second layer is an ethylene-vinyl acetate copolymer, polypropylene, High density polyethylene low density polyethylene, linear Low density polyethylene or a linear low density ethylene copolymer is. 15. Oriented synthetic resin film according to claim 2, 3, 4 or 6, characterized characterized in that the thermoplastic synthetic resin (mixture component) has carboxyl groups and has a melt index, compared to low density polyethylene, of no more than about 4, and the polymer for the second layer is an ethylene-vinyl acetate copolymer is. 16. Oriented synthetic resin film according to claim 1, 2, 3, 4 or 6, characterized characterized in that the thermoplastic synthetic resin (mixture component) is an organic one Contains anhydride. 17. Oriented synthetic resin film according to claim 10, characterized in that that the carboxyl groups are in the form of an anhydride. 18. Oriented, multi-layer synthetic resin film, consisting of (a) a first layer composed of a mixture of at least 40% and less than 100% of an ethylene-vinyl alcohol copolymer and more than 0% and less than 60% of a therim oriented compatible therewith State of thermoplastic resin and (b) a second and third polymer layer on the two surfaces of the first layer. 19. The composite film according to claim 18, characterized in that the Polymer masses for the second and third layers together with the polymer mixture co-extrude for the first layer. 20. The composite film according to claim 18, characterized in that the Ethylene vinyl alcohol copolymer sat at least about 35% ethylene building blocks contains. 21. The composite film according to claim 18, characterized in that the thermoplastic synthetic resin (component of the mixture) an ethylene-ethyl acrylate copolymer, an ethylene-acrylic acid copolymer, linear low density polyethylene linear ethylene copolymer of low density, an ionomeric polymer, an anhydride-modified one Polypropylene, an anhydride-modified ethylene-vinyl acetate copolymer Anhydride modified low density polyethylene, an anhydride modified Medium density polyethylene, anhydride modified high density polyethylene or partially saponified ethylene vinyl acetate copolymer. 22. The composite film according to claim 18, characterized in that the first layer is about 5 to 50 gauge thick. 23. Composite film according to one of claims 18 to 22, characterized in that that the thermoplastic synthetic resin (mixture component) contains carboxyl groups. 24. The composite film according to claim 23, characterized in that the The proportion of carboxyl groups is at least 0.5% of the thermoplastic synthetic resin. 25. Composite film according to one of claims 18 to 22, characterized in that that the thermoplastic synthetic resin (mixture component) has an effective melt index of at most about 10. 26. The composite film according to claim 23, characterized in that the thermoplastic synthetic resin (compound component) has an effective melt index of not more than about 10. 27. Composite film according to one of claims 18 to 22, characterized in that that-the polymer for the second layer is an ethylene-vinyl acetate copolymer, polyethylene high density, low density polyethylene, an ethylene-propylene copolymer, linear low density polyethylene or a linear ethylene copolymer lower Density is. 28. The composite film according to claim 23, characterized in that the Polymer for the second layer is an ethylene-vinyl acetate copolymer, polyethylene high density, low density polyethylene, an ethylene-propylene copolymer, linear low density polyethylene or a linear ethylene copolymer lower Density is. 29. The composite film according to claim 25, characterized in that the Polymer for the second layer is an ethylene-vinyl acetate copolymer, polyethylene high density, low density polyethylene, an ethylene-propylene copolymer, a linear low density polyethylene or a linear ethylene copolymer low density is. 30. Composite film according to claim 26, characterized in that the Polymer for the second layer is an ethylene-vinyl acetate copolymer, polyethylene high density, low density polyethylene, an ethylene-propylene copolymer, a linear low density polyethylene or a linear ethylene copolymer low density is. 31. The composite film according to claim 26, characterized in that it has a total thickness of 0.038-0.076 mm and the polymer for the third layer is an ethylene-vinyl acetate copolymer, and wherein the thickness of the third layer is at least 50% of the thickness of the composite film. 32. Composite film according to claim 27, characterized in that it has a thickness of 0.038 to 0.076 mm and the polymer for the third layer Lthylene-vinyl acetate copolymer, and wherein the thickness of the third layer is at least 50% of the thickness of the composite film. 33. Composite film according to claim 31, characterized in that the The polymer for the second layer is an ethylene-vinyl acetate copolymer. 34. Composite film according to one of claims 18 to 21, characterized in that that it is 0.038-0.076 mm thick, the polymer for the third layer consists of an ethylene-vinyl acetate copolymer and the thickness of the third layer at least 50% of the thickness of the composite film BetFågt. 35. Composite film according to one of claims 18 to 22, characterized in that that the third layer acts as a moisture barrier to the moisture content the first layer to a value that is lower than the moisture concentration on the surface of the composite film, the surface being the third layer. 36. Composite film according to claim 34, characterized in that the The polymer for the second layer is an ethylene-vinyl acetate copolymer. 37. Composite film according to one of claims 18 to 22, characterized in that that the thermoplastic synthetic resin (component of the mixture) is an organic anhydride contains. 38. The composite film according to claim 26, characterized in that the Carboxyl groups are in the form of anhydride groups. 39.Biaxially oriented shrink bag made from a multi-layer, film extruded and oriented in tubular form, consisting of an inner layer, a heat-sealable layer, a second synthetic resin layer based on a ethylene-vinyl alcohol copolymer on one of the surfaces of the first layer and a third layer of one thermoplastic polymer on the other surface of the second layer, wherein the second layer is a mixture of 40 to 90% of an Ethylene-Vinvlalkohol-Coolvmerisats and 10 to 60% of an oriented / compatible thermoplastic Is polymer, and the polymer for the third layer is shared with the second Can extrude layer. 40. Shrink bag according to claim 39, characterized in that the Ethylene-vinyl alcohol copolymer at least about 35% ethylene basic building blocks contains. 41. Shrink bag according to claim 39, characterized in that the second layer is about 5 to 50 gauge thick. 42. Shrink bag according to claim 39, characterized in that the thermoplastic synthetic resin (component of the mixture) an xthylene-xthylacrylate copolymer, an ethylene acrylic acid copolymer, linear low density polyethylene linear ethylene copolymer of low density, an ionomeric polymer, an anhydride-modified one Polypropylene, an anhydride-modified ethylene-vinyl acetate copolymer Anhydride modified low density polyethylene, an anhydride modified Medium density polyethylene, an anhydride modified high density polyethylene or a partially saponified ethylene-vinyl acetate copolymer. 43. Shrink bag according to one of claims 39 to 42, characterized in that that the thermoplastic synthetic resin (mixture component) contains carboxyl groups. 44. Shrink bag according to claim 43, characterized in that the Proportion of carboxyl groups in the thermoplastic synthetic resin (component of the mixture) is at least 0.5% 45. Shrink bag according to one of claims 39 to 42, characterized in that the thermoplastic synthetic resin (component of the mixture) a melt index, compared to low density polyethylene, of no more than has about 4. 46. Shrink bag according to claim 43, characterized in that the thermoplastic. Synthetic resin (compound component) a melt index, in comparison to low density polyethylene, of no more than about 4. 47. Shrink bag according to one of claims 39 to 42, characterized in that that the polymer for the third layer is an ethylene-vinyl acetate copolymer, polyethylene high density, low density polyethylene, an ethylene-propylene copolymer, linear low density polyethylene or a linear ethylene copolymer lower Density is. 48. Shrink bag according to claim 43, characterized in that the Polymer for the third layer is an ethylene-vinyl acetate copolymer, polyethylene high density, low density polyethylene, an ethylene-propylene copolymer, linear low density polyethylene or a linear ethylene copolymer lower Density is. 49. Shrink bag according to claim 45, characterized in that the Polymer for the third layer is an ethylene-vinyl acetate copolymer, polyethylene high density, poly low density ethylene, - an ethylene-propylene copolymer, linear low density polyethylene or a linear ethylene copolymer lower Density is 50. Shrink bag according to claim 46, characterized in that the Polymer for the third layer an ethylene-vinyl acetate copolymer, polyethylene high density, low density polyethylene, an ethylene-propylene copolymer, linear low density polyethylene or a linear ethylene copolymer lower Density is. 51. Shrink bag according to claim 46, characterized in that the Composite film has a thickness of 0.038 to 0.076 mm, the polymer for the third layer an ethylene-vinyl acetate copolymer and the thickness of the first layer is at least 50% of the thickness of the composite film. 52. Shrink bag according to claim 51, characterized in that the The polymer for the first layer is an ethylene-vinyl acetate copolymer. 53. Shrink bag according to claim 39, 40 or 42, characterized in that that the thickness of the composite sheet is 0.038-0.076 mm, the polymer for the first Layer is an xthylene-vinyl acetate copolymer and the thickness of the first layer is at least 50% of the thickness of the composite film. 54. Shrink bag according to claim 53, characterized in that the The polymer for the third layer is an ethylene-vinyl acetate copolymer. 55. Process for the manufacture of biaxially oriented, multilayer Shrink films in tubular form, where the shrink film has a first layer, which is a mixture of 40 to 90% of an ethylene-vinyl alcohol copolymer and , 10 up to 60% of a thermoplastic polymer, and the first layer in oriented State a -. 'Compatible mixture, the shrink film a second and has a third layer on the opposite surfaces of the first layer, and the composition of the second and third layers is such that they with the first layer can be coextruded, characterized in that the first, second and third layer through a ring nozzle to form a continuous hose extruded, the hose cools, then heated to at least 980C and the hose lets collapse the collapsed tube through a first nip at a first speed, guides the hose through a second nip leads, which is arranged at a distance from the first nip, in a second Speed higher than the first speed., Inflating the hose and forms an air bubble between the first and second nips, the inflated one Hose cools down and collapses and in this way the hose between the first and second gap biaxially oriented. 56. The method according to claim 55, characterized in that the cooled, non-oriented hose is heated to at least 10,000. Thermoplastic synthetic resin molding compound, consisting of (a) an ethylene-vinyl alcohol copolymer in an amount of at least 40% of the total mass, (b) a thermoplastic Synthetic resin (component of the mixture) and (c) a mass containing carboxyl groups, being the sum of the thermoplastic synthetic resin and the carboxyl group-containing Mass does not exceed 60 g of the total mass and the quantitative ratio of thermoplastic Synthetic resin to mass containing carboxyl groups is at least 1: 1. 58. Molding composition according to claim 57, characterized in that the thermoplastic Synthetic resin an ethylene-ethyl acrylate copolymer, an ethylene-acrylic acid copolymer ' linear low density polyethylene, a linear ethylene copolymer lower Density, an ionomeric polymer, an anhydride-modified polypropylene, an anhydride modified ethylene-vinyl acetate copolymer 'an anhydride-modified polyethylene low density, an anhydride modified medium density polyethylene, an anhydride modified high-density polyethylene or a partially saponified ethylene-vinyl acetate copolymer is. 59. Molding composition according to claim 57 or 58, characterized in that it is in the form of a film. 60. Molding compound according to claim 59, characterized. That the film is oriented. 61. Film according to claim 1, 2, 3, 4, 18, 19, 21 or 22, characterized in that the thermoplastic synthetic resin (component of the mixture) is a radical of the formula as a molecular segment contains. 62. Film according to claim 61, characterized in that R2 to the Carbon atom is bound via an oxygen bond. 63. Film according to claim 62, characterized in that an aliphatic Rest is. 64. Synthetic resin molding compound, consisting of (a) an ethylene-vinyl alcohol copolymer in an amount of at least 40% and (b) a thermoplastic synthetic resin (mixture component) with a larger proportion of a polymer from the group of an ethylene-ethyl acrylate copolymer, an ethylene -Acrylic acid copolymer, linear low density polyethylene, a linear low density ethylene copolymer, an ionomeric polymer and a molecular segment of the formula 65. synthetic resin film, characterized in that it consists of a mixture of at least 40% of an ethylene-vinyl alcohol copolymer and a maximum of 60% of a thermoplastic Synthetic resin (mixture component) consists, this mixture component a Ethylene-ethyl acrylate copolymer, an Xthylen-Acr.ylsäur.e copolymer, linear Low density polyethylene, a linear low density ethylene copolymer, an ionomeric polymer, an anhydride-modified polypropylene, an anhydride-modified one Ethylene-vinyl acetate copolymer, an anhydride-modified polyethylene lower Density, an anhydride-modified medium density polyethylene, an anhydride-modified one High density polyethylene or a partially saponified ethylene-vinyl acetate copolymer is. 66. Film according to claim 65, characterized in that it has a second Has synthetic resin layer in contact with the first synthetic resin layer. 67. Composite film according to claim 66, characterized in that the synthetic resin for the second layer together with the synthetic resin for the first layer can extrude. 68. Composite film according to claim 66, characterized in that the Ethylene-vinyl alcohol copolymer contains at least about 35% ethylene basic components. 69. The composite film according to claim 66, characterized in that the The thickness of the first layer is approximately 5 to 50 gauge. 70. Composite film according to one of claims 65 to 69, characterized in that that the thermoplastic synthetic resin (component of the mixture) contains carboxyl groups. 71. Composite film according to one of claims 65 to 69, characterized in that that the thermoplastic synthetic resin (mixture component) has a melt index, im Compared to low density polyethylene, of no more than about 10 has. 72. Composite film according to claim 70, characterized in that the thermoplastic synthetic resin (compound component) a melt index, in comparison to low density polyethylene, of no more than about 10. 73. Composite film according to one of claims 66 to 69, characterized in that that the polymer for the second layer is an ethylene-vinyl acetate copolymer, polyethylene high density, low density polyethylene, an ethylene-propylene copolymer, a linear low density polyethylene or a linear ethylene copolymer low density is. 74. Composite film according to one of claims 66 to 69, characterized in that that the thermoplastic synthetic resin (mixture component) contains carboxyl groups and the polymer for the second layer is an ethylene-vinyl acetate copolymer, polypropylene, High density polyethylene, low density polyethylene, an ethylene-propylene copolymer, a linear low density polyethylene or a linear ethylene copolymer low density is. 75. Composite film according to one of claims 65 to 69, characterized in that that the thermoplastic synthetic resin (component of the mixture) has organic anhydride groups contains. 76. Composite film according to claim 70, characterized in that the Carboxyl groups are in the form of anhydride groups.