RU2846034C1 - High-barrier film for medical devices - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry and specifically to a multilayer barrier film for forming stoma and urostomy bags. Disclosed film includes: a barrier layer consisting of a copolymer of ethylene and vinyl alcohol; outer layers on both sides of the barrier layer and connected thereto by an adhesive layer, where the outer layers contain 49.5-95 wt. % polyolefin elastomer or ethylene vinyl acetate copolymer and 5-50.5 wt. % linear low density polyethylene; at least one intermediate noise-insulating layer between the adhesive layer and the outer layer, where the intermediate noise-insulating layer contains 63-95 wt. % ethylene copolymer and vinyl acetate or low density polyethylene and 5-37 wt. % linear low density polyethylene, wherein said adhesive ply comprises polyolefin with grafted maleic anhydride.

EFFECT: invention enables to produce a high-barrier film suitable for recycling, and a combination of satisfactory barrier properties against smell and moisture, strength characteristics for the entire period of use of the product, low noise during use, low temperature of forming a welded stoma bag to the plate and to itself.

5 cl, 6 dwg, 12 tbl, 7 ex

Description

The invention relates to the field of production of high-barrier films for forming ostomy and urostomy bags.

Stoma bags and other products for storing biological materials and medical waste have high requirements for gas and moisture barrier properties throughout the entire service life of the product. Also, an important parameter of such products is high strength properties and noiselessness during use.

A noiseless multilayer film for ostomies is known (US4687711A, published 18.08.1987), comprising: a barrier layer selected from the group consisting of vinylidene chloride copolymers and ethylene-vinyl alcohol copolymers; two outer layers, wherein each outer layer contains a mixture of an elastomeric polyolefin material, a thermoplastic copolymer of ethylene and vinyl acetate. The multilayer film is coextruded and hot blown.

The disadvantage of the known solution is the low environmental friendliness of the resulting material due to the use of chlorine compounds, the difficulty of subsequent recycling and disposal of products made from them.

A film for ostomy bags is known (US Patent No. 7,270,860, published on September 18, 2007) comprising a base layer that prevents odor, formed by a mixture or compound comprising an amorphous polyamide and an anhydride-modified olefin polymer or copolymer. The film also comprises two heat-sealable layers on both sides of the base layer and two surface layers based on an ethylene vinyl acetate copolymer.

The known solution has insufficient characteristics of moisture and odor impermeability and tensile strength, making it difficult to subsequently recycle and dispose of products made from them.

A multilayer film (EP3912601A1, published on 24.11.2021) is known for use in ostomy bags, comprising a barrier layer made of a chlorine-free amorphous polyamide resin and an olefin modified with maleic anhydride or an olefin modified with epoxy resin. The barrier layer is in contact on each side with binder layers, which are a resin grafted with maleic anhydride. The resin is one or more of ethylene-based copolymers, propylene-based copolymers, ethylene-octene polymers and styrene block copolymers. The inner layers are in contact with the binder layers and are one of ethylene-propylene copolymer and the opposite one of ethylene-octene resin and mixtures thereof. The inner layers are in contact with the outer layers, each of which is an ethylene vinyl acetate or ethylene methyl acrylate copolymer or a mixture thereof, or a polypropylene resin or a mixture thereof.

The known solution has insufficient characteristics of moisture and odor impermeability, tensile strength, and noiselessness during use, as well as the difficulty of recycling products made from them.

A bag is known that seals an unpleasant odor (patent US9580241B2, published 02/28/2017), made of a multilayer material including an inner layer and an outer layer, each of which consists of polyethylene or an ethylene-based copolymer, and an intermediate layer containing a barrier resin selected from polyamide, ethylene-vinyl alcohol copolymer (EVAC) or polybutylene terephthalate. The inner and outer layers contain an anti-adhesive and a surfactant.

The known solution has insufficient properties of noiselessness and strength, as well as unsatisfactory strength characteristics of the welded connection of the film to itself and the component parts (plates) of the stoma bag.

A multilayer barrier film is known (application US2015282978A1, published 08.10.2015), comprising a first layer containing at least one of EVOH and G-EVOH; and a second layer comprising one or more elastomeric norbornenes.

The known solution has insufficient noise-free and strength characteristics.

A polymer composition is known (international application WO2012088213A1, published on 28.06.2012) demonstrating low noise properties and comprising a thermoplastic polymer and an effective amount of a noise suppressor. The thermoplastic polymer comprises a polyolefin and preferably a cyclic polyolefin copolymer, a polyester, a polyamide, a styrene-based homopolymer or copolymer, a polycarbonate, a polyurethane, a halogen-containing polymer, an acrylate-based homopolymer or copolymer, a copolymer of an alkene-unsaturated carboxylic acid or an unsaturated carboxylic acid derivative, a homopolymer or copolymer containing vinyl alcohol, or a mixture of two or more of any of the said polymers.

The disadvantage of the known solution is the difficulty of subsequent recycling and disposal of products made from them. Unsatisfactory strength characteristics of the welded seam of the film material to the components of the stoma bag.

A multilayer gas- and odor-impermeable film is known (EP0787580, published 06.08.1997), comprising a barrier layer containing a copolymer of ethylene and vinyl alcohol or polyvinylidene chloride (PVDC), a first outer sealing layer based on a polyolefin, a second outer thermoplastic polyolefin layer adjacent to the skin, and at least one intermediate layer located between the main barrier layer and at least one of the outer layers. The intermediate layer contains an olefin elastomer, optionally mixed with a homopolymer and/or copolymer of ethylene.

The disadvantage of the known solution is the difficulty of subsequent recycling and disposal of products made from them. Unsatisfactory strength characteristics of the welded seam, both to itself and to the components of the stoma bag.

The technical task of the claimed invention is to create a high-barrier film with noise-insulating properties, high strength characteristics, with a low weld formation temperature and suitable for recycling.

The technical result is the creation of a high-barrier film suitable for recycling, and a combination of satisfactory barrier properties against odor and moisture, strength characteristics for the entire period of use of the product, low noise during use, low temperature of formation of the welded seam of the stoma bag to the plate and to itself.

The technical result is achieved in that the multilayer barrier film for forming ostomy and urostomy bags includes a barrier layer consisting of a copolymer of ethylene and vinyl alcohol, outer layers on both sides of the barrier layer and connected to it by means of an adhesive layer, and at least one intermediate noise-insulating layer between the adhesive layer and the outer layer, wherein the adhesive layer contains a polyolefin with grafted maleic anhydride, characterized in that the outer layers contain 49.5-95 wt.% of a polyolefin elastomer or ethylene vinyl acetate copolymer and 5-50.5 wt.% of linear low-density polyethylene, the intermediate noise-insulating layer contains 63-95 wt.% of ethylene vinyl acetate copolymer or low-density polyethylene and 5-37 wt.% of linear low-density polyethylene.

The multilayer film according to the present invention includes at least one barrier layer based on a random copolymer of ethylene and vinyl alcohol EVOH, adhesive layers on both sides of the barrier layer, noise-insulating layers based on a copolymer of ethylene and vinyl alcohol (EVA), and outer layers based on polyolefin elastomers.

The barrier layer is preferably made on the basis of a random copolymer of ethylene and vinyl alcohol CEVA with an ethylene content of 24-48 wt.%, most preferably 27-35 wt.%, with a melt flow limit (MFL) (190 °C / 2.16 kg) from 1 to 4 g/10 min, most preferably from 1.5 to 2.5 g/10 min. To reduce rigidity and improve noise-insulating properties, the thickness of the barrier layer can vary from 0.5 to 8% of the total film thickness, most preferably from 1.5 to 5%.

An adhesive based on maleic anhydride is used as the adhesive (glue) layers between the barrier and subsequent adjacent noise-insulating layers. Preferably, the adhesive layer is made on the basis of a concentrate or a ready-made composition of maleic anhydride monomer grafted to an olefin polymer chain to improve the interfacial adhesion between the barrier and noise-insulating layers. Since the barrier and adhesive layers have high rigidity, to reduce the noise-insulating properties, it is most preferable to use an adhesive concentrate mixed with metallocene linear low-density polyethylene (LLDPE) in a ratio of 10-90/90-10%, most preferably to use 30-70/70-30%, the thickness of the adhesive layers varies from 1.5 to 12% of the total film thickness, most preferably from 2 to 7%. It is recommended to use materials with a MFI of 0.5 - 5 g/10 min (190 °C / 2.16 kg), most preferably from 1.5 to 3.5 g/10 min (190 °C / 2.16 kg), a density of 0.890 - 0.940 g / cm ³ , most preferably a density of 0.905 - 0.930 g / cm ³ , a Shore hardness (Method D) from 0 to 50, most preferably from 20 to 30, as a maleic anhydride concentrate. It is recommended to use raw materials with a MFI of 0.5 - 3.5 g / 10 min (190 °C / 2.16 kg), most preferably from 1.5 to 2.5 g / 10 min (190 °C / 2.16 kg), a density of 0.900 - 0.940 as an additional LLDPE component. g/ ^cm3 , most preferably with a density of 0.910 - 0.930 g/ ^cm3 , Shore hardness (Method D) from 0 to 50, most preferably from 20 to 30.

Soundproofing layers mainly consist of ethylene vinyl acetate copolymer and have a Shore hardness (method A) of 60-91 units and a Vicat softening temperature of 35-80°C. It is recommended to use as EVA materials with a vinyl acetate content of 7 to 40 wt.%, most preferably from 14 to 28 wt.%, most preferably from 18 to 25 wt.%, a density of 0.930 - 0.960 g/ ^cm3 , most preferably a density of 0.940 - 0.950, a Shore hardness (Method A) of 40 to 95, most preferably from 60 to 80, a MFI of 0.5 - 4.5 g/10 min (190 °C / 2.16 kg), most preferably from 2.0 to 3.0 g/10 min (190 °C / 2.16 kg), with a melting point of 60 to 100 °C, most preferably from 70 to 90 °C. Preferably, the noise-insulating layers are formed from a mixture of components containing EVAA and impact-resistant metallocene linear low-density polyethylene (LLDPE) or low-density polyethylene (LDPE) in a ratio of 95-63/5-37%, most preferably using 85-80/15-20%, the thickness of the noise-insulating layers varies from 15 to 60% of the total film thickness, most preferably from 29 to 45%. As LLDPE it is preferable to use materials with a density of 0.910 - 0.930 g/ ^cm3 , most preferably a density of 0.915 - 0.920 g/ ^cm3 , a Shore hardness (Method D) from 0 to 50, most preferably from 20 to 30, a MFI of 0.5 - 3.5 g/10 min (190 °C / 2.16 kg), most preferably from 1.5 to 2.5 g/10 min (190 °C / 2.16 kg), with a melting point of 115 to 125 °C. As LDPE it is preferable to use materials with a density of 0.915 - 0.930 g/ ^cm3 , most preferably a density of 0.920 - 0.925 g/ ^cm3 , Shore hardness (Method D) from 0 to 50, most preferably from 20 to 30, MFI of 0.5 - 3.5 g/10 min (190 °C / 2.16 kg) most preferably from 1.5 to 2.5 g/10 min (190 °C / 2.16 kg), with a melting point from 103 to 110 °C. The use of metallocene linear low-density polyethylene in adhesive and noise-insulating layers allows for high strength characteristics, since the presence of a large amount of EVAH in the film worsens the physical and mechanical characteristics of the material.

Additionally, soundproofing layers may contain technological additives such as superconcentrates, processing (improving performance) or a mixture of them.

In order to impart a decorative effect to the stoma bags and to conceal the contents, it is recommended to introduce a superconcentrate of flesh-colored or other color, containing a filler that ensures the opacity of the film, into one or several layers, preferably into the sound-insulating ones. Superconcentrate is a concentrate of dyes, pigments or fillers and other active substances, based on a polyolefin matrix carrier to impart the required color to the fabric during extrusion. Preferably, the superconcentrate matrix consists of LLDPE, and the finished mixture has a density of 0.910 - 1.000 g / cm ³ and a MFI of 10 - 20 g / 10 min (190 ° C / 2.16 kg). Quantitatively, the introduction of the superconcentrate into one or several sound-insulating or other layers, depending on their thickness to the entire film, varies from the required optical density within the range from 0.1 to 0.9, most preferably from 0.3 to 0.6.

In order to improve the melt flow during the processing of raw materials, without the formation of inhomogeneities, optical defects, and to reduce carbon deposits at the points of contact of the material with the metal surface in the extruder, it is recommended to use specialized processing additives in an amount of 0.1 to 5%. As a processing additive, it is recommended to use well-known brands of manufacturers based on a carrier made of LLDPE, with the following properties: density of 0.910 - 0.950 g / cm ³ , most preferably density of 0.920 - 0.940 g / cm ³ , MFI 0.5 - 7 g / 10 min (190 ° C / 2.16 kg), most preferably from 2 to 4 g / 10 min (190 ° C / 2.16 kg).

The outer layers can be made of several components, preferably based on polyolefin elastomers or plastomers with a Shore A hardness of 40-91 units. The outer layers perform the function of heat-sealable layers for forming a welded seam of the stoma bag, both on itself and on the component parts, and are preferably made of a mixture of components of a polyolefin elastomer (POE) based on ethylene-octene and/or ethylene-hexene and/or ethylene-butene, and impact-resistant metallocene linear low-density polyethylene (LLDPE) or ethylene vinyl acetate copolymer (EVAC) in a ratio of 95-49.5/5-50.5 wt.%, most preferably 85-70/15-30 wt.%. The thickness of the outer layers varies in the range of 5-30% of the total film thickness, most preferably in the range of 10 to 20%. It is recommended to use as POE raw materials with a density of 0.865 - 0.910 g/ ^cm3 , most preferably a density of 0.880 - 0.902 g/ ^cm3 , a Shore hardness (Method A) from 40 to 95, most preferably from 60 to 80, a MFI of 0.5 - 4.5 g/10 min (190 °C / 2.16 kg), most preferably from 2.0 to 3.0 g/10 min (190 °C / 2.16 kg), with a melting point from 60 to 100 °C, most preferably from 70 to 90 °C. Additionally, the outer layers can contain at least one additive, for example: processing, sliding, anti-blocking, superconcentrate, etc.

Since the polymer film contains low-melting components that improve the welding of the fabric to itself and to the components of the stoma bag, a tendency to stick together during winding and storage in a roll (block effect) is possible during production. To eliminate this type of winding defects, it is recommended to use anti-blocking additives based on natural or synthetic fillers from well-known manufacturers with the following characteristics. The content of the active substance from 20 to 80% is most preferably from 30 to 50% with a particle size of 1 to 10 μm, most preferably in the range of 5-6 μm. Polymer matrix based on LDPE or LLDPE, most preferably LLDPE. The density of the anti-blocking additive is 1.1 - 1.5 g/ ^cm3 , most preferably a density of 1.25 - 1.40 g/ ^cm3 , MFI 2.5 - 5.5 g/10 min (190 °C / 2.16 kg), most preferably from 3.5 to 4.5 g/10 min (190 °C / 2.16 kg). The recommended dosage of the additive in the outer layers is from 1 to 10%, most preferably from 3 to 7%.

In order to improve web sliding (friction coefficient) against moving parts of the production line or against itself, it is recommended to additionally introduce slip (sliding) additives into the outer layers based on the active substance erucamide or oleamide from well-known manufacturers with the following characteristics. The content of the active substance is from 1 to 20%, most preferably from 3 to 8%. The polymer matrix is based on LDPE or LLDPE, most preferably LLDPE. The density of the slip additive is 0.900 - 1.20 g/ ^cm3 , most preferably a density of 0.92 - 0.95 g/ ^cm3 , MFI 2.5 - 5.5 g/10 min (190 °C / 2.16 kg), most preferably from 3.5 to 4.5 g/10 min (190 °C / 2.16 kg). The recommended dosage of the additive into the outer layers is from 1 to 10%, most preferably from 3 to 7%.

It is also possible to use a combined type of additives containing both an anti-block agent and a slip.

The proposed film material can be produced by any known method of melt extrusion molding, for example, blow molding, flat-slot molding, casting and other variations of extrusion known to specialists in this field.

Examples:

Example 1

The following components were used to produce the film according to example 1:

The barrier layer was made from a copolymer of ethylene and vinyl alcohol EVOH, with an ethylene content of 28 wt.%. MFR = 1.8 g/10 min. 190 °C / 2.16 kg).

Ethylene maleic anhydride copolymer was used for the adhesive layers. Characteristics of the ethylene maleic anhydride copolymer: MFR 2.1 g/10 min, Shore D hardness 40, density 0.938 g/cm ³ .

A mixture of LDPE, LLDPE ₁ components and technological additives was used for noise-insulating layers. LDPE characteristics: density 0.920 g/ ^cm3 , Shore A hardness 91, MFI 2 g/10 min, T _{melting point} 105 °C. LLDPE characteristics: density 0.920 g/ ^cm3 , Shore A hardness 90, MFI 1.8 g/10 min, T _{melting point} 125 °C. Additionally, technological pressing and superconcentrate additives were introduced into the layers.

A mixture of EVA, LLDPE ₂ and processing aids was used for the outer layers. EVA characteristics: vinyl acetate content in EVA 18%, density 0.940 g/ ^cm3 , Shore A hardness 90, MFI 2.6 g/10 min, _Tm 92 °C. LLDPE ₂ characteristics: density 0.915 g/ ^cm3 , Shore A hardness 90, MFI 1.5 g/10 min, _Tm 122 °C. Pressing, sliding and anti-blocking agents were used as processing aids.

Table 1

No. Layer name Name of components Content of components, wt.% Layer thickness 1 First outer layer SEVA
LLDPE ₂
Slip
Antiblock
Processing 70.5
20.0
3.5
4.0
2.0 14 microns 2 The first noise-insulating LDPE
LLDPE ₁
Super concentrate
Processing 78.0
15.0
6.0
1.0 9.5 microns 3 Second noise-insulating LDPE
LLDPE ₁
Processing 84.5
15.0
0.5 9.5 microns 4 First adhesive Adhesive 100,0 3.5 microns 5 Barrier SEVS 100,0 2 microns 6 Second adhesive Adhesive 100,0 3.5 microns 7 Third noise-insulating LDPE
LLDPE ₁
Processing 84.5
15.0
0.5 9.5 microns 8 The fourth noise-insulating EVA
LLDPE ₁
Super concentrate
Processing 78.0
15.0
6.0
1.0 9.5 microns 9 Outer layer SEVA
LLDPE ₂
Slip
Antiblock
Processing 70.5
20.0
3.5
4.0
2.0 14 microns

Example 2

To produce the film according to example 2, the following components were used:

The barrier layer was made of ethylene-vinyl alcohol copolymer EVOH, with an ethylene content of 44 wt.%, respectively. MFR = 5.5 g/10 min (190 °C/ 2.16 kg).

Ethylene maleic anhydride copolymer was used for the adhesive layers. Characteristics of the ethylene maleic anhydride copolymer: MFR 1.8 g/10 min, Shore D hardness 35, density 0.905 g/cm ³ .

A mixture of EVA, LLDPE ₁ and LDPE components, as well as technological additives, was used for noise-insulating layers. EVA characteristics: vinyl acetate content in EVA is 18 wt.%, density is 0.940 g/ ^cm3 , Shore A hardness is 86, MFI is 2.6 g/10 min, _Tm is 86 °C. LLDPE ₁ characteristics: density is 0.918 g/ ^cm3 , Shore D hardness is 48, MFI is 1.5 g/10 min, _{Tm is} 121 °C. LDPE characteristics: density is 0.910 g/ ^cm3 , Shore A hardness is 90, MFI is 2 g/10 min, _Tm is 105. Technological pressing additives and superconcentrate are additionally introduced into the layers.

A mixture of POE, LLDPE ₂ and processing aids was used for the outer layers. POE characteristics: density 0.890 g/ ^cm3 , Shore A hardness 75, MFI 1.0 g/10 min, _Tm 95 °C. LLDPE ₂ characteristics: density 0.915 g/ ^cm3 , Shore A hardness 90, MFI 1.5 g/10 min, _Tm 121 °C. Pressing, sliding and anti-blocking agents were used as processing aids.

Table 2

No. Layer name Name of components Content of components, wt.% Layer thickness 1 First outer layer POE
LLDPE ₂
Slip
Antiblock
Processing 61.5
30.0
4.5
3.0
1.0 14 microns 2 The first noise-insulating SEVA
LLDPE ₁
Super concentrate
Processing 59.0
30.0
10.0
1.0 10 microns 3 Second noise-insulating LDPE
LLDPE ₁
Processing 79.5
20.0
0.5 8 microns 4 First adhesive Adhesive 100,0 4 microns 5 Barrier SEVS 100,0 3 microns 6 Second adhesive Adhesive 100,0 4 microns 7 Third noise-insulating LDPE
LLDPE ₁
Processing 79.5
20.0
0.5 8 microns

8 The fourth noise-insulating SEVA
LLDPE ₁
Super concentrate
Processing 59.0
30.0
10.0
1.0 10 microns 9 Outer layer POE
LLDPE ₂
Slip
Antiblock
Processing 61.5
30.0
4.5
3.0
1.0 14 microns

Example 3

To produce the film according to example 3, the following components were used:

The barrier layer was made of ethylene-vinyl alcohol copolymer EVOH, with an ethylene content of 28 wt.%, respectively. MFR = 1.8 g/10 min, 190 °C / 2.16 kg).

Ethylene maleic anhydride copolymer and LLDPE were used for the adhesive layers. Characteristics of ethylene maleic anhydride copolymer: MFI 1.0 g/10 min, Shore D hardness 40, density 0.920 g/ ^cm3 , _Tm 124. Characteristics of LLDPE ₁ : density 0.925 g/ ^cm3 , Shore A hardness 90, MFI 0.9 g/10 min, _Tm 124 °C.

A mixture of EVA, LLDPE ₂ and LDPE components, as well as technological additives, was used for noise-insulating layers. EVA characteristics: vinyl acetate content in EVA is 18%, density is 0.935 g/ ^cm3 , Shore A hardness is 76, MFI is 2.5 g/10 min, T _{melting point} is 87 °C. LLDPE ₁ characteristics: density is 0.918 g/ ^cm3 , Shore D hardness is 48, MFI is 1.5 g/10 min, T _{melting point} is 121 °C. LDPE characteristics are density 0.910 g/ ^cm3 , Shore A hardness is 90, MFI is 2 g/10 min, T _{melting point is} 105 °C. Technological pressing additives and superconcentrate are additionally introduced into the layers.

A mixture of POE, LLDPE ₃ and processing aids was used for the outer layers. POE characteristics: density 0.885 g/ ^cm3 , Shore A hardness 86, MFI 1.2 g/10 min, _Tm 73 °C. LLDPE ₂ characteristics: density 0.917 g/ ^cm3 , Shore A hardness 90, MFI 1.0 g/10 min, _Tm 121 °C. Pressing, sliding and anti-blocking agents were used as processing aids.

Table 3

No. Layer name Name of components Content of components, wt.% Layer thickness 1 First outer layer LLDPE ₃
POE
Slip
Antiblock
Processing 50.5
40
3.5
4.0
2.0 10 microns

2 The first noise-insulating SEVA
LLDPE ₂
Super concentrate
Processing 71.0
12.0
15.0
2 14 microns 3 Second noise-insulating LDPE
LLDPE ₂
Processing 87.5
12.0
0.5 8 microns 4 First adhesive LLDPE ₁
Adhesive 70.0
30.0 3.5 microns 5 Barrier SEVS 100,0 3 microns 6 First adhesive LLDPE ₁
Adhesive 70.0
30.0 3.5 microns 7 Third noise-insulating LDPE
LLDPE ₂
Processing 87.5
12.0
0.5 8 microns 8 The fourth noise-insulating SEVA
LLDPE ₂
Super concentrate
Processing 71.0
12.0
15.0
2.0 14 microns 9 Outer layer LLDPE ₃
POE
Slip
Antiblock
Processing 50.5
40.0
3.5
4.0
2.0 10 microns

Example 4

To produce the film according to example 4, the following components were used:

The barrier layer was made of ethylene-vinyl alcohol copolymer EVOH, with an ethylene content of 38 wt.%, respectively. MFR = 3.9 g/10 min, 190 °C / 2.16 kg), density 1.160 g/cm ³

A mixture of ethylene maleic anhydride copolymer components with LLDPE was used for the adhesive layers. Characteristics of the ethylene maleic anhydride copolymer: MFI 1.8 g/10 min, Shore D hardness 40, density 0.905 g/ ^cm3 , _Tm 117 °C. Characteristics of LLDPE ₁ : density 0.920 g/ ^cm3 , Shore D hardness 45, MFI 2 g/10 min, _Tm 122 °C

A mixture of EVA, LLDPE and technological additives was used for noise-insulating layers. EVA characteristics: vinyl acetate content in EVA is 18%, density is 0.935 g/ ^cm3 , Shore A hardness is 76, MFI is 2.5 g/10 min, _{Tm is} 87 °C. LLDPE ₂ characteristics: density is 0.917 g/ ^cm3 , Shore A hardness is 90, MFI is 1 g/10 min, _{Tm is} 121 °C. Technological pressing and superconcentrate additives were additionally introduced into the layers.

A mixture of POE, LLDPE and processing aids was used for the outer layers. POE characteristics: density 0.902 g/ ^cm3 , Shore A hardness 91, MFI 1.2 g/10 min, _Tm 100 °C. _LLDPE characteristics: density 0.917 g/ ^cm3 , Shore A hardness 90, MFI 1 g/10 min, _Tm 121 °C. Pressing, sliding and antiblocking agents were used as processing aids.

Table 4

No. Layer name Name of components Content of components, wt.% Layer thickness 1 First outer layer POE
LLDPE ₂
Slip
Antiblock
Processing 65.0
25.0
4.0
5.0
1.0 9 microns 2 The first noise-insulating SEVA
LLDPE ₂
Super concentrate
Processing 71.0
12.0
15.0
2.0 17 microns 3 Second noise-insulating EVA
LLDPE ₂
Processing 87.0
12.0
1.0 7 microns 4 First adhesive LLDPE ₁
Adhesive 70.0
30.0 3.5 microns 5 Barrier SEVS 100 3 microns 6 First adhesive LLDPE ₁
Adhesive 70.0
30.0 3.5 microns

7 Third noise-insulating SEVA
LLDPE ₂
Processing 87
12.0
1.0 7 microns 8 The fourth noise-insulating SEVA
LLDPE ₂
Super concentrate
Processing 71.0
12.0
15.0
2.0 17 microns 9 Outer layer POE
LLDPE ₂
Slip
Antiblock
Processing 65.0
25.0
4.0
5.0
1.0 9 microns

Example 5

The following components were used to produce the film according to example 5:

The barrier layer was made of ethylene-vinyl alcohol copolymer EVOH, with an ethylene content of 38 wt.%, respectively. MFR = 3.9 g/10 min, 190 °C / 2.16 kg), density 1.160 g/cm ³

A mixture of ethylene maleic anhydride copolymer and LLDPE components was used for the adhesive layers. Characteristics of the ethylene maleic anhydride copolymer: MFI 1.8 g/10 min, Shore D hardness 40, density 0.905 g/ ^cm3 , _Tm 117 °C. Characteristics of LLDPE ₁ : density 0.920 g/ ^cm3 , Shore D hardness 45, MFI 2 g/10 min, _Tm 122 °C.

A mixture of EVA, LLDPE and technological additives was used for noise-insulating layers. EVA characteristics: vinyl acetate content in EVA is 18%, density is 0.935 g/ ^cm3 , Shore A hardness is 76, MFI is 2.5 g/10 min, _{Tm is} 87 °C. LLDPE ₂ characteristics: density is 0.917 g/ ^cm3 , Shore A hardness is 90, MFI is 1 g/10 min, _{Tm is} 121 °C. Technological pressing and superconcentrate additives were additionally introduced into the layers.

A mixture of POE, LLDPE and processing aids was used for the outer layers. POE characteristics: density 0.902 g/ ^cm3 , Shore A hardness 91, MFI 1.2 g/10 min, _Tm 99 °C. _LLDPE characteristics: density 0.917 g/ ^cm3 , Shore A hardness 90, MFI 1 g/10 min, _Tm 121 °C. Pressing, sliding and antiblocking agents were used as processing aids.

Table 5

No. Layer name Name of components Content of components, wt.% Layer thickness

1 First outer layer POE
LLDPE ₂
Slip
Antiblock
Processing 59.5
30.0
5.0
5.0
0.5 11.5 microns 2 The first noise-insulating SEVA
LLDPE ₂
Super concentrate
Processing 71.0
12.0
15.0
2.0 11.5 microns 3 Second noise-insulating SEVA
LLDPE ₂
Processing 87.0
12.0
1.0 10 microns 4 First adhesive LLDPE ₁
Adhesive 70.0
30.0 3 microns 5 Barrier SEVS 100,0 2.5 microns 6 First adhesive LLDPE ₁
Adhesive 70.0
30.0 3 microns 7 Third noise-insulating SEVA
LLDPE ₂
Processing 87.0
12.0
1.0 10 microns 8 The fourth noise-insulating SEVA
LLDPE ₂
Super concentrate
Processing 71.0
12.0
15.0
2.0 11.5 microns 9 Outer layer POE
LLDPE ₂
Slip
Antiblock
Processing 59.5
30.0
5.0
5.0
0.5 11.5 microns

Example 6

The following components were used to produce the film according to example 6:

The barrier layer was made of ethylene-vinyl alcohol copolymer EVOH, with an ethylene content of 28 wt.%, respectively. MFR = 1.8 g/10 min, 190 °C / 2.16 kg).

A mixture of ethylene maleic anhydride copolymer and LLDPE components was used for the adhesive layers. Characteristics of the ethylene maleic anhydride copolymer: MFI 1.8 g/10 min, Shore D hardness 40, density 0.905 g/ ^cm3 , _Tm 117 °C. Characteristics of LLDPE ₁ : density 0.920 g/ ^cm3 , Shore D hardness 45, MFI 2 g/10 min, _Tm 122 °C.

A mixture of EVA, LLDPE and technological additives was used for noise-insulating layers. EVA characteristics: vinyl acetate content in EVA is 18%, density is 0.935 g/ ^cm3 , Shore A hardness is 76, MFI is 2.5 g/10 min, _{Tm is} 87 °C. LLDPE ₂ characteristics: density is 0.917 g/ ^cm3 , Shore A hardness is 90, MFI is 1 g/10 min, _{Tm is} 121 °C. Technological pressing and superconcentrate additives were additionally introduced into the layers.

A mixture of POE, LLDPE and processing aids was used for the outer layers. POE characteristics: density 0.902 g/ ^cm3 , Shore A hardness 91, MFI 1.2 g/10 min, _Tm 99 °C. _LLDPE characteristics: density 0.917 g/ ^cm3 , Shore A hardness 90, MFI 1 g/10 min, _Tm 121 °C. Pressing, sliding and antiblocking agents were used as processing aids.

Table 6

No. Layer name Name of components Content of components, wt.% Layer thickness 1 First outer layer POE
LLDPE ₂
Slip
Antiblock
Processing 61.5
30.0
5.0
3.0
0.5 12 microns 2 The first noise-insulating SEVA
LLDPE ₂
Super concentrate
Processing 63.0
20.0
15.0
2.0 12.25 µm 3 Second noise-insulating SEVA
LLDPE ₂
Processing 87.0
12.0
1.0 9 microns 4 First adhesive LLDPE ₁
Adhesive 70.0
30.0 3 microns 5 Barrier SEVS 100,0 2.5 microns 6 First adhesive LLDPE ₁
Adhesive 70.0
30.0 3 microns 7 Third noise-insulating SEVA
LLDPE ₂
Processing 87.0
12.0
1.0 9 microns 8 The fourth noise-insulating SEVA
LLDPE ₂
Super concentrate
Processing 63.0
20.0
15.0
2.0 12.25 µm 9 Outer layer POE
LLDPE ₂
Slip
Antiblock
Processing 61.5
30.0
5.0
3.0
0.5 12 microns

Example 7

To produce the film according to example 7, the following components were used:

The barrier layer was made of ethylene-vinyl alcohol copolymer EVOH, with an ethylene content of 28 wt.%, respectively. MFR = 1.8 g/10 min 190 °C / 2.16 kg).

A mixture of ethylene maleic anhydride copolymer and LLDPE components was used for the adhesive layers. Characteristics of the ethylene maleic anhydride copolymer: MFI 1.8 g/10 min, Shore D hardness 40, density 0.905 g/ ^cm3 , _Tm 117 °C. Characteristics of LLDPE ₁ : density 0.920 g/ ^cm3 , Shore D hardness 45, MFI 2 g/10 min, _Tm 122 °C.

A mixture of EVA, POE components and technological additives was used for noise-insulating layers. EVA characteristics: vinyl acetate content in EVA is 18%, density is 0.935 g/ ^cm3 , Shore A hardness is 76, MFI is 2.5 g/10 min, _{Tm is} 87 °C. POE characteristics: density is 0.885 g/ ^cm3 , Shore A hardness is 86, MFI is 1.2 g/10 min, Tm _is 73 °C. Technological pressing and superconcentrate additives were additionally introduced into the layers.

A mixture of LLDPE, POE and processing aids was used for the outer layers. POE characteristics: LLDPE ₂ characteristics: density 0.917 g/ ^cm3 , Shore A hardness 90, MFI 1 g/10 min, _Tm 121 °C. POE characteristics: density 0.885 g/ ^cm3 , Shore A hardness 86, MFI 1.2 g/10 min, _Tm 73 °C. Pressing, sliding and antiblocking agents were used as processing aids.

Table 7

No. Layer name Name of components Content of components, wt.% Layer thickness 1 First outer layer LLDPE ₂
POE
Slip
Antiblock
Processing 61.5
30.0
5.0
3.0
0.5 12 microns 2 The first noise-insulating SEVA
POE
Super concentrate
Processing 63.0
20.0
15.0
2.0 12.25 µm 3 Second noise-insulating SEVA
POE
Processing 87.0
12.0
1.0 9 microns 4 First adhesive LLDPE ₁
Adhesive 70.0
30.0 3 microns 5 Barrier SEVS 100,0 2.5 microns 6 First adhesive LLDPE ₁
Adhesive 70.0
30.0 3 microns

7 Third noise-insulating EVA
POE
Processing 87.0
12.0
1.0 9 microns 8 The fourth noise-insulating SEVA
POE
Super concentrate
Processing 63.0
20.0
15.0
2.0 12.25 µm 9 Outer layer LLDPE ₂
POE
Slip
Antiblock
Processing 61.5
30.0
5.0
3.0
0.5 12 microns

For further comparison of the performance characteristics of the films obtained in Examples 1-7, materials of Chinese and European manufacture were selected as samples of analogues. The technical specification for the comparison materials is given in Table 8.

Table 8 - Performance characteristics of analog materials

Parameter name Chinese equivalent European analogue Thickness, µm 75 75 Tensile strength, N/ ^mm2 (longitudinal direction) 25 26 Tensile strength, N/ ^mm2 (transverse direction) 15 17 Elongation, % (longitudinal direction) 400 380 Elongation, % (transverse direction) 600 570 Oxygen permeability, ^cm3 / ^m2 /24h 14 9 Weld strength N/ ^mm2 (longitudinal direction) 20 25 Weld strength N/ ^mm2 (transverse direction) 15 19 Coefficient of friction (dynamic) 0.30 0.22

The priority indicator of films for ostomy and urostomy bags is resistance to penetration of odor of waste products during wear. Barrier properties of known patent solutions are based on the use of a polyvinylidene chloride (PVDC) copolymer barrier layer in the film. Determination of oxygen barrier properties was carried out according to ASTM D3985 at 50% humidity, temperature of 23 °C. Fig. 1 shows the results of measuring oxygen permeability for examples 1-7 and analog samples. Determination of vapor barrier properties was carried out according to ASTM F1249 at 90% humidity, temperature of 37.8 °C. Fig. 2 shows the results of measuring vapor permeability for examples 1-7 and analog samples.

Most manufacturers of ostomy bags, when choosing a barrier material, rely on oxygen limit values of no more than 14 ^cm3 / ^m2 ×24 h, the results obtained demonstrate full compliance with the specification, however, the design options example: 1-7 have property values slightly higher than their analogues. The results of measuring the vapor permeability properties showed comparable values for all materials within the range from 3.5 to 6 g/ ^m2 ×24 h. The European and Chinese analogues, as well as examples 4, 6, 7, have optimal properties.

The next step involved assessing the physical and mechanical characteristics, such as tensile strength and the strength of the welded joint of the web onto itself. The strength characteristics were measured according to ASTM D882. Fig. 3 shows the results of measuring the average tensile strength N/15 mm in the longitudinal and transverse directions.

Based on the results of measuring the strength characteristics in the longitudinal and transverse directions of the fabric (Fig. 3, 4), it can be concluded that the following materials have comparable tensile strength properties: example 2-7 and the European analogue, example 1 and the Chinese analogue have slightly lower values, which can have a negative impact on the use of the stoma bag.

The weld was formed at a temperature of 110 and 90 °C, a pressure of 40 N, a time of 0.5 s, through PETF, the weld strength measurements were carried out according to DIN55529:2012-09. Table 9 provides explanations for the weld behavior during the test, where 1 - the weld is hermetic and intact, 0 - the weld is hermetic but diverges during the test, x - the weld is not hermetic. Figs. 5, 6 show the results of the strength characteristics of the weld at 90 and 110 °C.

Table 9 - Weld seam measurement results

Welding temperature Example #1 Example #2 Example #3 Example #4 Example #5 Example #6 Example #7 Analogue Europe Analogue China 90 °C 0 1 1 1 1 1 1 X 0 110 °C 1 1 1 1 1 1 1 1 1

During the evaluation of the weld strength of the presented samples on itself, it was revealed that the European analogue has weld formation indicators somewhat lower than the presented samples, the Chinese analogue is comparable with examples 1-7, however, at a temperature of 90 °C, a tendency to decrease in strength is observed. Examples 4, 6, 7 have optimal stability.

To evaluate the softness and noiselessness of the films for examples 1-7 and similar materials, a series of blind tests with a focus group of 17 people was conducted. The focus group consisted of people of different ages and included both male and female audiences. As the main properties, it was proposed to tactilely evaluate the softness and noiselessness of 9 samples of film materials. All samples had identical dimensional characteristics: area 200 mm ² , thickness 75 μm ± 5%. For each film, it was proposed to evaluate the softness and noiselessness in a quantitative assessment from 1 to 10, where 1 is a hard and noisy film, 10 is a soft and noiseless film. Then, the average value of each parameter was calculated and a gradation was built from the softest to the hardest (1-9) and from the quietest to the noisiest (1-9). Table 10 shows the results of the blind test.

Table 10 - Results of softness and noiselessness measurements

Parameter name Example #1 Example #2 Example #3 Example #4 Example #5 Example #6 Example #7 Analogue Europe Analogue China Softness 9 8 7 5 6 2 3 1 4 Silence 9 8 7 4 5 3 2 1 6

From the results of the blind test to assess the softness and noiselessness of examples 1-7 with known analogues, it is clear that the European analogue of the manufacturer has the highest indicators, the most preferred version is example No. 7, the least preferred version is example No. 1.

The evaluation of the suitability of packaging for recycling is carried out in accordance with the CEFLEX instructions and the methodology of the Institute Interseroh Dienstleistungs Gmbh for the following types of packaging: Full PP, Full PE and Mixed PO (PP and PE). If the packaging contains PET, OPA, PVC polystyrene, foil, paper or biodegradable films (cellophane, PLA), then the evaluation of suitability for recycling is not applicable to this type of packaging. It should also be taken into account that the suitability of packaging for recycling can only be carried out if the packaging consists of at least 80% PP, PE, polyolefins or a PP/PE combination. Otherwise, the evaluation is not possible. Packaging may contain secondary granules in the composition of films, this will not affect the evaluation in any way, but on the contrary, it is even desirable, as it encourages the development of the secondary granules market.

The assessment is carried out in three stages: suitability for waste collection, sorting, suitability for mechanical processing into secondary granules. At each stage, the packaging receives points. After the assessment of suitability for recycling, a result in points (from 0 to 20) will be obtained, which can be converted into percentages and the assessment result can be classified. The assessment allows us to determine the degree of suitability for recycling from unsuitable for recycling to very good suitability. An example of the assessment will be described below using Example 1.

Conducting an assessment of the suitability of film for recycling

To carry out the assessment, it is necessary to use the available information (qualitative and quantitative composition, including the type and weight of each material in the sample composition.

The first stage of the assessment is suitability for waste collection. Since the film being assessed is Full PE and Mixed PO (PP and PE) and does not contain paper, such a film will always receive the maximum score at this stage of the assessment (2 points)

The second stage of evaluation is film sorting.

Minimum size. Sorting lines use BIR scanners to identify the package and then send it to the desired fraction, so the package size must be at least 20x20 mm. If this point is met, the package gets 2 points.

Identification capability. At this stage, the ability of the film to magnetize (to send the package to the desired recycling path using magnetic separators), surface properties (the type of plastic in the package, the thickness of the layers and the color are determined) and electrical conductivity (to determine the structure of the package in more detail and send it to the desired recycling path, for example, if there is foil inside the package) are studied. Since the film being evaluated is Full PE and Mixed PO, at this stage the package will pass all tests and receive the maximum score (4 points)

The third stage of the assessment is the suitability of the packaging for mechanical processing into secondary granules. This stage is divided into three parts, where a maximum of 4 points can be obtained for each.

Processing quality. Full PP or Full PE packaging receives the maximum score at this stage (4 points), since mono-material packaging does not spoil the quality of secondary granules. Mixed PO receives 3 points due to the deterioration of the quality of secondary granules due to the presence of both polypropylene and polyethylene components.

Separable parts that cannot be recycled. This section covers dispensers, caps, zippers, valves, etc. If dispensers, caps, zippers, and valves are made of the same materials as the packaging (PE or PP), the packaging will receive the maximum score (4 points) at this stage. If the packaging has a label, it must be made of PE or PP, if not (made of paper), the label must occupy no more than 30% of the packaging area and be easily peeled off.

Inseparable components and impurities. This section deals with printing, adhesives, various coatings. At this stage, the packaging can receive a maximum of 4 points.

When considering printing, it is necessary to remember that according to the CEFLEX instructions, only nitrocellulose (NC) and polyurethane (PU) paints and varnishes can be used (PVDC is prohibited) and the total weight in the package should be limited to 5%. Also, preference should be given to light, natural colors. Black and dark colors are highly undesirable. If the above conditions are met, the package still loses 1 point to the assessment, since printing worsens the quality of secondary granules.

When considering adhesives, it is important to remember that polyurethane, acrylic or natural rubber latex adhesives are permitted at a maximum weight of 5% of the total packaging structure. The preferred alternative to adhesive lamination is the use of cast lamination based on PE or PP.

Transparent coatings such as SiOx, AlOx and PVOH do not affect the quality of secondary granules, but are limited to 5% by weight of the total package structure. Metallization and EVOH (<5% by weight of the package) negatively affect the quality of the resulting secondary granules and this is -1 point to the assessment.

After completing all the above stages, the packaging will receive an assessment of its suitability for recycling. By summing up the points at each stage of the assessment, a final assessment in points (from 0 to 20) will be obtained.

Using Table 5, the scores can be converted to percentages to obtain a packaging recyclability score corresponding to the percentages in Table 11.

Table 11 - Assessment of suitability for recycling

Points Interest Result 19-20 95-100% Very good 16-18 80-90% Good

13-15 65-75% Limited 10-13 50-60% Significantly limited <10 <50% Insufficient Rating not possible - Non-recyclable

Further, using example 1, an assessment of suitability for recycling is made.

1. The first stage of evaluation is the compliance of the packaging with the collection system. Since the evaluated packaging is Full PE and does not contain paper, such film will always receive the maximum score at this stage of evaluation (2 points)

2. The second stage of evaluation is the sortability of the packaging. Since the packaging is larger than 20x20 mm, this is 2 points. Since the evaluated packaging is Full PE, it will undergo tests for the ability of the packaging to be magnetized, surface properties and electrical conductivity and will receive 4 points.

3. The third stage of evaluation is the suitability of the packaging for mechanical recycling. Since the packaging is Full PE, such packaging cannot be recycled in better quality, therefore 3 points. According to the calculation of the specific gravity of the film material, there is 4% EVOH in the composition, therefore -1 point.

4. The total number of points received by this package during the evaluation is 18 points, which, according to Table 12, is a good result.

Table 12 - Results of the assessment of suitability for recycling

Evaluation stage Score The first stage of assessment is the compliance of the packaging with the collection system Correspondence 2 The second stage of evaluation is the sortability of packaging Minimum size 2 Possibility of identification 4 The third stage of assessment is the suitability of packaging for mechanical recycling Quality of processing 3 Separable parts that cannot be recycled 4 Non-separable components and impurities 3 Result

Stage 1 2 of 2 Stage 2 6 of 6 Stage 3 9 of 12 Overall recyclability 18 of 20 Result Good

Since the CEVA content in examples 1-7 varies from 2.5 to 5% maximum, all versions will have 18 points with a "Good" recyclability rating. The European and Chinese equivalents contain PVDC barrier material and are not recyclable.

Claims (5)

1. A multilayer barrier film for forming ostomy and urostomy bags, comprising a barrier layer consisting of a copolymer of ethylene and vinyl alcohol, outer layers on both sides of the barrier layer and connected to it by means of an adhesive layer, and at least one intermediate noise-insulating layer between the adhesive layer and the outer layer, wherein the adhesive layer contains a polyolefin grafted with maleic anhydride, characterized in that the outer layers contain 49.5-95 wt.% of a polyolefin elastomer or ethylene vinyl acetate copolymer and 5-50.5 wt.% of linear low-density polyethylene, the intermediate noise-insulating layer contains 63-95 wt.% of ethylene vinyl acetate copolymer or low-density polyethylene and 5-37 wt.% of linear low-density polyethylene. 2. A multilayer barrier film for forming ostomy and urostomy bags according to claim 1, characterized in that the content of ethylene units in the ethylene-vinyl alcohol copolymer is 24-48 wt.%. 3. A multilayer barrier film for forming ostomy and urostomy bags according to claim 1, characterized in that the polyolefin elastomer is selected from ethylene-octene, ethylene-butene copolymers or mixtures thereof. 4. A multilayer barrier film for forming ostomy and urostomy bags according to claim 1, characterized in that the ethylene-vinyl acetate copolymer contains 7-40 wt.% vinyl acetate units. 5. A multilayer barrier film for forming ostomy and urostomy bags according to claim 1, characterized in that the adhesive layer is made from a mixture of 10-90 wt.% polyolefin with grafted maleic anhydride and 90-10 wt.% linear low-density polyethylene.