JP5323294B2 - Stomatological pouch formed from chlorine-free multilayer thin film with a barrier layer of polyamide blend - Google Patents

Description

  The present invention relates to a chlorine-free multilayer thin film having a barrier layer made of a polyamide mixture and a hole making bag formed from the thin film.

Problems to be solved by the prior art and the invention

  The perforating membrane should have excellent odor barrier properties to avoid functional disturbances to the user and should minimize noise when bent or wrinkled. Typically, a foraminous thin film utilizes polyvinylidene chloride (PVDC) or a copolymer of vinylidene chloride and a monomer such as methyl acrylate or vinyl chloride as a gas barrier layer of a multilayer thin film. ing. Such a multilayer thin film exhibits good resistance to odor propagation and relatively low noise. However, they are considered harmful to the environment when conventionally incinerated in many countries. The chlorinated polymer is considered to generate hydrochloric acid as a by-product of incineration and cause hydrochloric acid released from the combustion gas of the incinerator. Furthermore, chlorinated polymers are believed to form toxic dioxin derivatives that are byproducts of incineration that are retained in ash, and there are problems with solid waste disposal methods.

  Unfortunately, thin films formed from chlorine-free barrier resins are harder and noisier than conventional thin films utilizing PVDC-based resins and do not meet the characteristics of conventional chlorinated thin films for perforation. Thus, it can be manufactured by coextrusion from raw materials that are free of chlorine and can be used easily, and is heat-fusible, excellent in flexibility, and noisy when bent or wrinkled. There is a need to provide a multilayer thin film that is small and impervious to fecal odors.

  US Pat. No. 5,567,489 discloses a multilayer barrier film in which the chlorine-free barrier layer is made of amorphous nylon, crystalline nylon, a copolymer of ethylene and vinyl alcohol, or a mixture thereof. The data presented in the above patents show that it is a quiet multilayer thin film comparable to a general commercial chlorinated thin film, but experience has shown that such a chlorine-free thin film. Was found to be significantly noisier than the chlorine-containing thin films used in the manufacture of pouches. General knowledge has shown that chlorine-free barrier resins are highly elastic and hard and are not suitable for production of low-noise thin films for hole making. This is true for all nylon (polyamide) barrier resins, whether crystalline or amorphous. It also includes hydrolyzed ethylene-vinyl acetate copolymers known as ethylene-vinyl alcohol copolymers and high nitrile-containing acrylonitrile or methacrylonitrile copolymers known as nitrile resins. This is also true for other known chlorine-free barrier resins.

  Other references describing techniques relating to chlorine-free multilayer thin films include US Pat. Nos. 5,496,295, 5,643,375, 5,087,713 and 5,895,694.

Means for solving the problem

An important aspect of the present invention is that amorphous nylon (polyamide) becomes an odor barrier by mixing nylon with an olefin polymer or copolymer modified with an anhydride having a density of 0.89 g / cm ³ or less. It was found that the noise characteristics of a multilayer thin film used as a layer can be effectively reduced without affecting the barrier characteristics. The olefin polymer or copolymer modified with anhydride should be in the range of about 10-30% of the total barrier layer weight, and preferably in the range of 15-25%.

  The multilayer thin film has at least one skin layer made of ethylene polymer or copolymer, preferably two skin layers, and an adhesive adhesive layer interposed between each skin layer and the mixed amorphous nylon barrier layer. Yes. Each tacky adhesive layer consists primarily of an ethylene polymer modified with an anhydride, such as a polyethylene or ethylene / vinyl acetate copolymer containing anhydride groups that can promote adhesion with a polyamide-containing barrier layer. .

  As a result, the heat-sealable multilayer thin film has a very excellent odor barrier property, and at the same time, is a known chlorine-free thin film in which the odor barrier layer is formed of nylon, ethylene-vinyl alcohol copolymer or nitrile resin. Since it is relatively soft (low elasticity) and quiet compared to it, it is particularly useful for a hole making procedure. With respect to the generation of noise when bending, the chlorine-free multilayer thin film of the present invention is comparable to a conventional pore-forming thin film having a chlorine-containing barrier thin film. Therefore, a bag formed of the multilayer thin film of the present invention has characteristics comparable to a high-quality bag formed of a chlorine-containing component and does not adversely affect the environment.

  The features, advantages and objects of the invention will be apparent from the following detailed description and drawings.

  The chlorine-free multilayer film of the present invention can be produced by standard coextrusion techniques including casting or blow molding. In the multilayer thin film, an adhesive layer is preferably interposed between five layers, that is, the skin layer and the barrier layer, and a chlorine-free barrier thin film is preferably sandwiched between the two heat-sealed skin layers. However, the advantages of the present invention can also be achieved at least partially in a three-layer structure having a barrier layer, a single skin layer, and an adhesive layer.

FIG. 1 shows a chlorine-free multilayer thin film 10 having an odor barrier layer 11 sandwiched between adhesive layers 12 and 13 and skin layers 14 and 15. The odor barrier layer 11 basically consists of a mixture of an amorphous polyamide (nylon) resin and an olefin polymer or copolymer modified with an anhydride. Unlike crystalline polyamides, which are fully aliphatic, amorphous polyamides have a partially aromatic structure, typically a condensation of an aliphatic diamine and an aromatic diacid, or an equal molar amount of diacid combined with the diamine. Manufactured by doing. Although any amorphous polyamide resin could be used, advantageous results are obtained with the polyamide resin marketed by DuPont under the name “Selar PA3426”. Selar PA3426 is believed to be substantially amorphous having a density of about 1.19 g / cm ³ . Selar PA3426 has higher melt strength than conventional crystalline nylon and can be used under a wide range of processing conditions. Selar PA3426 is produced by condensation of hexamethylenediamine, terephthalic acid and isophthalic acid, where 65-80% of the polymer is a derivative of hexamethylene-isophthalamide.

The amorphous polyamide resin constituting the chlorine-free barrier layer is a main component of the mixture and occupies 70 to 90% by weight of the mixture. The olefin polymer or copolymer modified with anhydride is about 10-30% by weight of the total barrier layer weight, preferably 15-25% by weight. The density of the olefin polymer modified with anhydride should be less than 0.89 g / cm ³ , and preferably less than 0.87 g / cm ³ . Olefin polymers modified with anhydrides with a density greater than 0.89 g / cm ³ are effective as reinforcing agents, but they can reduce the elastic modulus and noise of thin films obtained with low density polymers. Absent. The olefin polymer or copolymer is functionalized by treatment with an unsaturated carboxylic anhydride. Although the mechanism of the improvement by the anhydride is not completely elucidated, it is considered that a graft reaction occurs between the polymer and the unsaturated anhydride. It is believed that unsaturated carboxylic anhydrides can be used to provide functional groups, and maleic anhydride appears to be particularly effective for that purpose. The amount of maleic anhydride required to functionalize the olefin polymer is very low and less than 2% by weight. The density of the olefin polymer is not affected by such small amounts of anhydride modification. An example of an olefin polymer modified with an anhydride is the product “Fusabond MN493D” manufactured by DuPont. Fusabond MN493D is an ethylene-octene copolymer modified with 0.5% maleic anhydride and has a density of 0.869 g / cm ³ . Although known to function as a crystalline nylon reinforcement, Fusabond MN493D is expected to reduce the elastic modulus and noise of amorphous nylon without destroying or reducing the odor barrier properties of the barrier layer 11. There is an effect that is not possible. Similar effects can be achieved with modified olefin polymers with relatively low density anhydrides such as ethylene-propylene copolymers and ethylene-propylene-diene terpolymers (EPM and EPDM). EPM and EPDM have a density of 0.85 to 0.86 g / cm ³ and are suitable for improvement with maleic anhydride. Due to the immiscible nature of these mixtures, mixing of nylon with anhydride modified olefin polymers is performed using a pair of screw compound extruders with screws rotating in the same or opposite directions. be able to. As a result, the olefin phase can be uniformly dispersed in the nylon phase. The mixture is extruded, cut into pellets, and then extruded into a thin film.

  The skin layers 14, 15 are formed of an ethylene-based polymer or a copolymer of ethylene and an alpha olefin such as hexane or octene. A suitable resin is a copolymer of ethylene and an octene comonomer under the action of a metallocene catalyst, such as an ethylene-octene copolymer sold under the name “Exact 8201” from Exxon Chemical.

  Adhesive layers 12 and 13 must be able to bond both the skin layer and the barrier layer. Polyethylene, ethylene-vinyl acetate copolymer (EVA), or ethylene-methyl acrylate copolymer (EMA) modified with functional anhydride groups is considered particularly preferred. EVA-based anhydride-modified resins such as “Bynel 3860” or “Bynel 3861” or polyethylene-based anhydride-modified resins such as “Bynel 41E557” are all made by DuPont and are preferred. I know. It is believed that the function of these anhydride-modified resins that act as adhesion promoters is due to the interaction of the anhydride groups in the adhesive layer and the nylon amine groups in the barrier layer.

  The total thickness of the multi-layered film in the case of 5 layers should be in the range of about 2-5 mils, preferably in the range of about 3-4 mils. For the barrier layer 11, the thickness should be in the range of 0.1 to 1.0 mil. The lower limit (0.1 mil) is determined by the capability of the extrusion molding machine, and the upper limit (1.0 mil) is the physical value obtained by the barrier layer when obtaining a multilayer thin film having a low elastic modulus and low noise characteristics. It is decided by the characteristic. The thickness of the barrier layer is preferably in the range of about 0.2 to 0.4 mil, and 0.3 mil is optimal considering all factors such as softness, quietness, and ease of extrusion. It is thought that. Conversely, the skin layers 14 and 15 are made much thicker than the barrier layer sandwiched between them. For example, the skin layer can have a thickness in the range of about 0.5-2.5 mils, but is preferably 1-2 mils, approximately an order of magnitude relative to the thickness of the odor barrier layer 11. Can be big.

  FIG. 2 shows an exemplary pouch 16 having walls 16a and 16b formed from the multilayer film of FIG. Pneumoplasty is an operation that creates an opening in order to discharge waste products between two luminal organs or from the luminal organs outside the body. The membranes face each other along the outer periphery of the bag, indicated at 17, and are contoured with a sealed, heat-sealed skin layer. The wall of the bag has an opening 18 for receiving a fistula. A fistula refers to an opening that is surgically made between luminal organs or from the luminal organs to the outside of the body in order to pass bodily fluids and discharges. An adhesive attachment ring 19 is attached around the opening for attachment to the skin surface of the patient's surroundings. The bag is depicted as a one-piece instrument as shown, but if desired, the bag can be a two-piece perforation instrument if a mechanical coupling ring is used in place of the adhesive attachment ring 19 It becomes one part.

In order to better understand the present invention, examples are shown below, but the technical scope of the present invention is not limited to the following examples.
Example 1
Example 1 shows the properties of a mixture of amorphous nylon (Selar PA3426 from DuPont) and polyolefin modified with anhydride (Fusabond MN493D from DuPont). These resins were mixed and granulated using a twin screw compound extruder. The mixed resin was extruded into a three layer A / B / A thin film structure using a Killion extruder. A is polyethylene and B is a mixture of nylon. Since there is no adhesive layer, the polyethylene skin layer A can be peeled off from the nylon mixture layer B, and the single layer B of various blends can be tested against a single layer thin film made of 100% amorphous nylon (Selar PA3426). It was. The Secant Modulus at 2% elongation of a single layer thin film was measured in the stretch direction (MD) and its perpendicular direction (TD) according to ASTM D882 at a strain rate of 0.1 inch / inch. The results are shown in Table 1 below.

This shows that the addition of Fusabond MN493D to Selar PA3426 reduces the secant elastic modulus. A low secant modulus indicates that the mixed resin is softer than 100% amorphous nylon. The reduction in the secant modulus further allows the production of a soft and quiet nylon-based multilayer film, as shown in the examples below.
(Example 2)
Five layers of thin films were produced by co-extrusion casting according to the present invention. The total thickness of the thin film was 3.3 mils, and the barrier layer thickness was 0.32 mils. The structure of the thin film is A / B / C / B / A. A is a polyethylene-based resin (Exxon modified by adding 5% anti-blocking suspension concentrate (EXT4226TSE from A-Charman) and 3% low density polyethylene (LD200.48 from Exxon Chemical). Exact 8201) manufactured by Kagaku. B is an adhesive layer made of an ethylene-vinyl acetate copolymer (Bynel 3601 manufactured by DuPont) modified with an anhydride. C represents a mixture of 15 parts by weight of an elastic polyolefin (Fusabond MN493D) modified with an anhydride to 85 parts by weight of amorphous nylon (Selar PA3426).

  The thin film is cut into a size of 4 inches × 4 inches as shown in FIG. 3A, and the square sheet 20 is fixed to the fixed member 21 as shown in FIG. 3B. Attached to the attached cylindrical piece 22, both ends 23 of the sheet 20 were joined to form a cylinder shape. One end side 25 of the cylinder 24 is fixed to the cylindrical piece 22, and the other end side 26 of the cylinder 24 is 70 cycles / minute at an angle of 15 degrees in the direction of the arrow 28 with respect to the shaft 27 of the cylinder 24. The noise generated by the reciprocating vibration was measured with a noise level meter. For comparison, the same test was performed on a commercially available thin film for pore making (a comparative example) having a chlorine-containing barrier. The results are shown in Table 2 below.

In Table 2, dBA is a weighted average considering the perception of human sound over the entire frequency range, and dB in the frequency bands of 8 kHz and 16 kHz represents noise in a higher frequency range and indicates the pitch of the sound. Therefore, the dBA and dB values in Table 2 indicate that the thin film sample, which is an example of the present invention, is much quieter than the comparative sample whose center layer is based on PVDC.
(Example 3)
Five layers of thin films were produced according to the present invention by co-extrusion casting. As a result, a thin film having a total thickness of 3.2 mils and a barrier layer thickness of 0.28 mils was obtained. The structure of the thin film is A / B / C / B / A and the same composition as the thin film of Example 2 except that the adhesive layer B is polyethylene-based (Bynel 41E557 manufactured by DuPont). It is. The film was tested for quietness as described in Example 2. The results are shown in Table 3 below. Table 3 includes comparative examples of commercially available thin films for pore surgery having a PVDC chlorine-containing barrier layer.

Similar to Example 2, the dBA, 8 kHz and 16 kHz dB values in Table 3 indicate that the thin film sample of Example 3 is considerably quieter than the comparative sample where the center layer is PVDC.
Example 4
The films of Examples 2 and 3 were tested for odor transmission according to the provisions of British Standard 7127, Part 101, Addition G. The method tests the odor transmission of colonic and ileostomy bag materials, according to the British Standards Institute in London.

  Both of the above thin films showed that the improvement of the nylon barrier layer did not deleteriously affect the odor barrier properties of the thin film as a result of the test.

  In addition, a quantitative test of the barrier properties of the thin film of Example 2 was performed using dimethyl disulfide, indole and skatole, three compound models of fecal odor. For comparison, the same test was performed on a commercial foraminous thin film having a chlorine-containing (PVDC) barrier layer. Exhaust gas analysis was performed by gas chromatography using a flame ionization detector. Table 4 below shows the permeation time (minutes) and the concentration of each component in the exhaust airflow after 60 hours.

  Better barrier properties can be expected for thin films with long permeation times and low concentrations in gases. The thin film of Example 2 is superior to the thin film of the comparative example containing chlorine in these respects, and shows that it has an excellent function as a stool odor barrier.

  Although specific examples of the present invention have been described in detail in the above embodiments, those skilled in the art can make modifications without departing from the technical scope of the present invention.

Effect of the invention

  Since the chlorine-free multilayer thin film of the present invention is configured as described above, it is soft, has low noise when bent, has excellent odor barrier properties, and does not contain chlorine, so it is suitable as a pouch for pore surgery. Can be used.

  It is sectional drawing of the Example of the multilayer barrier thin film of this invention.   FIG. 2 is a front view of a pouch for pouches formed from the multilayer barrier thin film of FIG. 1.   It is a figure explaining the test method of the quietness of a thin film, Fig.3 (a) is a perspective view of a sheet | seat for a test, FIG.3 (b) is a figure which shows a testing machine and its test method.

DESCRIPTION OF SYMBOLS 10 ... Chlorine-free multilayer thin film 11 ... Odor barrier layer 12, 13 ... Adhesive layer 14, 15 ... Skin layer 16 ... Bag 16a, 16b ... Wall 17 ... Outer peripheral edge part 18 ... Opening part 19 ... Mounting ring

Claims (9)

A pouch having two side walls, each side wall being coextruded with at least one heat-sealable skin layer and an adhesive layer interposed between the skin layer and the barrier layer A non-chlorine multilayer thin film having the barrier layer, the skin layers of each side wall facing each other and thermally fused along the peripheral edge of the bag, and the barrier layer of each side wall is made of an amorphous polyamide resin. An odor barrier layer comprising an olefin polymer or copolymer modified with an anhydride mixed at 10 to 30% by weight of the total barrier layer, and the olefin polymer or copolymer modified with the anhydride. The coalesce has a density of 0.89 g / cm ³ or less, the skin layer on each side wall is an ethylene polymer or copolymer or a mixture thereof, and the adhesive layer on each side wall is an anhydride Improved ethylene polymer or copolymer Pore-forming surgery for a bag that contains, characterized in that the.
Wherein the olefin polymer or anhydride to improve the copolymer, 0.1% to 2% of a bag according to claim 1, wherein maleic anhydride.
The olefin polymer or copolymer, 0.5% ethylene and improved maleic anhydride - bag of claim 1 wherein the octene copolymer.
A pair of the skin layer and the adhesive layer are provided on one surface of the barrier layer, and another pair of the skin layer and the adhesive layer are provided on the other surface of the barrier layer. The bag according to claim 1 or 3 .
The bag according to claim 4 , wherein the skin layer is polyethylene or a copolymer of ethylene and alpha olefin.
The bag according to claim 4 , wherein the adhesive layer is polyethylene modified with an anhydride or an ethylene-vinyl acetate copolymer modified with an anhydride.
The bag according to claim 4, wherein the barrier layer has a thickness of 0.2 to 0.4 mil, and the chlorine-free multilayer thin film has a total thickness of 3 to 4 mil.
The amorphous polyamide resin, hexamethylenediamine, a condensate of terephthalic acid and isophthalic acid, and the 65% to 80% is, hexamethylene - claim 1 bag according is derived from isophthalamide.
The olefin polymer or copolymer, a bag of claim 1 wherein 15 to 25% total barrier layer weight per.

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