Method for manufacturing an article comprising a rubbery film-based article firmly secured to a substrate

Abstract

To provide a method of manufacturing an article including a rubbery film base article, at least a portion of which is rigidly fixed to a base material.SOLUTION: The present invention relates to a method of manufacturing an article including a rubbery film base article, at least a portion of which is rigidly fixed to a base material, including the steps of: a) preparing a film base article made of an un-crosslinked thermoplastic rubber; b) bringing at least a portion of the film base article into contact with the base material to form a contact region between the film base article and the base material; and c) heat sealing at least a portion of the contact region at a temperature of 190 to 250°C for at least a second.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for making an article comprising a rubbery film-based article at least a portion of which is firmly secured to a substrate. [Background technology]

[0002] Rubber-like film-based articles must be firmly attached to a substrate in several applications. In some applications, the substrate is also made of rubber or a rubber-like material, even the same rubber or rubber-like material as the rubber-like film-based article. Thus, in these applications, two or more rubber films can be bonded together to form a multilayer structure. Alternatively, different components of the article are bonded together to form a final article with a complex design, some or all of which are made of rubber or a rubber-like material. In other applications, the substrate is made of a non-rubber material, such as polyurethane, polyethylene terephthalate, nylon, or polyethylene. For example, a certain balloon catheter includes a balloon as a film-based article made of rubber or a rubber-like material, which is fixed to a tube, e.g., as a substrate made of polyurethane. In other applications, a surgical glove as a film-based article made of rubber is bonded to a sleeve, e.g., as a substrate made of polyethylene, or to a fabric substrate, e.g., the arm portion of a surgical gown. Other examples are rubbery breathable films for wound dressings, rubber seals in protective clothing, shoes with rubber soles, clothing with rubber parts, etc.

[0003] Typically, rubber film-based articles, i.e., articles made of one or more films each made of vulcanized or crosslinked rubber, are secured to substrates made of rubber, rubber-like materials, non-rubber polymeric materials, or fabrics, respectively, by glue or adhesive. However, this method has several drawbacks. First, the seal strength of the glue bond is insufficient in several cases, or the seal strength, while initially acceptable, decreases over time to unacceptable values, thereby limiting the service life of these articles. Furthermore, most glues are not heat-resistant and soften with increasing temperature, which also limits the service life of these articles. In addition, the peel strength and impact resistance of glue bonds are typically quite low. Furthermore, reproducibly securing two complex-shaped components to each other with glue is a challenge. Summary of the Invention [Problem to be solved by the invention]

[0004] In view of the above, the object underlying the present invention is to provide a method for manufacturing an article comprising a rubbery film-based article at least a portion of which is firmly secured to a substrate, which method does not require the use of glues, adhesives, etc., yet results in an article in which the rubbery film-based article is firmly and permanently secured to the substrate. [Means for solving the problem]

[0005] According to the invention, the object is a method for manufacturing an article comprising a rubbery film-based article at least partly firmly fixed to a substrate, comprising the following steps: a) providing a film-based article made of a non-crosslinked thermoplastic rubber; b) contacting at least a portion of the film-based article with a substrate to form a contact area between the film-based article and the substrate; and c) heat-sealing at least a portion of the contact area at a temperature of 190-250°C for at least 1 second This is satisfied by providing a method comprising:

[0006] The use of a non-crosslinked thermoplastic rubber film-based article allows the film-based article to be heat-sealed to a substrate, which is not possible when vulcanized, i.e., crosslinked, rubber is used. Heat sealing results in a strong, particularly permanently strong bond between the substrate and the film-based article. In particular, when a non-crosslinked thermoplastic rubber film-based article is heat-sealed to a substrate made of the same or a different non-crosslinked thermoplastic rubber, an impressively high seal strength is obtained. Therefore, the use of glue is completely unnecessary, and the above-mentioned disadvantages associated with the use of glue are avoided in the method according to the present invention. However, by appropriately selecting a non-crosslinked thermoplastic rubber material, a film-based article having the rubber-like mechanical properties required for the application, such as suitable tensile strength, suitable elasticity, suitable modulus, suitable puncture resistance, etc., i.e., properties equivalent to those of a vulcanized rubber film-based article, can be produced and used in the article.

[0007] The term "non-crosslinked thermoplastic rubber" means, according to the invention, any thermoplastic elastomer, ie any copolymer having thermoplastic as well as elastomeric properties.

[0008] By "copolymer" is meant, according to the present invention, any polymer comprising two or more monomers, i.e., biopolymers, terpolymers, quaterpolymers, and even more monomer containing polymers.

[0009] "Film-based article" according to the present invention refers to any article made of one or more films having a thickness of 20 mm or less, such as gloves, catheter balloons, shoe soles, etc. Thus, the term "film-based article" also encompasses films, or in other words, films are considered as film-based articles in this patent application. DETAILED DESCRIPTION OF THE INVENTION

[0010] In step a), a film-based article made of a non-crosslinked thermoplastic rubber is provided. The film-based article made of a non-crosslinked thermoplastic rubber is an article that comprises at least 50% by weight, preferably at least 75% by weight, more preferably at least 90% by weight, even more preferably at least 95% by weight, and even more preferably at least 98% by weight. Most preferably, the film-based article made of a non-crosslinked thermoplastic rubber is entirely made of the respective rubber.

[0011] Preferably, the non-crosslinked thermoplastic rubber used in step a) of the method according to the invention is a thermoplastic styrenic block copolymer, which makes it possible to produce film-based articles with suitable rubber-like mechanical properties, such as suitable tensile strength, elasticity, modulus and puncture resistance.

[0012] Examples of suitable thermoplastic styrenic block copolymers are those selected from the group consisting of styrene-isoprene-styrene block copolymers (SIS), styrene-isobutylene-styrene block copolymers (SIBS), styrene-butadiene-styrene block copolymers (SBS), styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymers (SEEPS), and any combination of two or more of the foregoing thermoplastic styrenic block copolymers.

[0013] Good results are obtained particularly when the thermoplastic styrenic block copolymer is a styrene-isoprene-styrene block copolymer (SIS).

[0014] According to a particularly preferred embodiment of the invention, the non-crosslinked thermoplastic rubber used in step a) of the process according to the invention is a branched block copolymer of general formula (I): ABY-(BA) n(I) (In the formula, each A is independently a polymer block composed of at least 80 mole percent alkenyl aromatic hydrocarbon; the content of A by weight of the total weight of the polymer is in the range of 5-20%; Y is the residue of a coupling agent having a functionality greater than 2; the degree of branching is n+1, where n is an integer from 2 to 4; each B is independently an olefinically unsaturated polymer block composed of at least 80 mole % of one or more conjugated dienes; The block copolymers have coupling efficiencies ranging from 70 to 100%.

[0015] Films made from this material not only have suitable mechanical properties, such as excellent tensile strength and elasticity, but are also heat sealable, resulting in heat sealed articles with very high sealing strength.

[0016] Particularly good results are obtained when each A block independently has a weight average molecular weight in the range of 10,000 to 12,000 g / mol and / or each B block independently has a weight average molecular weight in the range of 80,000 to 120,000 g / mol. According to the present invention, molecular weight is determined according to ASTM 3536 using monodisperse polystyrene standards.

[0017] The concept of the present invention can be further developed by providing that the non-crosslinked thermoplastic rubber used in step a) is a branched block copolymer of general formula (I) each A is independently a polymer block composed of at least 90 mole % alkenyl aromatic hydrocarbon; the content of A by weight of the total weight of the polymer is in the range of 9-12%; each B is independently an olefinically unsaturated polymer block composed of at least 90 mole % of one or more conjugated dienes; It is proposed to be a block copolymer with coupling efficiency in the range of 84-100%.

[0018] Even more preferably, the branching degree is 4 and the coupling efficiency is 90-100%.

[0019] In a further development of the inventive concept, the non-crosslinked thermoplastic rubber used in step a) of the process according to the invention is a branched block copolymer of general formula (I), where each B is a polymer block composed of at least 90 mol % of isoprene and each A is a polymer block composed of at least 90 mol % of styrene. In this embodiment, the non-crosslinked thermoplastic rubber used in step a) is a branched SIS.

[0020] Thus, most preferably, the non-crosslinked thermoplastic rubber used in step a) of the process according to the invention is a branched block copolymer of general formula (I) each A is independently a polymer block composed of at least 90 mole % styrene; the content of A by weight of the total weight of the polymer is in the range of 9-12%; Y is the residue of a coupling agent having a functionality greater than 2; the degree of branching is n+1, where n is an integer from 2 to 4; each B is independently an olefinically unsaturated polymer block composed of at least 90 mole % isoprene; The block copolymers have coupling efficiencies ranging from 84 to 100%. each A block independently has a weight average molecular weight in the range of 10,000 to 12,000 g / mol; Each B block independently has a weight average molecular weight in the range of 80,000 to 120,000 g / mol.

[0021] The present invention is not particularly limited with respect to the thickness of the film, and the film-based article prepared in step a) can be made from this film as long as the film has sufficiently good mechanical properties and is not too thick to be heat-sealed any further. For example, the film of the film-based article prepared in step a) can have a thickness of 1 μm to 10 mm, preferably 10 μm to 1 mm, more preferably 50 μm to 500 μm, and most preferably 150 μm to 250 μm.

[0022] The present invention is not particularly limited with respect to the method for preparing the film-based article prepared in step a). The easy and cost-effective method for manufacturing the film-based article prepared in step a) allows the preparation of even film-based articles with complex shapes with minimal dimensional tolerances. An example of this method is the coagulation dipping method using a non-crosslinked thermoplastic rubber latex. The coagulation dipping method is based on first immersing a mold having a surface profile matching the surface profile of the film to be formed in a coagulation agent to bond the coagulation agent to the surface of the mold, and then immersing the thus-treated mold in rubber latex to form a polymer film. The coagulation agent on the surface of the mold causes the rubber contained in the latex to coagulate and precipitate on the surface of the mold, resulting in a film-based article in the shape of the surface profile of the mold. As stated above, the term "latex" is specifically used in the present invention to mean a dispersion of particles of non-crosslinked thermoplastic rubber in a medium, preferably an aqueous medium.

[0023] More specifically, the coagulation immersion method comprises the following steps: i) immersing the former in a coagulant solution; ii) removing the mold from the coagulant solution and drying the mold; iii) dipping the dried mold into a latex of a non-crosslinked thermoplastic rubber to form a film-based article made of the non-crosslinked thermoplastic rubber on the mold; iv) removing the mold with the film-based article thereon from the latex and pre-curing the film; v) optionally leaching the film-based article in water; vi) curing the film-based article; and vii) Removing the film-based article from the mold may include:

[0024] Typically, the mould is washed and dried in an oven, for example at about 100°C, before use in step i).

[0025] Preferably, the coagulant solution is an aqueous solution containing one or more different alkaline earth metal salts. Good results are obtained, in particular, with aqueous solutions containing calcium salts, such as calcium chloride or calcium nitrate, which have sufficiently high solubility in water. The content of alkaline earth metal salt(s) in the aqueous solution may be between 5 and 40% by weight, for example, 10 to 20% by weight, for example, about 15% by weight. An immersion time of 15 to 60 seconds, preferably 25 to 40 seconds, is usually sufficient to bond a sufficient amount of coagulant to the surface of the mold.

[0026] The mold removed from the coagulant solution in step ii) can be dried in an oven at a temperature between 90 and 110°C, and then immersed in a latex of a non-crosslinked thermoplastic rubber in step iii) to form a film-based article made of the non-crosslinked thermoplastic rubber on the mold. The latex is preferably an aqueous dispersion of the non-crosslinked thermoplastic rubber in water, and the latex preferably has a concentration of the non-crosslinked thermoplastic rubber of 50 to 80% by weight, more preferably 60 to 70% by weight, and most preferably 63 to 67% by weight. To achieve a specific uniform distribution of the non-crosslinked thermoplastic rubber particles in the latex, it is suggested that the latex contain a small amount of surfactant, preferably an anionic surfactant such as a rosinate salt. The latex used in step iii) can be diluted to a concentration of 30 to 35% by weight of the non-crosslinked thermoplastic rubber.

[0027] Latex is made in the following steps: a) emulsifying a solution of non-crosslinked thermoplastic rubber with soap in a high shear mixer; b) removing the solvent from the formed emulsion; c) adjusting the solids content of the resulting solvent-free emulsion; and d) pasteurizing the resulting latex It can be prepared by a method comprising:

[0028] The mold with the film-based article thereon, removed from the latex, is pre-cured in step iv) preferably at a temperature between 90 and 110°C for 30 to 60 seconds, preferably at a temperature between 95 and 105°C for 50 to 70 seconds, for example about 30 seconds or about 60 seconds.

[0029] After removing the film-based article from the mold in step v), the film-based article is optionally leached in water, preferably warm water, in step vi) (1-10 minutes in water having a temperature of 40-60°C, e.g., about 5 minutes in water having a temperature of about 50°C) to remove residual chemicals, such as surfactants, from the film-based article, and then the film-based article is finally cured in step vii). Good results are obtained particularly when curing is carried out at 80-150°C for 10-30 minutes, more preferably at 100-120°C for 15-25 minutes.

[0030] Regarding the substrate, the present invention is not particularly limited as long as the substrate can be heat-sealed to the film-based article. For example, the substrate can be made of a material selected from the group consisting of non-crosslinked thermoplastic rubber, polyamide, polyester, thermoplastic polyurethane, and any combination of two or more of the above materials.

[0031] In terms of the resulting seal strength, the best results are achieved when the substrate (the film-based article to which it is fixed by heat sealing) is made of a non-crosslinked thermoplastic rubber, most preferably the same non-crosslinked thermoplastic rubber as the film-based article. In particular, the substrate may be a film-based article, and more specifically, two identical film-based articles in this embodiment, so that they can be fixed to each other by heat sealing. In this case, a seal strength higher than 20 N / 25 mm can be obtained. In this embodiment, an article having a multilayer structure can be produced by heat-sealing two or more films or formed film-based articles made of the same or at least very similar materials to each other. Alternatively, this embodiment can be used to produce highly complex molded articles by heat-sealing the components of the final structure to each other.

[0032] The substrate may, in another embodiment, be a fabric, such as a fabric made of wool or a thermoplastic polymer, the porous surface structure of such fabrics supporting heat sealing.

[0033] According to the present invention, heat sealing is carried out in step c) at a temperature of 190-250°C for at least 1 second. Preferably, heat sealing is carried out within this temperature range for at least 5 seconds, more preferably at least 10 seconds, even more preferably at least 20 seconds, even more preferably at least 30 seconds, and most preferably at least 50 seconds, for example about 60 seconds. There is no particular upper limit to the heat sealing time, and it may be 240 seconds, 180 seconds, or 120 seconds.

[0034] According to a particularly preferred embodiment of the present invention, in particular when using film-based articles made with block copolymers of general formula (I), the heat-sealing is carried out in step c) at a temperature of 190 to 230°C, more preferably at a temperature of 190 to 220°C, even more preferably at a temperature of 195 to 210°C, for example at a temperature of about 200°C.

[0035] Furthermore, the heat sealing is preferably carried out in step c) at atmospheric pressure or slightly above atmospheric pressure.

[0036] Heat sealing can be performed with any commercially available heat sealing device, such as using a heat seal bar, which allows the pressure and temperature during heat sealing to be the same, or at least essentially the same, over the heat seal contact area.

[0037] In most applications, the heat sealing in step c) is performed along a line on the contact area formed in step b) between the film-based article and the substrate. However, it is also possible to heat-seal the film-based article to the substrate along two or more lines, all of which may be within the border area of ​​the film-based article and / or the substrate. Typically, the width of the heat-sealed area is 3-5 mm.

[0038] As presented above, very high seal strengths can be obtained depending on the materials of the film and substrate of the film-based article. Thus, preferably, the seal strength of the heat-sealed contact area between the film-based article and the substrate is at least 5 N / 25 mm, more preferably at least 5 N / 25 mm, even more preferably at least 6 N / 25 mm, even more preferably at least 7 N / 25 mm, even more preferably at least 9 N / 25 mm, even more preferably at least 12 N / 25 mm, even more preferably at least 15 N / 25 mm, and most preferably at least 20 N / 25 mm. According to the present invention, seal strength is measured as defined in ASTM F88-F88M. For example, seal strength can be determined using an Instron 3365 tensile instrument. Each tail of a sample of the film-based article is clamped in opposing grips of the tensile instrument, and the seal remains unsupported during the test. A grip separation speed of 500 mm / min may then be used, and the force is measured by a load cell on the Instron 3365 tensile instrument, with results reported in Newtons / 25 mm.

[0039] Due to the high seal strength obtainable with the method according to the invention, the method does not require the use of glue or adhesive coatings, and therefore preferably the method according to the invention is carried out without the use of glue or adhesive coatings.

[0040] Furthermore, the method according to the present invention preferably does not include any corona discharge treatment.

[0041] A further aspect of the present invention is an article comprising a rubbery film-based article at least a portion of which is firmly secured to a substrate, which can be obtained using the method described above.

[0042] The concept of the present invention is further developed to provide a film-based article having the following properties: i) a tensile strength of at least 19 MPa; ii) a 10% Young's modulus of less than 0.25 MPa; and iii) a modulus of at least 5.6×10 at 120° C. 5 and a complex modulus in Pa·s, and a seal strength in the heat-sealed contact area between the film-based article and the substrate of at least 5 N / 25 mm, preferably at least 5 N / 25 mm, more preferably at least 6 N / 25 mm, even more preferably at least 7 N / 25 mm, even more preferably at least 9 N / 25 mm, even more preferably at least 12 N / 25 mm, even more preferably at least 15 N / 25 mm, and most preferably at least 20 N / 25 mm. More preferably, the film-based article provided in step a) has at least two of the above properties i), ii) and iii), and most preferably, the film-based article provided in step a) has all three properties i), ii) and iii). Tensile strength is preferably measured according to ASTM D412. Young's modulus in Pa is calculated according to the equation E = tensile stress / tensile strain = (F * L) / (A *The tensile properties described by this equation are measured according to ASTM D412. Complex modulus is determined according to ISO 6721-4:2019.

[0043] The article according to the present invention may comprise a surgical glove as the rubbery film-based article and a surgical gown or the arm portion of the surgical gown as the substrate, the contact area between the surgical glove and the surgical gown being preferably at the end portion opposite the finger portion of the glove and at an appropriate position on the surgical gown so as to fit the person wearing it.

[0044] In an alternative embodiment of the present invention, the article comprising a film-based article and a substrate is a rubbery film-based article, and the substrate and the film-based article are, independently of one another, selected from the group consisting of gloves, customized garments, entertainment industry articles, shoe soles, and any combination of two or more of the foregoing forms.

[0045] In a further alternative embodiment of the present invention, the article comprises a catheter balloon as the rubbery film-based article and a catheter tube made of a thermoplastic polymer, preferably a thermoplastic polyurethane, as the substrate.

[0046] In a further alternative embodiment of the present invention, the article comprises as a substrate a breathable film for a wound dressing, a sleeve for a rubber glove or a rubber seal for protective clothing.

[0047] As set out above, in accordance with the present invention, it is possible, and indeed preferred, that the film-based article and substrate are not secured to one another by a glue or adhesive coating.

[0048] The invention will now be illustrated by way of non-limiting examples. [Example]

[0049] [Example 1] to [Example 3] A film made of a non-crosslinked thermoplastic rubber was prepared by a coagulation dipping method using Cariflex IR2GL1 diluted to 35% by weight solids as a latex, distributed by Cariflex Pte. Ltd. This Cariflex IR2GL1 is a latex of a block copolymer included in the general formula (I), and the preparation includes the following steps: The mold or former was washed and dried at 100°C. The mould was immersed in a coagulant solution, i.e. an aqueous solution containing 15% by weight of calcium nitrate, The mold was removed from the solution and dried at 100°C. The mold was immersed in the above-mentioned latex, The mold with the latex film formed on it was removed from the latex and pre-cured at 100°C for 1 minute. The latex film on the mold was leached in water having a temperature of 50°C for 5 minutes. The film on the mold was cured in an oven at 120°C for 20 minutes. The mold with the formed film was cooled to ambient temperature and then the film was removed from the mold.

[0050] The resulting film of non-crosslinked thermoplastic rubber was then cut into strips 25 mm wide and 0.30 mm thick.

[0051] The above procedure was repeated to obtain films of non-crosslinked thermoplastic rubber with a width of 25 mm and thicknesses of 0.22 mm and 0.43 mm, respectively.

[0052] In Example 1, strips 0.22 mm thick, in Example 2 strips 0.30 mm thick, and in Example 3 strips 0.43 mm thick were sealed together. The strips were placed on top of each other and sealed together with a manually operated Rajasystem along a line of contact having a width of 2-3 mm and a length of 25 mm, and pressure was applied manually to the heat sealing device. The temperature measured offline during sealing was 190-220°C.

[0053] The seal strength of the heat-sealed contact area was then measured using an Instron 3365 tensile instrument. Each tail of the laminated heat-sealed film sample was clamped in opposing grips of the tensile instrument, leaving the seal unsupported during the test. A grip separation speed of 500 mm / min was then used, and the force was measured with a load cell on the Instron 3365 tensile instrument, with the results recorded in Newtons / 25 mm. Additionally, if failure, i.e., failure of one of the two films or in the seal area, was initiated, this was noted and recorded.

[0054] The following results were obtained:

[0055] [Table 1]

[0056] [Example 4] to [Example 11] Strips of uncrosslinked thermoplastic rubber film having a width of 25 mm and a thickness of 0.30 mm, as described for Examples 1-3, were heat-sealed to substrates made of other materials under the conditions described above for Examples 1-3. These were film strips made of polyurethanes distributed by Huntsman as PU Irogran® and having product codes 1778E4506 (Example 4), A85E4993 (Example 5), A85E4994 (Example 6), and A92E5670 (Example 7), polyurethanes distributed by Gerlinger Industries (Example 8), nylon (Example 9), polyester (Example 10), and polyethylene (Example 11).

[0057] The following results were obtained:

[0058] [Table 2]

[0059] Comparative Example Example 1 was repeated, except that a strip of film formed from Cariflex IR2GL1 was heat sealed to a strip made from isoprene rubber latex, Cariflex IR0401, rather than being heat sealed to another strip of the same film.

[0060] Heat sealing was not achieved.

Claims

1. 1. A method of manufacturing an article comprising a rubbery film-based article at least a portion of which is secured to a substrate, comprising the steps of: a) providing a film-based article made of a non-crosslinked thermoplastic rubber, The non-crosslinked thermoplastic rubber is a block copolymer of general formula (I): A-BY-(B-A) n (I) (In the formula, each A is independently a polymer block composed of at least 90 mole percent alkenyl aromatic hydrocarbon; the content of A by weight of the total weight of the polymer is in the range of 9-12%; Y is the residue of a coupling agent having a functionality greater than 2, the degree of branching is n+1, and n is an integer from 2 to 4; each B is independently an olefinically unsaturated polymer block composed of at least 90 mole percent of one or more conjugated dienes; the block copolymer has a coupling efficiency in the range of 84 to 100%; each A block independently has a weight average molecular weight in the range of 10,000 to 12,000 g / mole; each B block independently has a weight average molecular weight in the range of 80,000 to 120,000 g / mol, said molecular weight being determined in accordance with ASTM 3536 using monodisperse polystyrene standards; and A film-based article is prepared by a coagulation dipping process using a non-crosslinked thermoplastic rubber latex, the coagulation dipping process comprising the following steps: i) immersing the former in a coagulant solution; ii) removing the mold from the coagulant solution and drying the mold; iii) dipping the dried former into said latex to form a film-based article on the former; iv) removing the mold from the latex and pre-curing the latex together with the film-based article; v) leaching the film-based article in water; vi) curing the film-based article; and vii) Removing the film-based article from the mold. Including; b) contacting at least a portion of the film-based article with a substrate to form a contact area between the film-based article and the substrate, wherein the substrate is made of one or more materials selected from the group consisting of polyamide, polyester, thermoplastic polyurethane, fabric, and any combination of two or more of the foregoing materials; and c) heat-sealing at least a portion of the contact area at a temperature of 190-250°C for at least 1 second Including, the seal strength of the heat-sealed contact area between the film-based article and the substrate is at least 5 N / 25 mm; and The method wherein at least a portion of the article is firmly secured to the substrate without the use of glue or an adhesive coating.

2. The method of claim 1, wherein the block copolymer of general formula (I) is selected from the group consisting of styrene-isoprene-styrene block copolymer (SIS), styrene-isobutylene-styrene block copolymer (SIBS), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), and any combination of two or more of the above-mentioned thermoplastic styrenic block copolymers.

3. 2. The method of claim 1, wherein in formula (I), each B is a polymer block composed of at least 90 mol % isoprene and each A is a polymer block composed of at least 90 mol % styrene.

4. The method according to any one of claims 1 to 3, wherein the film of the film-based article provided in step a) has a thickness of from 10 μm to 1 mm.

5. The method according to any one of claims 1 to 3, wherein the heat sealing is carried out at a temperature of 190 to 250°C for at least 10 seconds.

6. The method of any one of claims 1 to 3, wherein the seal strength of the heat-sealed contact area between the film-based article and the substrate is at least 6 N / 25 mm.

7. A method according to any one of claims 1 to 3, wherein no corona discharge treatment is performed.

8. An article comprising a substrate and a rubbery film-based article at least partially secured to the substrate without the use of glue or adhesive coating, (i) the rubbery film-based article is made of a non-crosslinked thermoplastic rubber; (ii) the substrate is made of a material selected from the group consisting of polyamide, polyester, thermoplastic polyurethane, fabric, and any combination of two or more of the foregoing materials; and (iii) the film-based article is at least partially in contact with the substrate to form a contact area, and at least a portion of the contact area is heat-sealed; the seal strength of the heat-sealed contact area between the film-based article and the substrate is at least 5 N / 25 mm; The non-crosslinked thermoplastic rubber is a block copolymer of general formula (I): A-BY-(B-A) n (I) (In the formula, each A is independently a polymer block composed of at least 90 mole percent alkenyl aromatic hydrocarbon; the content of A by weight of the total weight of the polymer is in the range of 9-12%; Y is the residue of a coupling agent having a functionality greater than 2, the degree of branching is n+1, and n is an integer from 2 to 4; each B is independently an olefinically unsaturated polymer block composed of at least 90 mole percent of one or more conjugated dienes; the block copolymer has a coupling efficiency in the range of 84 to 100%; each A block independently has a weight average molecular weight in the range of 10,000 to 12,000 g / mole; An article wherein each B block independently has a weight average molecular weight in the range of 80,000 to 120,000 g / mole, said molecular weights being determined in accordance with ASTM 3536 using monodisperse polystyrene standards.

9. The film of the film-based article has a tensile strength of at least 19 MPa, a 10% Young's modulus of less than 0.25 MPa, and a modulus of at least 5.6 x 10 at 120°C. ５ 9. The article of claim 8, having a complex modulus of 0.1 Pa·s and a seal strength of at least 5 N / 25 mm in the heat-sealed contact area between the film and the substrate of the film-based article.

10. i) the rubbery film-based article has the form of a surgical glove and the substrate is a surgical gown or the arm portion of a surgical gown; or ii) the film-based article and the substrate are rubbery film-based articles, and the substrate and the film-based article are, independently of one another, selected from the group consisting of gloves, customized garments, entertainment industry articles, shoe soles, and any combination of two or more of the foregoing forms; or iii) the rubbery film-based article has the form of a catheter balloon and the substrate is a catheter tube made of thermoplastic polyurethane, or iv) An article according to claim 8 or 9, wherein the substrate is a breathable film for a wound dressing, a sleeve for a rubber glove or a rubber seal for protective clothing.

11. The article of any of claims 8 to 10, wherein the film-based article and the substrate are not secured to one another by a glue or adhesive coating.

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