Layered material

Abstract

The present invention relates to a layered material comprising a substrate and one or more layers A, wherein one or more layers A comprise 50 weight% or more of a branched copolyester, wherein the weight% is based on the total weight of said one or more layers A, and the branched copolyester has a melting temperature of 125°C to 185°C and a Mz / Mw of 3.5 or more, and a melt flow index (MFI) of 10 g / 10 min or less when measured at 190°C with 2.16 kg. Additionally, the present invention relates to a film comprising one or more layers A.

Description

Technology Field

[0001] The present invention relates to a layered material, a method for manufacturing a layered material, a film suitable for application to a layered material, and an application of a layered material. Background Technology

[0002] Laminated materials are known and are applied, for example, to the inflatable protective cushions of vehicles, also known as airbags. These protective cushions prevent passengers from frontal or side collisions. Such cushions must comply with numerous requirements. Particularly in the case of side applications, these cushions must be able to maintain a specific pressure for a specific period of time. In the event of a vehicle rollover, the gas inside the cushion must remain inside for a longer period to prevent passengers from being ejected from the vehicle and to prevent passenger injury.

[0003] The laminated materials currently used in airbags are manufactured by laminating foil onto a fabric layer, for example, as described in US6607797. A disadvantage of these gas bag materials is that the materials used exhibit insufficient hydrolytic resistance and / or heat resistance. Another solution is to use copolyester, for example, as described in WO18230721. A disadvantage of the above solution is that the foil must be manufactured using a blown film process that requires the use of a support layer or a three-layer film. This support layer must be discarded after production, which makes the process expensive or requires the use of a thicker solution, thereby requiring more cost and material.

[0004] Accordingly, the object of the present invention is to provide a laminated material comprising a layer that can be manufactured by a blown film process without the need for a support layer and / or can exist with a thinner thickness.

[0005] This objective is obtained by a laminated material comprising a substrate and one or more layers A, wherein one or more layers A comprise 50 weight% or more of branched copolyester, where weight% is based on the total weight of layers A, and the branched copolyester has a melting temperature of 125°C to 185°C, a Mz / Mw of 3.5 or more, and a melt flow index (MFI) of 10 g / 10 min or less when measured at 190°C with 2.16 kg.

[0006] Surprisingly, the laminated material of the present invention can achieve sufficient adhesion to a substrate while allowing for stable blown film characteristics with easy manufacturing, a high blowing rate, and excellent melt stability.

[0007] "Multilayer" is understood herein to include two or more layers, and potentially three or more or even four or more layers, and may include even more than four layers depending on the intended use of the laminated material. The maximum number of layers in a multilayer varies depending on the intended use and may be up to 10.

[0008] "(Co)polyester" is understood to include both polyester and copolyester in this specification.

[0009] "(Co)polyamide" is understood herein to include both polyamide and copolyamide.

[0010] Melting temperature (T) of thermoplastic materials and especially copolyesters m) is typically measured using a differential scanning calorimeter (DSC) in accordance with ISO 11357-3:2011 under a nitrogen atmosphere. The melting temperature is defined as the peak temperature determined using a heating rate of 10°C / min during the second heating, and is therefore the maximum height of the endothermic temperature in the thermogram associated with the highest temperature melting peak. The instrument must be calibrated with an indium standard. An aluminum pan is used to hold a small amount, preferably 5 to 10 mg, of the thermoplastic copolyester elastomer. The sample is heated at a constant rate of 10°C / min to a temperature at least 20°C higher than the highest melting temperature, preferably at least 240°C. Subsequently, the sample is cooled at a rate of 10°C / min to a temperature of 0°C or lower, more preferably at -50°C or lower, to remove any variable thermal history. Subsequently, the sample is heated again at a constant rate of 10°C / min to a temperature at least 20°C higher than the highest melting temperature, preferably at least 240°C. Brief explanation of the drawing

[0011] FIGS. 1 through 6 schematically illustrate various embodiments of a laminated material. Dotted lines indicate surfaces that can be partially or substantially completely buried, as further shown in FIGS. 5 and 6, respectively. Figure 1 illustrates a stacked material comprising a substrate and one layer A. Figure 2 illustrates a stacked material in which an additional layer B exists between the substrate and layer A. Figure 3 illustrates a stacked material similar to Figure 1, where an additional layer B is located on the opposite side of the substrate. Figure 4 shows a stacked material in which a substrate is in contact with layer A and an additional layer B. FIG. 5 illustrates a schematic diagram in which layer A is partially embedded in a substrate, which may be a case in which the substrate contains voids, such as in the case of a woven or nonwoven fabric. The substrate is indicated by a circle, and the arrow indicates the maximum thickness of layer A. FIG. 6 illustrates a schematic diagram in which layer A is almost completely embedded in a substrate, which may be a case where the substrate contains voids, such as in the case of a woven or non-woven fabric. The substrate is indicated by a circle, and the arrow indicates the maximum thickness of layer A. Figure 7 illustrates an example of a SEC chromatogram with integration limit (vertical line) and reference line (horizontal line) settings for measuring molar mass moment and molar mass distribution values ​​based on the refractive index (RI) and differential viscosity chromatogram (IV-DP). Specific details for implementing the invention

[0012] substrate

[0013] The laminated material according to the present invention includes a substrate.

[0014] "Substrate" is defined herein as a material on which a process is performed to produce a laminated material, preferably the process is to bond a film, and more preferably the process is to laminate a film to produce a laminated material.

[0015] The substrate can be selected from various materials and forms and depends on the intended use of the laminated material. The substrate may be in the form of, for example, woven fabric, nonwoven fabric, film, laminate, fabric, plate, sheet, foam, and combinations thereof. When applied, for example, to an airbag, more preferably to a side curtain airbag, the substrate is preferably a woven fabric, such as, for example, textile.

[0016] The substrate may comprise various materials, such as plastics including, for example, polyamides, polyesters, polyolefins, polyurethanes, and copolymers and / or mixtures thereof. The substrate may also comprise other materials, such as, for example, wood, cotton, linen, glass, metal, and combinations of plastics and other materials. For use in airbags, the substrate is preferably a woven fabric comprising polyamide, copolyamide, polyester, or copolyester, more preferably polyester or copolyester, as this facilitates recycling; more preferably, the substrate is a one-piece woven fabric comprising (co)polyester, and even more preferably, the substrate is substantially composed of (co)polyester.

[0017] One piece woven (OPW) is known as a product made using a special weaving technique that eliminates the sewing process. Using OPW, it is possible to create bags that can be made with a single weave structure.

[0018] Preferably, the material of the substrate has a melting temperature measured by DSC according to ISO 11357-3:2011, wherein the melting temperature is higher than the melting temperature of the branched copolyester of layer A, preferably at least 20°C higher, and more preferably at least 30°C higher. This facilitates the lamination of layer A onto the substrate. If the substrate comprises various materials, the melting temperature of the substrate is preferably defined as the maximum melting temperature of the individual materials.

[0019] The substrate may include voids, for example, if the form is a woven fabric, a nonwoven fabric, a foam, or a one-piece woven fabric. When applied directly to the substrate, layer A may be partially embedded in the substrate as schematically shown in FIG. 5. In this case, the thickness of layer A is defined as the maximum thickness indicated by the arrow in FIG. 5. When an additional layer B is applied directly to the substrate, this layer may also be partially embedded in the substrate.

[0020] Floor A

[0021] The laminated material according to the present invention comprises one or more layers A, also referred to as “layer A”. Layer A comprises a branched copolyester having a melting temperature of 125°C to 185°C and an Mz / Mw of 3.5 or more when measured by DSC according to ISO 11357-3:2011, and an MFI of 10 g / min or less when measured by 2.16 kg at 190°C.

[0022] Layer A comprises at least 50 weight%, more preferably at least 65 weight%, and more preferably at least 80 weight% of branched copolyester, wherein the weight percentage is based on the total weight of Layer A. Layer A is also substantially composed of branched copolyester.

[0023] Layer A comprises a branched copolyester having a melting temperature of 130°C to 175°C, more preferably 140°C to 165°C, and even more preferably 145°C to 160°C. The melting temperature of the branched copolyester can be adjusted by the amount of hard segments and / or soft segments, and by the type of hard segments and / or soft segments. Preferably, the branched copolyester comprises hard segments PBT and PBI, compared to a branched copolyester comprising only PBT as a hard segment, which reduces the melting temperature of the branched copolyester.

[0024] Layer A may contain additional additives, such as, for example, heat stabilizers, colorants, nucleating agents, UV stabilizers, lubricants, and plasticizers. Typically, these additional additives are present in Layer A in an amount of 10 weight% or less, preferably 5 weight% or less, with respect to the total weight of Layer A.

[0025] Layer A may be in contact with the substrate as shown in FIG. 1, but may also be separated by an additional layer B as shown in FIG. 2. Layer A may also be partially embedded in the substrate, which is preferably the case where the substrate is a woven fabric. This particular situation is schematically illustrated in FIG. 5. Layer A may also be almost completely embedded in the substrate as schematically illustrated in FIG. 6.

[0026] Layer A can be manufactured by various methods, such as extrusion coating, cast film processes, and blown film processes. Preferably, Layer A is manufactured by a blown film process. Surprisingly, Layer A containing 50 weight percent or more of branched copolyester based on the total weight of Layer A (said that the branched copolyester has a melting temperature of 125°C to 185°C and an Mz / Mw of 3.5 or more, and an MFI of 10 g / 10 min or less when measured at 190°C with 2.16 kg) allows for manufacturing by a simple blown film process. The advantages of Layer A manufactured by a blown film process are that the support layer can be omitted, a higher processing speed can be used during the manufacture of Layer A, a lower thickness can be obtained and / or a higher expansion rate can be achieved, which consequently provides a wider film width. Layer A can be manufactured as a single layer, but Layer A can also be manufactured as a multilayer including at least one additional layer B.

[0027] Branched copolyester

[0028] Layer A comprises a branched copolyester having a melting temperature of 125°C to 185°C and an Mz / Mw of 3.5 or more, and an MFI of 10 g / 10 min or less when measured at 190°C with 2.16 kg.

[0029] "Copolyester" is understood herein as a polymer comprising a hard segment and a soft segment of polyester. The hard segment of the polyester may be, for example, polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polybutylene isophthalate (PBI), polyethylene isophthalate (PEI), polyethylene naphthalate, polybutylene naphthalate, and polypropylene naphthalate, and combinations thereof. Preferably, the hard segment is a combination of PBT and PBI, as this is readily available and allows for a lower melting temperature of the copolyester.

[0030] The soft segment may be selected from a wide range of polymers, for example, polytetramethylene oxide (PTMO), polyethylene oxide (PEO), polypropylene oxide (PPO), block copolymers of poly(ethylene oxide) and poly(propylene oxide), linear aliphatic polycarbonates, polybutylene adipate (PBA), derivatives of dimeric fatty acids or dimeric fatty acid diols, linear aliphatic polyesters, or combinations thereof. Preferably, the soft segment comprises polytetramethylene oxide (PTMO) because it provides sufficient hydrolytic stability.

[0031] The branched copolyester has an Mz / Mw of 3.5 or more, preferably 3.7 or more, more preferably 3.9 or more. The branched copolyester has an Mw / Mn of 2.1 or more, more preferably 2.2 or more, even more preferably 2.3 or more, and most preferably 2.4 or more. A higher Mz / Mw value indicates a higher degree of branching, which is advantageous for processing the branched copolyester into a film.

[0032] Number average molecular weight (Mn), weight average molecular weight (Mw), and Z average molecular weight (Mz) can be determined by the size exclusion (SEC) method as described below. The SEC method for molar mass measurements is generally described in ASTM: D5296-11 (2011). Additionally, ASTM standard D 5226-98 (2010) defines the solvents that can be used for polymer analysis. For thermoplastic copolyester elastomers, hexafluoroisopropanol containing 0.1 wt% potassium trifluoroacetate is used. All size exclusion chromatography measurements are performed on a Viscotek GPCMax VE2001 solvent / sample module system equipped with a TDA305 triple detector array. Three PFG linear XL columns from PSS Polymer Standards Service GmbH are used for chromatographic separation. The detector and column are operated at 35°C. In conventional size exclusion chromatography, the polymer is dissolved in hexafluoroisopropanol containing 0.1 wt% potassium trifluoroacetate at a concentration ranging from 1.0 to 1.5 mg / mL, which is also used as an eluent in SEC analysis at a flow rate of 0.8 mL / min. Molar mass and molar mass distribution are determined by a triple detection method using refractive index, differential viscosity, and orthogonal light scattering signals. Refractive index indices (dn / dc's) in the range of 0.22 to 0.24 mL / g are used for the calculation of molecular weight mean and molar mass distribution. The calculation of molar mass moment and molar mass distribution is performed using OmniSEC software version 4.7. The refractive index is determined by the integration of the entire refractive index chromatogram. The integration limit for the calculation of molar mass moment and molar mass distribution is set by considering the start and end of the differential viscosity chromatogram recorded for the sample of interest. Figure 7 provides an example of setting the integration limit.Further details regarding these calculations can be found in the literature [Niehaus, DE, Jackson, C. “Size exclusion chromatography of step-growth polymers with cyclic species: theoretical model and data analysis methods”, Polymer 41 (2000), 259-268].

[0033] If a multi-branched copolyester is present in layer A, the total amount of branched copolyester must be at least 50 weight% for layer A, and Mz / Mw, Mw / Mn, melt temperature, and MFI values ​​must be measured for the total amount of branched copolyester.

[0034] The MFI of the branched copolyester is 10 g / 10 min or less when measured at 2.16 kg at 190°C. The MFI can be measured according to ISO 1133-1, procedure B. The measurement is performed using a standard die with an opening of about 2 mm and a melting time of 300 seconds. The amount of sample to be weighed is 4.5 to 5.0 g. Before weighing, the material is dried at 150°C for 2 hours. Preferably, the branched copolyester has an MFI of 7 g / 10 min or less when measured at 2.16 kg at 190°C, more preferably 5 g / 10 min or less, and most preferably 3 g / 10 min or less, as this makes handling easier, particularly when manufactured by a blown film process. If the MFI is very low when measured at 2.16 kg at 190°C, the melt flow stability is not sufficient to be measured at this weight, and a higher weight of 10 kg must be applied. In this case, the MFI is preferably 25 g / 10 min or less, more preferably 20 g / 10 min or less when measured at 190°C with 10 kg.

[0035] Branched copolyesters can be manufactured by known methods, including melt polymerization and, generally, melt finishing to obtain the desired MFI. Other manufacturing techniques include, for example, reactive extrusion using a compound having two or more reactive groups in the copolyester, for example, an epoxy, carbodiimide, or isocyanate group, after melt polymerization. Examples of isocyanate compounds include methylene diphenyl diisocyanate (MDI), liquid methylene diphenyl diisocyanate (1-MDI), polymeric MDI, triphenyl diisocyanate, dianiside diisocyanate, diphenyl ether diisocyanate, naphthalene diisocyanate, isocyanate, phenylenethiocyanate, triphenylmethane triisocyanate, triphenylmethane triisocyanate, diisocyanate methyl ester, methoxylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, diisocyanate dimer, isopropylidene bis(4-cyclohexyl isocyanate), dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, etc. Two or more isocyanates may also be used. These can be used in an amount of, for example, 0.01 weight% to 2.00 weight% for branched copolyesters.

[0036] Branching is achieved by using a branching agent in the process of manufacturing branched copolyesters.

[0037] "Branching agent" is known by itself and is understood herein to be a molecule having three or more functional groups capable of reacting with a monomer, oligomer, or polymer to introduce branching into the polymer. Branching agents include, for example, trimethylolpropane (TMP), di(trimethylolpropane), pentaerythritol, dipentaerythritol, tripentaerythritol, trimethyl trimellitate, tributyl trimellitate, 2-hydroxymethyl-1,3-propanediol, trioctyl trimellitate (TOTM), and trihexyl trimellitate (THTM). The branching agent may be used in an amount of 0.01 wt% to 2.00 wt% relative to the branched copolyester, depending on the degree of branching required.

[0038] Layered material

[0039] The laminated material may optionally include one or more additional layers B. One or more additional layers B may be located between the substrate and layer A (Fig. 2), but when layer A and the substrate are in contact with each other, one or more additional layers B are located on the opposite side of layer A (Fig. 4) or on the opposite side of the substrate (Fig. 3). The laminated material may also include a plurality of additional layers B, for example, at both locations opposite the two-sided layer A and / or opposite the two-sided substrate. The plurality of additional layers B may be the same material, but may also include different materials.

[0040] Layer B can be manufactured together with Layer A, thus as a film comprising two or more layers. Layer B may also be manufactured separately and then added during the manufacture of the laminated material.

[0041] Layer B may comprise various materials, e.g., polyester, copolyester, polyamide, copolyamide, thermoplastic polyurethane, polyolefin, grafted polyolefin, or a combination thereof, and may be a single layer or a multilayer. Preferably, Layer B comprises a branched copolyester, as this has the advantage of further stabilizing melt stability during blown film processing. More preferably, Layer B comprises the branched copolyester T used in Layer A. m Higher melting temperature T mB It includes a material having the advantage that when laminated to a substrate, layer A melts and flows partially or potentially completely into the open structure of the substrate, as shown in FIGS. 5 and FIGS. 6, respectively, while layer B is not deformed and maintains its strength.

[0042] Layer B may contain additional additives, such as, for example, heat stabilizers, colorants, nucleating agents, UV stabilizers, lubricants, and plasticizers. Generally, these additional additives are present in Layer B in an amount of at least 10 weight%, preferably at least 5 weight%, of the total weight of Layer B.

[0043] Layer B can be manufactured by a method as disclosed, similar to Layer A. Preferably, Layers A and B are manufactured together by a multilayer film process using a blown film process.

[0044] The laminated material according to the present invention can be manufactured by a process known in itself, such as laminating layer A to a substrate, or by using an adhesive to apply layer A to a substrate.

[0045] "Laminating" is understood herein to include a heating and pressure application step in which a substrate or layer A is melted. Preferably, layer A and / or B are melted and the substrate remains substantially solid. Most preferably, layer A is melted and the substrate remains substantially solid.

[0046] Film containing layer A

[0047] The present invention also relates to a film suitable for application to a laminated material comprising a substrate, said film comprising or composed of one or more layers A comprising a branched copolyester having a melting temperature of 125°C to 185°C and a melting temperature of 3.5 or more Mz / Mw, and having an MFI of 10 g / 10 min or less when measured at 190°C with 2.16 kg. All preferred details and embodiments disclosed above also expressly indicate preferred details and embodiments relating to this film, particularly the branched copolyester.

[0048] Preferably, the film is 1*10 -5 Up to 100*10 -3 mm, more preferably 1 x 10⁻⁶ -5 mm to 60*10 -3 mm, more preferably 1*10 -5 mm to 50*10 -3 mm, most preferably 1 x 10⁻⁶ -5 mm to 40*10 -3 It has a thickness of mm.

[0049] Preferably, the film is manufactured by a blown film process, as this process allows for easy manufacturing. In one embodiment, the film consists of layer A. In another embodiment, the film comprising one or more layers A further comprises another layer referred to as layer B below. The above embodiment referring to layer B also relates to a film according to the present invention comprising one or more layers A and further comprising layer B.

[0050] In a preferred embodiment, the film according to the present invention comprises one or more layers A and layer B and is manufactured by a blown film process. More preferably, the film according to the present invention comprises one or more layers A and layer B as disclosed above, wherein layer B is a branched copolyester T used in layer A. m Higher melting temperature T mB It includes a material having This has the advantage that when a film comprising layers A and B is laminated to a substrate, layer A melts and flows partially or potentially completely into the open structure of the substrate, while layer B remains undeformed and maintains its strength. Most preferably, layer B is a (co)polyester, as this facilitates the recycling of the film.

[0051] The film according to the present invention can be advantageously used in the manufacture of airbags, most preferably in the manufacture of side curtain airbags, where protection against gases and / or liquids, for example, or protection against mechanical effects is required.

[0052] Preferably, the film according to the present invention comprises or is composed of a branched copolyester, wherein the branched copolyester comprises a hard segment of polybutylene terephthalate (PBT) and polybutylene isophthalate (PBI), and a soft segment of polytetramethylene oxide (PTMO), polyethylene oxide (PEO), polypropylene oxide (PPO), a block copolymer of poly(ethylene oxide) and poly(propylene oxide), a linear aliphatic polycarbonate, a polybutylene adipate (PBA), a derivative of a dimeric fatty acid or a dimeric fatty acid diol, a linear aliphatic polyester, or a combination thereof. More preferably, the soft segment is polytetramethylene oxide (PTMO).

[0053] The laminated material is suitable for a wide range of applications, including airbags, particularly side curtain airbags, roofs, house wrap applications, protective films, and medical applications such as drapes.

[0054] Examples

[0055] Comparative substance A is Hytrel® 4056 (available from Dupont). Hytrel® 4056 is a thermoplastic copolyetherester based on polytetramethylene oxide (PTMO) soft segments and PBT / PBI hard segments with a molecular weight of 1000. The melting temperature of Hytrel® 4056 is 150°C and the MFI is 5 g / 10 min (2.16 kg, 190°C, ISO 1133-1, Procedure B).

[0056] Comparative Material B is a copolyester comprising a PBT / PBI hard segment and a polytetramethylene oxide (PTMO) with a molecular weight of 1000 as a soft segment. The melting temperature of Comparative Material B is 162°C and the MFI is 4.5 (2.16 kg, 190°C, ISO1133-1, Procedure B). Comparative Material B was prepared via a two-step process. First, a base polymer with a relatively low viscosity was prepared using a melt polymerization process known to those skilled in the art. In the second step, reactive extrusion was performed using varying amounts of liquefied diphenylmethylene diisocyanate (l-MDI) to increase viscosity and achieve the desired MFI as specified in Table 1. The reactive extrusion process was carried out on a ZSK40MC+ extruder (operating at 200 rpm) with a throughput of 54 kg / hr and a barrel temperature of 250°C. Comparative Material B had an l-MDI content of 0.56 wt%.

[0057] Materials 1 to 4 were prepared by adding a branching agent to comparative material B at the feed throat of a reactive extrusion device and increasing the amount of l-MDI.

[0058] Material 1 contains 0.4 m / m% trimethylolpropane, 1.3 to 1.5 m / m% l-MDI and 100-0.4-[l-MDI-material 1]+[l-MDI-comparative B] m / m% comparative material B as branching agents.

[0059] Substances 2, 3 and 4 contain 0.3 m / m% pentaerythritol, 1.2 to 1.6 m / m% l-MDI and 100-0.3-[l-MDI-substance]+[l-MDI-comparative B] m / m% comparative substance B as branching agents.

[0060] Material 2 has 1.55 wt% l-MDI, material 4 has 1.25 wt% l-MDI, and both materials 1 and 3 have 1.45 wt% l-MDI, where wt% is relative to the total amount of material.

[0061] The melt strength of the tested material was typically measured using the Rheotens test according to ISO 16790:2005. The Rheotens test indicates the drawability of a molten polymer, which is important for many industrial processes such as extrusion, fiber spinning, film blowing, and blow molding. High melt strength is an indicator of excellent bubble stability and / or a higher blowing rate during the film blowing process.

[0062] The experimental setup for measuring melt strength consisted of a capillary extrusion rheometer (Gottfert Rheograph 75) and a Leotens device (Leotens 71.97, manufacturer: Goettfert) as a take-up device. The force measurement range of the Leotens 71.97 is 0 to 2.0 N, and the resolution is 1 mN. The melt strength results presented here followed the following measurement protocol. First, the samples were dried under vacuum at 80°C for at least 14 hours. Then, the granules were fed into the preheated rheometer oven (T = 190°C, diameter = 12 mm) of the capillary rheometer (filling time < 1 min) and waited for 5 minutes to allow the granules to melt. A capillary die with L / D = 30 / 2 mm and a flat angle of incidence (180°) was used for all materials to extrude the melt into a filament. The piston speed of the rheometer was V 피스톤 It was set to 0.049 mm / s, resulting in a filament speed of 1.8 mm / s. The drawdown distance between the die exit and the take-up wheel was set to 10 cm to allow for isothermal conditions. The wheel gap was set to 0.2 mm, and silicone oil was sprayed onto the wheel to prevent sticking of the extruded strand. The laboratory temperature and humidity were controlled to 22±2 ℃ and 45±5 rH, respectively. At the start of the experiment, the take-up speed of the Leotens wheel was set to the filament exit speed at which tension becomes zero. The acceleration of the take-up wheel was 1.2 mm / s 2 The setting was applied, and the speed began to increase slowly until the polymer filament broke. Tensile force versus drawdown speed was analyzed, and the corresponding melt strength values ​​were reported. Melt strength measurements were repeated at least three times for each sample, and the mean and standard deviation of the melt strength values ​​are reported in Table 1. The dependence of melt strength on temperature was also investigated, and the expected decrease in melt strength was observed as the temperature in the rheometer oven increased.

[0063] The elongation characteristics of these materials, namely melt strength, were successfully measured; however, at high speeds, all filaments began to adhere to the wheel, making it impossible to report the drawdown ratio. Since stable tensile strength was obtained in all experiments, absolute melt strength values ​​could be reported. As no filament breakage was observed, the drawdown ratio could not be reported for any material.

[0064] substance substance Hard segment (weight%) Soft segment (weight%) T m (℃) Mn Mw Mw / Mn Mz / Mw MFI [g / 10 min] at 190℃, 2.16 kg MFI at 190℃, 10 kg [g / 10 min] Melting strength [cN] Comparative substance A 55 45 150 34200 73000 2.1 3.0 5.0 0.6±0.1 Comparative substance B 45 55 162 39600 78000 2.0 1.8 4.5 0.5±0.1 Matter 1 45 55 155 47900 113000 2.4 4.0 1.1 7.2±0.8 Matter 2 45 55 155 55100 143000 2.6 12.1 0.5 6.0±0.5 Matter 3 45 55 155 49100 125000 2.5 8.2 2.5 16.6 Matter 4 45 55 155 43500 92000 2.1 5.1 4.7 0.7±0.1

[0065] Materials 1 to 4 can be suitably used in a blown film process without the need for a support layer and / or may exist at a lower thickness to obtain a film according to the present invention. Surprisingly, the film can be manufactured by a blown film process without the need for a support layer, or a film exhibiting a lower thickness can be manufactured. By laminating these films onto a substrate, a laminated material according to the present invention can be obtained.

[0066] Surprisingly, the melt strength of materials 1 and 2 was much higher than that of comparative materials A and B. Melt strength is an indicator of the expected blowing rate and bubble stability when the materials are used in the blowing film process.

Claims

Claim 1 A layered material comprising a substrate and one or more layers A, wherein the one or more layers A comprise 50 weight percent or more of branched copolyester based on the total weight of the one or more layers A, and the branched copolyester has a melting temperature of 125°C to 185°C and a Mz / Mw of 3.5 or more, and a melt flow index (MFI) of 10 g / 10 min or less when measured at 190°C with 2.16 kg. Claim 2 A laminated material in which layer A is attached to a substrate, as described in paragraph 1. Claim 3 In paragraph 1, one or more layers A are 1*10 -5 mm to 100*10 -3 A laminated material having a maximum thickness of mm. Claim 4 A laminated material according to claim 1, comprising an additional layer B comprising a polyester, a copolyester, a polyamide, a copolyamide, a thermoplastic polyurethane, a polyolefin, or a combination thereof. Claim 5 In paragraph 4, a laminated material in which layer B is attached to layer A. Claim 6 In paragraph 5, a laminated material in which layer A is attached to a substrate. Claim 7 A laminated material according to claim 1, wherein layer A comprises 80 weight percent or more of branched copolyester based on the total weight of layer A. Claim 8 A laminated material according to claim 1, wherein layer A comprises a branched copolyester comprising a hard segment of polybutylene terephthalate (PBT) and polybutylene isophthalate (PBI), and a soft segment of polytetramethylene oxide (PTMO), polyethylene oxide (PEO), polypropylene oxide (PPO), a block copolymer of poly(ethylene oxide) and poly(propylene oxide), a linear aliphatic polycarbonate, a polybutylene adipate (PBA), a derivative of a dimeric fatty acid or a dimeric fatty acid diol, a linear aliphatic polyester, or a combination thereof. Claim 9 A method for manufacturing a laminated material according to any one of claims 1 to 8, comprising the step of laminating a film including layer A to a substrate. Claim 10 A manufacturing method according to claim 9, wherein a film comprising layer A is manufactured by a blown film process. Claim 11 A film comprising or composed of one or more layers A, wherein the layer A comprises 50 weight percent or more of branched copolyester based on the total weight of the layer A, wherein the branched copolyester has a melting temperature of 125°C to 185°C and a Mz / Mw of 3.5 or more, and a melt flow index (MFI) of 10 g / 10 min or less when measured at 190°C with 2.16 kg. Claim 12 A film according to claim 11, wherein one or more layers A comprise 80 weight percent or more of branched copolyester based on the total weight of one or more layers A. Claim 13 A film according to claim 11, wherein the branched copolyester has a melting temperature of 140°C to 160°C and a melt flow index (MFI) of 5 g / 10 min or less when measured at 190°C with 2.16 kg. Claim 14 A film according to any one of claims 11 to 13, wherein the branched copolyester comprises a hard segment of polybutylene terephthalate (PBT) and polybutylene isophthalate (PBI), and a soft segment of polytetramethylene oxide (PTMO), polyethylene oxide (PEO), polypropylene oxide (PPO), a block copolymer of poly(ethylene oxide) and poly(propylene oxide), a linear aliphatic polycarbonate, a derivative of polybutylene adipate (PBA) or a dimeric fatty acid or a dimeric fatty acid diol, a linear aliphatic polyester, or a combination thereof. Claim 15 In paragraph 14, a film in which the soft segment comprises or is made of polytetramethylene oxide (PTMO).

Images