Blowed films, methods of producing the same, and articles

Abstract

The present invention relates to a blown film comprising a spiroglycol-based polyester, a method of producing said blown film and an article comprising said blown film.

Description

[0001] describe Invention Field

[0002] The present invention relates to a blown film comprising a spirocyclic glycol-based polyester, a method for producing the blown film, and an article comprising the blown film. background

[0003] Thermoplastic polyesters, such as polyethylene terephthalate (PET), are versatile and highly useful polymers. They are widely used in many different film applications, such as industrial and consumer product packaging, construction, agriculture, and medical applications, because they typically exhibit many advantageous properties.

[0004] In fact, the versatility of thermoplastic polyesters allows for customization to meet specific application requirements. At the same time, thermoplastic polyesters typically exhibit excellent mechanical properties, including high tensile strength and impact resistance. These characteristics make them ideally suited for packaging films, for example, that need to withstand handling, transportation, and storage without compromising the integrity of the contents.

[0005] In addition, polyesters such as PET possess excellent optical and barrier properties and are easily printable. These properties are advantageous in packaging applications, for example: good optical properties provide high transparency and clarity, allowing consumers to see the packaged goods; barrier properties against moisture, gases, and odors allow for effective control of shelf life; and the possibility of printing on them enables informative packaging designs.

[0006] Furthermore, recycling systems for thermoplastic polyesters such as PET have been established, and the lightweight nature of thermoplastic polyesters can also help reduce transportation costs and carbon emissions, making them an effective environmentally friendly option. Invention Overview

[0007] The applicant notes that, despite the particularly advantageous properties of thermoplastic polyesters such as PET, films made from such polymers are currently primarily produced via cast film / stretching techniques, even though such techniques are subject to numerous technical and performance limitations.

[0008] For example, cast film / stretching technology is not cost-effective and is limited in productivity because significant amounts of waste are generated during the production of cast films due to dimensional irregularities and / or poor layer distribution at the film edges. The applicant also notes that the cost-effectiveness and productivity of the process can be further negatively impacted if such trimmed material is not effectively recycled.

[0009] The applicant also noted that precise control of film thickness and optical properties is a challenge in cast film / stretching technology, and this may also affect the suitability of such films for applications requiring specific film thickness and optical properties, such as packaging, where thin and transparent films are often required.

[0010] The applicant also noted that film blow molding technology offers several advantages over cast film / stretching technology. In particular, the applicant noted that film blow molding is generally more efficient in terms of cost-effectiveness, reduced material waste, lower production costs, and faster production speeds and continuous film production; more efficient in thickness control, as film blow molding allows for precise, flexible, and versatile control of film thickness by adjusting process variables such as air pressure, die gap, and extrusion rate; and more efficient in optical properties. The stretching and orientation of polymer molecules during the blow molding process can also reduce haze and improve light transmittance, making the film more visually appealing and suitable for applications where product visibility is important, such as packaging and display purposes.

[0011] At the same time, the applicant noted that attempts to apply the technology to currently known and used thermoplastic polyesters such as PET have been hampered by the performance of such polymers during film blow molding processes, and that such attempts often necessitate the engineering of specific new polymer grades or the use of special machinery or setups, thereby negatively impacting competitiveness with other materials more suitable for film blow molding.

[0012] Therefore, the applicant believes there is a need in the art to develop suitable thermoplastic polyesters for film blow molding technology.

[0013] Surprisingly, the applicant discovered that this requirement could be successfully met by using a specific series of spirocyclic glycol-based polyesters, which proved suitable for film blow molding technology.

[0014] Therefore, in a first aspect, the present invention relates to a blown film comprising a spirocyclic diol-based polyester comprising a diol component and a dicarboxylic acid component, wherein the diol component comprises, based on the total amount of the diol component, residues of a diol having a spirocyclic diol structure represented by formula (1) from 5 mol% to 65 mol% of the diol component:

[0015] Where R 1 and R 2 Each of the following organic groups is independently represented: aliphatic groups having 1 to 10 carbon atoms, alicyclic groups having 3 to 10 carbon atoms, and aromatic groups having 6 to 10 carbon atoms.

[0016] Surprisingly, the applicant has discovered that this spirocyclic diol-based polyester is suitable for efficient processing to produce blown films, which exhibit a combination of mechanical and optical properties, making them suitable for a wide range of film applications, such as industrial and consumer product packaging, construction, agriculture, medical, and healthcare applications.

[0017] In another aspect, the present invention also relates to the use of a spirocyclic diol-based polyester as defined in the first aspect of the invention for the production of blown films; and to a method for producing blown films, the method comprising the step of blown film production of a spirocyclic diol-based polyester as defined above.

[0018] The applicant indeed noted with surprise that the properties of the blown film thus obtained make it particularly suitable for the production of many products.

[0019] Therefore, in another aspect, the present invention also relates to an article selected from the group consisting of: bags, containers, packaging, pouches, shrink films, strips, agricultural films, greenhouse coverings, mulch films, silage films, vapor barrier films, roofing membranes, geomembranes, laminated articles, surgical drapes, gowns, fabrics, protective covers, linings, window films for heat reduction, protective films for solar panels, and wrapping materials, said article comprising a blown film according to the first aspect of the present invention.

[0020] The advantages of these other aspects of the invention have been disclosed with respect to the blown film according to the first aspect of the invention, and will not be repeated here. Detailed description of the invention

[0021] In a first aspect, the present invention relates to a blown film comprising a spirocyclic diol-based polyester comprising a diol component and a dicarboxylic acid component, wherein the diol component comprises, based on the total amount of the diol component, from 5 mol% to 65 mol% of residues of a diol having a spirocyclic diol structure represented by formula (1):

[0022] Where R 1 and R 2 Each of the following organic groups is independently represented: aliphatic groups having 1 to 10 carbon atoms, alicyclic groups having 3 to 10 carbon atoms, and aromatic groups having 6 to 10 carbon atoms.

[0023] Surprisingly, the applicant has indeed discovered that this spirocyclic diol-based polyester is suitable for efficient processing to produce blown films, which exhibit a combination of mechanical and optical properties, making them suitable for a wide range of film applications, such as industrial and consumer product packaging, construction, agriculture, medical, and healthcare applications.

[0024] Within the framework of this description and in the appended claims, unless otherwise indicated, all numerical entities representing quantities, parameters, percentages, etc., shall be understood to be preceded by the term "about" in all cases. Furthermore, all ranges of numerical entities include all possible combinations of maximum and minimum values ​​and include all possible intermediate ranges, except those specifically pointed out below.

[0025] Unless otherwise defined, all technical and scientific terms used herein generally have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0026] As used in this article, the articles “a” and “an” refer to one or more (i.e., at least one) grammatical object of that article. By instance, “an element” means one or more elements.

[0027] As used herein, the term “about” will be understood by those skilled in the art and will vary to some extent depending on the context in which it is used. As used herein, when referring to measurable values ​​such as quantities, durations of time, and similar values, the term “about” means including a variation of ±20% or ±10% from the specified value, including ±5%, ±1%, and ±0.1%, because such variation is suitable for carrying out the disclosed methods.

[0028] The present invention may contain one or more features disclosed below in one or more aspects of the present invention.

[0029] The blown film according to the present invention comprises a spirocyclic diol-based polyester, wherein the spirocyclic diol-based polyester comprises a diol component and a dicarboxylic acid component. The diol component of the spirocyclic diol-based polyester comprises residues of a diol having a spirocyclic diol structure represented by formula (1) in amounts ranging from 5 mol% to 65 mol% based on the total amount of the diol component.

[0030] Preferably, in the spirocyclic diol-based polyester, the diol component comprises, based on the total amount of the diol component, from 20 mol% to 55 mol%, more preferably from 30 mol% to 45 mol%, residues of the diol having a spirocyclic diol structure represented by formula (1).

[0031] Preferably, the diol having a spirocyclic diol structure is 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]undecane)diethanol).

[0032] The diol component of the spirocyclic diol-based polyester advantageously comprises at least one other diol. Preferably, the diol component comprises residues derived from at least one other diol selected from the group consisting of: ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutanediol; alicyclic diols such as 1,3-cyclohexanediethanol, 1,4-cyclohexanediethanol, 1,2-decahydronaphthalenediethanol, 1,3-decahydronaphthalenediethanol, ... 1,4-Decahydronaphthalenediethanol, 1,5-Decahydronaphthalenediethanol, 1,6-Decahydronaphthalenediethanol, 2,7-Decahydronaphthalenediethanol, tetrahydronaphthalenediethanol, norbornenediethanol, tricyclodecanediethanol, 5-hydroxymethyl-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane and pentacyclododecanediethanol; alkylene oxide adducts of bisphenols such as 4,4′-(1-methylethylidene)bisphenol, methylene bisphenol (bisphenol F), 4,4′-cyclohexylene bisphenol (bisphenol Z) and 4,4′-sulfonyl bisphenol (bisphenol S); and alkylene oxide adducts of aromatic dihydroxy compounds such as hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylbenzophenone and alkylene diols represented by formula (2).

[0033] Where R 3 and R 4 Each of the following organic groups is independently represented: aliphatic groups having 1 to 10 carbon atoms, alicyclic groups having 3 to 10 carbon atoms, and aromatic groups having 6 to 10 carbon atoms.

[0034] In a preferred embodiment, the other diol is selected from the group consisting of ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol; more preferably, the other diol is ethylene glycol.

[0035] Preferably, in the spirocyclic diol-based polyester, the diol component comprises residues derived from the at least one other diol, ranging from 35 mol% to 95 mol%, more preferably from 45 mol% to 80 mol%, and even more preferably from 55 mol% to 70 mol%, based on the total amount of the diol component.

[0036] In a preferred embodiment, in the spirocyclic diol-based polyester, the diol component comprises 20 mol% to 55 mol%, more preferably 30 mol% to 45 mol%, of the diol having a spirocyclic diol structure and 45 mol% to 80 mol%, more preferably 55 mol% to 70 mol%, of at least one other diol, wherein the diol having a spirocyclic diol structure is 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, and the other diol is selected from the group consisting of ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol, and 1,4-cyclohexanediol; more preferably, the other diol is ethylene glycol.

[0037] The spirocyclic diol-based polyester according to the present invention comprises a dicarboxylic acid component.

[0038] Preferably, the dicarboxylic acid component comprises 80 mol% to 100 mol% of terephthalic acid-derived residues based on the total amount of the dicarboxylic acid component.

[0039] In embodiments of the invention, the dicarboxylic acid component of the spirocyclic diol-based polyester advantageously comprises at least one dicarboxylic acid other than terephthalic acid.

[0040] Preferably, the dicarboxylic acid component comprises from 0 mol% to 20 mol% based on the total amount of the dicarboxylic acid component. The mol% is derived from residues of at least one dicarboxylic acid other than terephthalic acid, wherein the dicarboxylic acid other than terephthalic acid is selected from the group consisting of: isophthalic acid, phthalic acid, 2-methylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid, biphenyl dicarboxylic acid, tetrahydronaphthalenedicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, decahydronaphthalenedicarboxylic acid, norbornanedicarboxylic acid, tricyclodecanedicarboxylic acid, pentacyclododecanedicarboxylic acid, isophoronedicarboxylic acid, 3,9-bis(2-carboxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, trimellitic acid, pyromellitic acid, pyromellitic tetracarboxylic acid and tricarboxylic acid.

[0041] The spirocyclic diol-based polyesters according to the invention may also advantageously include polydiol units, for example, polydiol units comprising residues of ternary or higher valence polyols derived from, for example, glycerol, trimethylolpropane, pentaerythritol, etc.

[0042] The spirocyclic diol-based polyesters according to the present invention can be produced by any suitable known method without particular limitation. For example, the spirocyclic diol-based polyesters can be produced by transesterification or direct esterification, which can be carried out by melt polymerization or solution polymerization. Those known in the polymer field as transesterification catalysts, esterification catalysts, etherification inhibitors, polymerization catalysts, various stabilizers such as heat stabilizers and light stabilizers, and polymerization modifiers can all be used. Examples of transesterification catalysts include compounds of manganese, cobalt, zinc, titanium, and calcium. Examples of esterification catalysts include compounds of manganese, cobalt, zinc, titanium, and calcium. Examples of etherification inhibitors include amine compounds.

[0043] Examples of polycondensation catalysts include compounds of germanium, antimony, tin, and titanium. Examples of heat stabilizers include various phosphorus compounds, such as phosphoric acid, phosphorous acid, and phenylphosphonic acid. Additionally, various additives can be used in the production of polyester resins, such as light stabilizers, antistatic agents, lubricants, antioxidants, and release agents.

[0044] Suitable methods for producing spirocyclic diol-based polyesters according to the present invention can also be found, for example, in patent references EP1164155A1 and EP1535945A1.

[0045] A diol having a spirocyclic diol structure represented by formula (1) can be added at any stage in the production of the spirocyclic diol-based polyester according to the invention. For example, the diol having a spirocyclic diol structure can be added after the esterification or transesterification reaction. In the direct esterification method, water can be used to maintain the stability of the slurry.

[0046] The spirocyclic diol-based polyesters according to the invention advantageously exhibit one or more properties that make the polyester particularly suitable for film blow molding.

[0047] Preferably, when measured at a constant temperature of 25°C using an Ubbelohde viscometer in a mixed solvent of phenol and 1,1,2,2-tetrachloroethane in a mass ratio of 6:4, the spirocyclic glycol-based polyester exhibits an intrinsic viscosity ranging from 0.40 dL / g to 1.5 dL / g, more preferably from 0.50 dL / g to 1.0 dL / g, and even more preferably from 0.55 dL / g to 0.75 dL / g.

[0048] Preferably, when measured according to ASTM D7426, the spirocyclic glycol-based polyester exhibits a glass transition temperature of 95°C–110°C.

[0049] Preferably, the spirocyclic glycol-based polyester exhibits a melt flow index of 5 g / 10 min to 25 g / 10 min, more preferably from 7 g / 10 min to 18 g / 10 min, even more preferably from 10 g / 10 min to 18 g / 10 min, and even more preferably from 16 g / 10 min to 18 g / 10 min, measured at 250°C according to ISO 1133.

[0050] Preferably, the molecular weight distribution of the spirocyclic diol-based polyester of the present invention is from 1.5 to 12.0, more preferably from 2 to 10.0, and even more preferably from 2.2 to 8.0. The molecular weight distribution can be adjusted to the range of 2.5 to 12.0 by any technique known to those skilled in the art for this purpose, such as appropriately selecting the amount and timing of addition of the diol having a spirocyclic diol structure represented by formula (1), the molecular weight of the polyester, the polymerization temperature, and the additives.

[0051] Spirocyclodiol-based polyesters according to the present invention are known in the market; for example, one type of spirocyclodiol-based polyester is sold by Perstorp AB under the trademark Akestra™. Akestra™ is available in three different qualities: Akestra™ 90, Akestra™ 100, and Akestra™ 110.

[0052] The blown film according to the present invention comprises at least one spirocyclic diol-based polyester as defined above.

[0053] The blown film may advantageously have a single-layer film structure or a multi-layer film structure.

[0054] When the blown film according to the invention has a multilayer film structure, preferably, the spirocyclic diol-based polyester as defined above is included in at least one layer of the multilayer structure.

[0055] In an embodiment of the present invention, the blown film according to the present invention has a single-layer film structure.

[0056] Preferably, according to the embodiments of the present invention, the blown film comprises from 10 wt% to 100 wt%, more preferably from 15 wt% to 90 wt%, and even more preferably from 20 wt% to 60 wt% of the spirocyclic diol-based polyester based on the total weight of the blown film.

[0057] Preferably, according to the embodiments of the present invention, the blown film comprises at least one other polymer, more preferably polyester, and even more preferably polyethylene terephthalate, in an amount of 0 wt% to 90 wt%, more preferably 10 wt% to 85 wt%, and even more preferably 40 wt% to 80 wt% based on the total weight of the blown film.

[0058] In a preferred embodiment, according to the embodiments of the present invention, the blown film comprises, based on the total weight of the blown film, 10 wt% to 90 wt%, more preferably 20 wt% to 60 wt% of the spirocyclic glycol-based polyester and 90 wt% to 10 wt%, more preferably 40 wt% to 80 wt% of at least one other polymer, said other polymer being polyethylene terephthalate.

[0059] The blown film according to this embodiment of the invention exhibits a unique and advantageous set of mechanical and optical properties, making it particularly suitable for several applications, such as industrial and consumer product packaging, construction applications, agricultural applications, medical applications, and healthcare applications.

[0060] The blown film according to this embodiment of the invention advantageously exhibits a suitable combination of optical properties, tensile properties, impact resistance and tear resistance.

[0061] In another embodiment of the invention, the blown film according to the invention has a multilayer film structure.

[0062] Preferably, according to the embodiments of the present invention, the blown film comprises at least one layer comprising a polyester based on spirocyclic diol as defined above.

[0063] Preferably, the at least one layer comprises, based on the total weight of the layer, 10 wt% to 100 wt%, more preferably 10 wt% to 90 wt%, and even more preferably 20 wt% to 60 wt% of the spirocyclic glycol-based polyester.

[0064] Preferably, the at least one layer comprises at least one other polymer, more preferably polyester, or even more preferably polyethylene terephthalate, in an amount of 0 wt% to 90 wt%, more preferably 10 wt% to 90 wt%, more preferably 40 wt% to 80 wt% based on the total weight of the layer.

[0065] In a preferred embodiment, the blown film according to the invention has a multilayer film structure of the type selected from the group consisting of: AB, ABA, BAB, wherein layer A comprises or is composed of a spirocyclic diol-based polyester as defined above, and layer B comprises or is composed of polyethylene terephthalate.

[0066] The blown film according to this embodiment of the invention exhibits a unique and advantageous set of mechanical and optical properties, making it particularly suitable for several applications, such as industrial and consumer product packaging, construction applications, agricultural applications, and medical applications.

[0067] The blown film according to this embodiment of the invention advantageously exhibits a suitable combination of optical properties, tensile properties, impact resistance and tear resistance.

[0068] Because polyethylene terephthalate (PET) is used in combination with the spirocyclic diol-based polyester according to the invention, the PET contained in any embodiment of the blown film according to the invention can be any grade known to those skilled in the art, and there are no particular limitations. This significantly helps to broaden the application range of PET, overcoming limitations on the use of specific film grades and special equipment. Advantageously, the PET can also be wholly or partially, for example, recycled PET grades.

[0069] Even without their strict limitations, the poly(ethylene terephthalate) can exhibit one or more preferred properties.

[0070] Preferably, the poly(ethylene terephthalate) exhibits an intrinsic viscosity ranging from 0.4 dL / g to 1.2 dL / g when measured according to ASTM D4603.

[0071] The spirocyclic glycol-based polyester and blown films according to the invention may also advantageously contain various additives, such as light stabilizers, UV absorbers, antistatic agents, heat stabilizers, plasticizers, extenders, matting agents, drying regulators, precipitation inhibitors, surfactants, antioxidants, etherification inhibitors, release agents, flow improvers, drying oils, waxes, fillers, colorants, reinforcing agents, foaming agents, surface smoothers, leveling agents, and curing accelerators, provided that they do not prejudice the purpose of the invention.

[0072] Due to the properties and characteristics of spirocyclic diol-based polyesters as defined above, the applicant has found that blown films can be efficiently produced, which exhibit a combination of mechanical and optical properties, making them suitable for many different film applications, such as industrial and consumer product packaging, construction applications, agricultural applications, medical applications, and healthcare applications.

[0073] In another aspect, the invention also relates to the use of spirocyclic diol-based polyesters as defined in the first aspect of the invention for the production of blown films, and also to a method for producing blown films.

[0074] Notably, according to one of these other aspects of the invention, a method for producing blown films is provided, the method comprising the steps of: blown film onto at least one polymer feed comprising at least one spirocyclic diol-based polyester comprising diol units and dicarboxylic acid units, wherein the diol units comprise from 5 mol% to 65 mol% of units derived from diols having a spirocyclic diol structure represented by formula (1) based on the total amount of diol units.

[0075] Where R 1 and R 2 Each of the following organic groups is independently represented: aliphatic groups having 1 to 10 carbon atoms, alicyclic groups having 3 to 10 carbon atoms, and aromatic groups having 6 to 10 carbon atoms.

[0076] The advantages of the uses and methods of these other aspects of the invention have been disclosed with respect to the blown films according to the first aspect of the invention, and will not be repeated here.

[0077] In the uses and methods according to these other aspects of the invention, spirocyclic diol-based polyesters as defined in the first aspect of the invention are used. Therefore, the preferred characteristics of such spirocyclic diol-based polyesters have already been defined above in relation to the same components in other aspects of the invention, and thus will not be repeated here.

[0078] The uses and methods according to these aspects of the invention advantageously relate to the use of film blow molding machines or equipment, which can be any film blow molding machine or equipment known to those skilled in the art for thermoplastic materials, due to the processing properties of the spirocyclic diol-based polyester according to the invention, and therefore are not particularly limited. This significantly contributes to making the blown films according to the invention cost-competitive and sustainable, and also overcomes the current limitations of film blow molding with thermoplastic polyesters such as PET.

[0079] The method according to this other aspect of the invention includes a step of film blow molding at least one polymer feed.

[0080] Preferably, the polymer feed comprises at least one other polymer, more preferably polyester, and even more preferably polyethylene terephthalate.

[0081] In a preferred embodiment of the method according to this other aspect of the invention, the obtainable blown film is a blown film according to the first aspect of the invention.

[0082] It is worth noting that the blown film obtainable by the method according to the invention can advantageously be a blown film having a single-layer film structure or a multi-layer film structure as defined above with respect to any embodiment of the blown film according to the first aspect of the invention.

[0083] Preferably, in the film blow molding step, the polymer is fed into the extrusion or co-extrusion process to form a single-layer film structure or a multi-layer film structure.

[0084] The properties of the blown film according to the present invention make it particularly suitable for the production of various articles.

[0085] Therefore, in another aspect, the present invention also relates to an article selected from the group consisting of: bags, containers, packaging materials, pouches, shrink films, strips, agricultural films, greenhouse coverings, mulch films, silage films, vapor barrier films, roofing films, geomembranes, laminated articles, surgical drapes, gowns, fabrics, protective covers, linings, window films for heat dissipation, protective films for solar panels, and wrapping materials, said article comprising blown films according to the first aspect of the present invention, or blown films obtained by the method of producing blown films according to the present invention.

[0086] The advantages of the article according to this other aspect of the invention have been disclosed with respect to the blown film according to the first aspect of the invention, and will not be repeated here.

[0087] Further features and advantages of the invention will become more apparent from the following description of some preferred embodiments of the invention through the following non-limiting examples. Experimental Section

[0088] method 1) Intrinsic viscosity (IV): Intrinsic viscosity was measured using an Ubbelohde viscometer at a constant temperature of 25°C in a mixed solvent of phenol and 1,1,2,2-tetrachloroethane in a mass ratio of 6:4.

[0089] 2) Melt viscosity: Melt viscosity was measured using a Capirograph 1C available from Toyo Seiki Co., Ltd. under the following conditions: Measurement temperature: 240°C; Preheating time: 1 min; Nozzle diameter: 1 mm; Nozzle length: 10 mm; Shear rate: 100 s. -1 .

[0090] 3) Melt Flow Index (MFI): The melt flow index was measured at 250°C and 2.16 kg by weight using a CEAST Melt Flow Junior instrument according to ISO 1133. The measurement was performed on polyester granules that had been pre-dried to a moisture content of 143 ppm (Karl Fischer titration).

[0091] 4) Tear Resistance: Elmendorf tear strength is tested in both the longitudinal and transverse directions of the film to determine tear resistance, and measured according to ASTM D1922-15 (pendulum type: 200 g). All tested samples were conditioned at 23°C and 50% RH for at least three days prior to measurement. The results are the obtained average values.

[0092] 5) Impact Resistance: Impact resistance was measured according to ASTM D 3420-14, and the puncture resistance of the plastic film was also measured. The fixation device consisted of a probe attached to the end of an Elmendorf pendulum (type: 200 g) and a pneumatic clamp for securing the film sample. The device measured impact / puncture resistance as the probe pierced the sheet of plastic film. All tested samples were conditioned at 23°C and 50% RH for at least three days prior to measurement. The results are the average values ​​obtained.

[0093] 6) Tensile Properties: Tensile tests were performed on the film in both the longitudinal and transverse directions according to ISO 527-3 to measure yield stress, tensile strength, yield elongation, and elongation at break. The equipment used was a Zwick Z10 benchtop tensile tester with a 500 N load cell. A uniaxial elongation rate of 20 mm / min was used. Strip samples were measured at 23°C and 50% RH (ISO 527-3 Type 2). All tested samples were conditioned at 23°C and 50% RH for at least three days prior to measurement. The tensile results are the average values ​​obtained.

[0094] Example 1 - Preparation of Polyesters Based on Spirocyclic Diols A mixture of 13,313 g (69 mol) of dimethyl terephthalate (“DMT”), 3,844 g (62 mol) of ethylene glycol, and 18,871 g (62 mol) of 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane was heated to 200 °C under a nitrogen atmosphere in the presence of 0.03 mol of manganese acetate tetrahydrate based on 100 mol of DMT to carry out transesterification.

[0095] After the amount of distilled methanol reached 90% or more of its stoichiometric amount, 0.01 mol of antimony(III) oxide and 0.06 mol of triphenyl phosphate (hereinafter referred to as "TPP") (each based on 100 mol of DMT) were added to the reaction mixture. The temperature was gradually increased and the pressure gradually decreased, eventually reaching 280 °C and 0.1 kPa or lower to carry out polymerization. Polymerization was terminated when the reaction product reached a predetermined melt viscosity of approximately 2500 Pa*s, thereby obtaining a polyester containing approximately 50 mol% spirocyclic diol units. 1 H-NMR (400 MHz) was used to measure the content of spirocyclic diol units in the polymer.

[0096] Polyesters were also characterized by measuring their intrinsic viscosity (0.7 dl / g), Tg (112℃), and melt flow index (7.7 g / 10 min).

[0097] Example 2 - Preparation of blown films comprising spirocyclic diol-based polyesters according to Example 1 The spirocyclic glycol-based polyester pellets according to Example 1 were dried in a Mortto compressed air dryer until the moisture content was 206 ppm (Karl Fischer titration).

[0098] The dried granules were then mixed with 2 wt% of slip additive masterbatch (Crodamide VRX-BE-(HU)) and then fed into a Lab Tech LE20-30 film blow molding machine under the following operating conditions: - Screw speed: 36 rpm - Tank area temperature: 255℃ to 260℃ - Pressure control setting: 87 bar - Die head temperature: 240℃ - Blower speed: 1000 rpm -Pinch roller speed: 3.5 m / min - Rewinding speed: 3.4 m / min -Pinch roller pressure: 0.4 bar The resulting blown film has a thickness of approximately 30 micrometers and appears clear, transparent, and free of defects. Its mechanical properties were characterized. The results are reported in Table 1 below.

[0099] Table 1

[0100] Example 3 - Preparation of a blown film comprising a spirocyclic diol-based polyester and poly(ethylene terephthalate) in a weight ratio of 60 / 40 according to Example 1 The spirocyclic glycol-based polyester pellets according to Example 1 were dried in a Mortto compressed air dryer until the moisture content was 111 ppm (Karl Fischer titration).

[0101] Sixty parts by weight of these dried granules of spirocyclic glycol-based polyesters were compounded with 40 parts by weight of polyethylene terephthalate (“PET”, Papet Cool, bottle grade, IV 0.8 dL / g) in the presence of 0.8 wt% slip additive masterbatch (CrodamideVRX-BE-(HU)) in a Coperion twin-screw extruder operated under the following conditions: - Screw speed (min) -1 ): 400 - Output (kg / h): 6 -Specific mechanical energy (kWh / kg): 0.338 -Temperature distribution in the barrel area (°C): 185-260-280x2-275x3-270-250-235 - Pressure (bars): 32 The resulting compound is then fed into a Lab Tech LE20-30 film blow molding machine and operated under the following conditions: - Screw speed (rpm): 45 -Temperature distribution in the barrel area (°C): 260-270x2-255x2 - Pressure (bars): 41 - Die head temperature (°C): 250 - Blower speed (rpm): 1060 -Pinch roller speed (m / min): 3 - Rewinding speed (m / min): 3.3 -Pinch roller pressure (bar): 0.4 The resulting blown film has a thickness of approximately 60 micrometers and appears clear, transparent, and free of defects. Its mechanical properties were characterized. The results are reported in Table 2 below.

[0102] Example 4 - Preparation of a blown film comprising a spirocyclic diol-based polyester and poly(ethylene terephthalate) in a weight ratio of 20 / 80 according to Example 1 The spirocyclic glycol-based polyester pellets according to Example 1 were dried in a Mortto compressed air dryer until the moisture content was 111 ppm (Karl Fischer titration).

[0103] 20 parts by weight of these dried spirocyclic glycol-based polyester granules were compounded with 80 parts by weight of polyethylene terephthalate (“PET”, Papet Cool, bottle grade, IV 0.8 dL / g) in the presence of 1.6 wt% slip additive masterbatch (Crodamide VRX-BE-(HU)) in a Coperion twin-screw extruder operated under the following conditions: - Screw speed (min) -1 ): 400 - Output (kg / h): 72 -Specific mechanical energy (kWh / kg): 0.380 -Temperature distribution in the barrel area (°C): 185-260-280x2-275x3-270-250-235 - Pressure (bars): 32 The resulting compound is then fed into a Lab Tech LE20-30 film blow molding machine and operated under the following conditions: - Screw speed (rpm): 45 -Temperature distribution in the barrel area (°C): 260-270x2-255x2 - Pressure (bars): 55 - Die head temperature (°C): 250 - Blower speed (rpm): 1060 -Pinch roller speed (m / min): 3 - Rewinding speed (m / min): 3.3 -Pinch roller pressure (bar): 0.4 The blown film thus obtained has a thickness of approximately 50 micrometers, and it appears clear, transparent, and free of defects. Its mechanical properties were characterized. The results are reported in Table 2 below.

[0104] Table 2 .

Claims

1. A blown film comprising a spirocyclic diol-based polyester, said spirocyclic diol-based polyester comprising a diol component and a dicarboxylic acid component, wherein said diol component comprises, based on the total amount of the diol component, from 5 mol% to 65 mol% of residues of a diol having a spirocyclic diol structure represented by formula (1): Where R 1 and R 2 Each of the following organic groups is independently represented: aliphatic groups having 1 to 10 carbon atoms, alicyclic groups having 3 to 10 carbon atoms, and aromatic groups having 6 to 10 carbon atoms.

2. The blown film according to claim 1, wherein the diol component comprises from 20 mol% to 55 mol% of residues of the diol having a spirocyclic diol structure represented by formula (1) based on the total amount of the diol component.

3. The blown film according to claim 1 or 2, wherein the diol having a spirocyclic diol structure is 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

4. The blown film according to any one of claims 1 to 3, wherein the diol component comprises residues derived from at least one other diol selected from the group consisting of: ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

5. The blown film according to claim 4, wherein the other diol is ethylene glycol.

6. The blown film according to claim 4 or 5, wherein the diol component comprises from 35 mol% to 95 mol% residues derived from the at least one other diol.

7. The blown film according to any one of claims 1 to 6, wherein the dicarboxylic acid component comprises from 80 mol% to 100 mol% of terephthalic acid-derived residues based on the total amount of the dicarboxylic acid component.

8. The blown film according to any one of claims 1 to 7, wherein the blown film has a single-layer film structure or a multi-layer film structure.

9. The blown film according to any one of claims 1 to 8, wherein the blown film has a single-layer film structure, and the blown film comprises from 10 wt% to 100 wt% of the spirocyclic diol-based polyester based on the total weight of the blown film.

10. The blown film according to any one of claims 1 to 9, wherein the blown film has a single-layer film structure, and the blown film comprises, based on the total weight of the blown film, 20 wt% to 60 wt% of the spirocyclic diol-based polyester and 40 wt% to 80 wt% of at least one other polymer, said other polymer being polyethylene terephthalate.

11. Use of a spirocyclic diol-based polyester in the production of blown films, wherein the spirocyclic diol-based polyester comprises a diol component and a dicarboxylic acid component, and wherein the diol component comprises, based on the total amount of the diol component, from 5 mol% to 65 mol% of residues of a diol having a spirocyclic diol structure represented by formula (1): Where R 1 and R 2 Each of the following organic groups is independently represented: aliphatic groups having 1 to 10 carbon atoms, alicyclic groups having 3 to 10 carbon atoms, and aromatic groups having 6 to 10 carbon atoms.

12. A method for producing blown film, comprising the following steps: Film blow molding is performed on at least one polymer feed comprising at least one spirocyclic diol-based polyester containing diol units and dicarboxylic acid units, wherein the diol units comprise from 5 mol% to 65 mol% of units derived from diols having a spirocyclic diol structure represented by formula (1) based on the total amount of diol units: Where R 1 and R 2 Each of the following organic groups is independently represented: aliphatic groups having 1 to 10 carbon atoms, alicyclic groups having 3 to 10 carbon atoms, and aromatic groups having 6 to 10 carbon atoms.

13. The use according to claim 11 or the method according to claim 12, wherein the spirocyclic diol-based polyester is a spirocyclic diol-based polyester according to any one of claims 1 to 10.

14. An article selected from the group consisting of: bags, containers, packages, pouches, shrink films, strips, agricultural films, greenhouse coverings, mulch films, silage films, vapor barrier films, roofing films, geomembranes, laminated articles, surgical drapes, gowns, fabrics, protective covers, linings, window films for heat dissipation, protective films for solar panels, and wrapping materials, said article comprising a blown film according to any one of claims 1 to 10 or a blown film obtainable by the method of claim 12.

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