Biodegradable polyester and adhesive packaging film made therefrom

Abstract

A biodegradable aliphatic-aromatic polyester for producing packaging films, the polyester having a Poisson's ratio (RVE) of 800 to 1700, comprising units of at least one dicarboxylic acid and at least one diol, wherein Mn is ≥40,000 and Mw / q is ≤90,000, wherein q is the weight percentage of polyester oligomers having a molecular weight of ≤10,000.

Description

[0001] The present invention relates to biodegradable aliphatic-aromatic polyesters particularly suitable for the production of adhesive films for packaging, said polyesters comprising units derived from at least one dicarboxylic acid and at least one diol, said polyesters being characterized by a specific range of coefficient of friction compared to conventional biodegradable polyesters.

[0002] Another object according to the present invention is a stretchable packaging film comprising said biodegradable polyester.

[0003] Packaging films, known as "cling films", are known in the trade and literature. Typically, these films are 6 to 20 μm thick and are used, for example, to wrap food products before placing them in a refrigerator or packaging them in a container.

[0004] An important and useful feature of such films is their ability to adhere to both themselves and other non-adhesive surfaces without the addition of adhesives. This property enables a user to wrap one or more layers of film around an object (e.g., food on a plate), thus sealing it airtight.

[0005] Another feature is transparency, which enables users of such films to identify the object wrapped therein without having to open the object.

[0006] In EP 2 632 970, the applicant describes a biodegradable polyester particularly suitable for producing adhesive films comprising units derived from at least one dicarboxylic acid and at least one diol, characterized by a coefficient of friction greater than 10. The biodegradable polyester described in EP 2 632 970 enables the production of packaging films characterized by a high ability to adhere to themselves and other surfaces, which is particularly advantageous because it allows for relatively easy use, especially, but not exclusively, for protecting food trays. However, if the adhesion capacity is too high, this can make unwinding the film difficult, both in industrial and finished product use, and can lead to film rupture during packaging. Due to transverse stretching, rupture occurs primarily in the longitudinal direction of the film.

[0007] Therefore, there is a particular need for biodegradable polyesters suitable for the production of packaging films having optimal mechanical properties, excellent transparency properties and a reduced tendency to break without increasing the percentage of breakage over the entire useful life of the product. All of the above limitations have now been overcome by the polyesters according to the present invention.

[0008] The present invention therefore relates to biodegradable aliphatic-aromatic polyesters particularly suitable for the production of packaging films, said polyesters having a Poisson's ratio of 800 to 1700, preferably 1000 to 1400, and comprising units derived from at least one dicarboxylic acid and at least one diol, and having:

[0009] -Mn≥40000

[0010] -Mw / q≤90000,

[0011] Wherein q is the weight percentage of polyester oligomers with a molecular weight of ≤10,000 as determined by GPC,

[0012] Wherein Poisson's ratio is calculated as the ratio of shear viscosity to melt strength (MS), the coefficient of friction of the polyester film is 5 to 10.

[0013] Shear viscosity was determined according to ASTM D3835-90 “Standard Test Method for Determining Properties of Polymer Materials by means of a Capillary Rheometer” using a capillary tube with a diameter of 1 mm and L / D = 30 at a flow rate of γ = 103.7 s -1 The flow gradient is determined at 180°C, while the melt strength (MS) is determined according to ISO 16790:2005 at 180°C and γ = 103.7s -1 A capillary with a diameter of 1 mm and L / D = 30 was used at 6 mm / s. 2 The test was conducted under a constant acceleration and a tensile length of 110 mm.

[0014] According to the standard method, the melt strength (MS) value is expressed in Newtons. However, in this specification and examples, for ease of reading, the melt strength (MS) value is reported in "gram-strength" according to the following conversion: 1N = 102 g-strength; 1cN = 1.02 g-strength. Therefore, the value obtained in Newtons is converted to gram-strength by multiplying the value by 0.0098.

[0015] The aliphatic-aromatic polymers according to the present invention are also characterized by a melt strength of from 0.7 to 2.5, more preferably from 0.8 to 2.1.

[0016] In a particularly preferred aspect according to the present invention, the shear viscosity is from 800 Pas to 1200 Pas, preferably from 900 Pas to 1150 Pas; as for the molecular weights "Mn" and "Mw", these are measured by gel permeation chromatography (GPC); "q" = weight percentage of polyester oligomers having a molecular weight ≤ 10,000 by GPC.

[0017] The present invention also relates to a packaging film comprising the biodegradable polyester and a method for producing the film.Preferably, the polyester has a melting point of 55°C to 170°C and an elastic modulus greater than 50 MPa.

[0018] The coefficient of friction (COF) represents a material's resistance to sliding. For the polyesters according to the present invention, the COF is determined according to a modification of ASTM Standard D1894, "Static and kinetic coefficients of friction of plastic films and sheets." Therefore, according to the present invention, the COF is measured using the following method.

[0019] A sample of the polyester according to the present invention, in the form of a flexible stretch film having a thickness of 3 to 50 microns, preferably 6 to 25 microns, is wrapped around a glass slide covering a support surface measuring approximately 150 mm x 300 mm x 2 mm in thickness. The film sample must adhere perfectly to the glass slide and must present a smooth surface without wrinkles. To achieve this, a brush can be used to apply moderate pressure to remove any bubbles that may have formed between the film and the glass slide. The slide is placed in a horizontal position, and a stainless steel slide weighing 200 ± 5 grams and measuring 63.5 mm x 5 mm thick is placed on top. To improve the adhesion of the slide to the surface of the film, moderate pressure is manually applied to its surface. A load cell is connected to one end of the slide via a nylon thread. The load cell is positioned on the moving crossbar of the dynamometer and can move at a constant speed of 10 mm / minute. The coefficient of friction is defined as the ratio of the force (F) recorded by the dynamometer at the moment of loss of adhesion between the slide and the film (the tangential friction force that resists sliding) to the weight (Fg) acting perpendicularly on the two contact surfaces (the weight of the steel slide).

[0020] Preferably, the polyester according to the present invention has a gel fraction of less than 5%, more preferably less than 3%, even more preferably less than 1%. The gel fraction is determined by: 1 ) in chloroform, then filter the mixture on a 25 μm to 45 μm sieve and measure the weight of the material retained on the filter mesh (X 2 ). The gel fraction is determined as the ratio of the weight of the material thus obtained to the weight of the sample, i.e. (X2 / X1)×100.

[0021] In the aliphatic-aromatic polyester according to the invention, the aromatic part comprises predominantly at least one polyfunctional aromatic acid and the aliphatic part comprises at least one aliphatic dicarboxylic acid and at least one aliphatic diol.

[0022] Polyfunctional aromatic acids are understood to mean dicarboxylic aromatic compounds of the phthalic acid type and their esters as well as heterocyclic dicarboxylic aromatic compounds of renewable origin and their esters. Particular preference is given to 2,5-furandicarboxylic acid and its esters as well as terephthalic acid and its esters and mixtures thereof.

[0023] Renewable sources are those products obtained from sources that, by their inherent properties, regenerate naturally within the timescale of human life and, by extension, whose use does not endanger natural resources for future generations. Typical examples of renewable sources are plant crops.

[0024] Aliphatic dicarboxylic acids are understood to mean dicarboxylic acids having 2 to 22 carbon atoms in the main chain and their esters. Dicarboxylic acids, their esters, and mixtures thereof from renewable sources are preferred, and among these, adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and mixtures thereof are preferred. In a particularly preferred embodiment, the aliphatic dicarboxylic acids of the biodegradable polyester according to the invention comprise at least 50% by mole of azelaic acid, adipic acid, or mixtures thereof, relative to the total moles of the aliphatic dicarboxylic acids.

[0025] Also included are dicarboxylic acids having unsaturation within the chain, such as itaconic acid and maleic acid.

[0026] In the polyesters according to the invention, diols are understood to be compounds with two hydroxyl groups. 13 Aliphatic diols are preferred.

[0027] Examples of the aliphatic diol include 1,2-ethanediol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, 2-methyl-1,3-propanediol, dianhydrosorbitol, dianhydromannitol, dianhydroiditol, cyclohexanediol, cyclohexanemethanediol, and mixtures thereof. Among them, 1,4-butanediol, 1,3-propylene glycol, 1,2-ethanediol, and mixtures thereof are particularly preferred. In a particularly preferred form, the diols of the biodegradable polyester according to the invention comprise at least 50% by mole, preferably at least 80% by mole, of 1,4-butanediol relative to the total diols by mole.

[0028] The aliphatic aromatic polyesters are characterized by a polyfunctional aromatic acid content of 30 to 70 mol %, preferably 40 to 60 mol %, relative to the total dicarboxylic acid content calculated on moles.

[0029] To the aliphatic-aromatic polyester according to the invention, it is possible to suitably add an aliphatic polyester obtained from at least one aliphatic dicarboxylic acid and from 0% to 30% of at least one aliphatic diol.

[0030] Advantageously, the polyester according to the invention may be added with a branching compound selected from the group consisting of polyfunctional molecules such as, for example, polyacids, polyols and mixtures thereof, in an amount of less than 0.5%, preferably less than 0.2%, by mole, relative to the total content of dicarboxylic acids by mole.

[0031] Examples of polyacids are: 1,1,2-ethanetricarboxylic acid, 1,3,5-pentatricarboxylic acid, malic acid, citric acid, tartaric acid, 3-hydroxyglutaric acid, mucic acid, trihydroxyglutaric acid, hydroxyisophthalic acid, derivatives thereof and mixtures thereof.

[0032] Examples of polyols are: glycerol, hexanetriol, sorbitol, trimethylolethane, trimethylolpropane, mannitol, 1,2,4-butanetriol, xylitol, 1,1,4,4-tetrakis(hydroxymethyl)cyclohexane, arabitol, adonitol, iditol and mixtures thereof.

[0033] The polyesters according to the invention may advantageously contain comonomers of the hydroxy acid type in a percentage not exceeding 30% and preferably not exceeding 20% by mole relative to the total content of dicarboxylic acids by mole. The polyesters may be present in a random or block-type distribution of the recurring units.

[0034] Preferred hydroxy acids are D- and L-lactic acid, glycolic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid and octadecanoic acid. Preferred are hydroxy acids of the type having 3 or 4 carbon atoms in the main chain.

[0035] Mixtures of different polyesters according to the invention are also included in the present invention.

[0036] Within the meaning according to the present invention, biodegradable polyesters are understood to be polyesters which are biodegradable according to EN 13432.

[0037] The polyesters according to the invention can be used in a mixture with one or more polymers of synthetic or natural origin, whether biodegradable or not, including when obtained by a reactive extrusion process.

[0038] Preferably, the reactive extrusion process is performed by adding peroxides, epoxides or carbodiimides.

[0039] Preferably, the reactive extrusion process is carried out using an amount of peroxide ranging from 0.001% to 0.2% and preferably from 0.01% to 0.1% by weight relative to the sum of the polymers fed to the reactive extrusion process.

[0040] As far as the addition of epoxides is concerned, these are preferably used in amounts of 0.1 to 2%, more preferably 0.2 to 1% by weight of the sum of the polymers fed to the reactive extrusion process.

[0041] If carbodiimides are used, these are preferably used in amounts of 0.05 to 2%, more preferably 0.1 to 1% by weight, based on the sum of the polymers fed to the reactive extrusion process.

[0042] Mixtures of these peroxides, epoxides and carbodiimides may also be used.

[0043] Examples of peroxides that can advantageously be used are selected from the group of dialkyl peroxides, for example: benzoyl peroxide, lauroyl peroxide, isononanoyl peroxide, di-(tert-butylperoxyisopropyl)benzene, tert-butyl peroxide, dicumyl peroxide, α,α′-di(tert-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne, di(4-tert-butylcyclohexyl)peroxydicarbonate, dihexadecyl peroxydicarbonate, dimyristyl peroxydicarbonate, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane, di(2-ethylhexyl)peroxydicarbonate, and mixtures thereof.

[0044] Examples of epoxides that can be advantageously used are all polyepoxides from epoxidized oils and / or styrene-glycidyl ether-methyl methacrylate, glycidyl ether-ethyl methacrylate, including those having a molecular weight range of 1000 to 10000 and an epoxide number per molecule ranging from 1 to 30 and preferably from 5 to 25; and epoxides selected from the group comprising diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, 1,2-butylene oxide, polyglycerol polyglycidyl ether, isoprene diepoxide, and alicyclic diepoxides, 1,4-cyclohexanedimethanol diglycidyl ether, glycidyl 2-methylphenyl ether, glycerol propoxylated triglycidyl ether, 1,4-butanediol diglycidyl ether, sorbitol polyglycidyl ether, glycerol diglycidyl ether, tetraglycidyl ether of m-xylenediamine and diglycidyl ether of bisphenol A, and mixtures thereof.

[0045] Catalysts can also be used to increase the reactivity of the reactive groups. In the case of polyepoxides, for example, fatty acid salts can be used. Calcium stearate and zinc stearate are particularly preferred.

[0046] Examples of carbodiimides that can be advantageously used are those selected from the group consisting of poly(cyclooctylenecarbodiimide), poly(1,4-dimethylenecyclohexylenecarbodiimide), poly(cyclohexylenecarbodiimide), poly(ethylenecarbodiimide), poly(butylenecarbodiimide), poly(isobutylenecarbodiimide), poly(nonylenecarbodiimide), poly(dodecylenecarbodiimide), poly(neopentylenecarbodiimide), poly(1,4-dimethylenephenylenecarbodiimide), poly(2,2′,6,6′-tetraisopropyldiphenylenecarbodiimide) D), poly (2,4,6-triisopropyl-1-phenylenecarbodiimide) ( P-100), poly (2,6-diisopropyl-1,3-phenylenecarbodiimide) (

[0014] Poly(tolylcarbodiimide), poly(4,4'-diphenylmethanecarbodiimide), poly(3,3'-dimethyl-4,4'-biphenylenecarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly(naphthylenecarbodiimide), poly(isophoronecarbodiimide), poly(cumenecarbodiimide), p-phenylenebis(ethylcarbodiimide), 1,6-hexamethylenebis(ethylcarbodiimide), 1,8-octamethylenebis(ethylcarbodiimide), 1,10-decamethylenebis(ethylcarbodiimide), 1,12-dodecamethylenebis(ethylcarbodiimide), and mixtures thereof.

[0047] In particular, the polyesters according to the invention can be used in a mixture with biodegradable polyesters of the dicarboxylic acid-diol type, of the hydroxy acid type or of the polyester-ether type.

[0048] As far as the biodegradable polyesters of the dicarboxylic acid-diol type are concerned, they may be aliphatic or aliphatic-aromatic.

[0049] The biodegradable aliphatic polyesters from dicarboxylic acid-diols comprise aliphatic dicarboxylic acids and aliphatic diols, while the biodegradable aliphatic-aromatic polyesters have an aromatic portion consisting mainly of polyfunctional aromatic acids of both synthetic and renewable origin, while the aliphatic portion consists of aliphatic dicarboxylic acids and aliphatic diols.

[0050] The biodegradable aliphatic aromatic diol polyester is preferably characterized in that the aromatic acid content is from 30 to 90 mol %, preferably from 45 to 70 mol %, relative to the acid component.

[0051] Preferably, the polyfunctional aromatic acid of synthetic origin is a dicarboxylic aromatic compound of the phthalic acid type and its esters, preferably terephthalic acid.Preferably, the polyfunctional aromatic acid of renewable origin is selected from the group comprising 2,5-furandicarboxylic acid and its esters.

[0052] Particularly preferred are biodegradable aliphatic-aromatic polyesters derived from dicarboxylic acid-diols, wherein the aromatic diacid component consists of a mixture of polyfunctional aromatic acids of synthetic and renewable origin.

[0053] The aliphatic dicarboxylic acids of the biodegradable polyesters from dicarboxylic acid-diols are aliphatic dicarboxylic acids and their esters having 2 to 22 carbon atoms in the main chain. Preferred are dicarboxylic acids, their esters and mixtures thereof from renewable sources, with adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and mixtures thereof being preferred.

[0054] Examples of aliphatic diols in biodegradable diacid-diol polyesters include 1,2-ethanediol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, 2-methyl-1,3-propanediol, dianhydrosorbitol, dianhydromannitol, dianhydroiditol, cyclohexanediol, cyclohexanemethanediol, and mixtures thereof. Among these, 1,4-butanediol, 1,3-propylene glycol, and 1,2-ethanediol, and mixtures thereof, are particularly preferred.

[0055] Preferably, the mixture of the polyester according to the invention and the above-mentioned biodegradable diol-diacid polyester is characterized in that the content of said biodegradable polyester varies from 5% to 95% w / w, more preferably from 10% to 90% w / w, relative to the sum of the weight of the copolyester according to the invention and the latter, respectively.

[0056] It is also possible to mix the polyesters according to the invention with more than one aliphatic-aromatic polyester having an aromatic portion consisting predominantly of polyfunctional aromatic acids of both synthetic and renewable origin or mixtures thereof.

[0057] The polyesters according to the invention and both binary and ternary mixtures of said polyesters are also particularly preferred.

[0058] Regarding the polyester mixtures according to the present invention, biodegradable polyesters from preferred hydroxy acids include: poly L-lactic acid, poly D-lactic acid and poly DL-lactic acid stereocomplexes, poly-ε-caprolactone, polyhydroxybutyrate, polyhydroxybutyrate-valerate, polyhydroxybutyrate-propionate, polyhydroxybutyrate-hexanoate, polyhydroxybutyrate-decanoate, polyhydroxybutyrate-dodecanoate, polyhydroxybutyrate-octadecanoate, poly-3-hydroxybutyrate-4-hydroxybutyrate.

[0059] Preferably, the mixture of the polyester according to the invention with the above-mentioned biodegradable hydroxy acid polyester is characterized in that the content of said biodegradable polyester varies from 1% to 20% weight / weight, more preferably from 1% to 15% weight / weight, relative to the sum of the weight of the copolyester according to the invention and the latter, respectively.

[0060] Said mixture is advantageously obtained by a reactive extrusion process of the polyester according to the invention with said polylactic acid polymer, preferably in the presence of an organic peroxide such as those mentioned above.

[0061] The polyester according to the present invention can also be used in a mixture with a polymer of natural origin (e.g. starch, cellulose, chitin, chitosan, alginate, proteins such as gluten, zein, casein, collagen, gelatin, natural gums, purified, hydrolyzed, alkalized or unprocessed lignin, etc., or derivatives thereof). Starch and cellulose can be modified, including, for example, starch or cellulose esters with a degree of substitution of 0.2 to 2.5, hydroxypropylated starch, starch modified with a fatty chain, and cellophane. Starch mixtures are particularly preferred. Starch can also be used in both unstructured and gelled forms or as a filler. Starch can be a continuous phase or a dispersed phase, or it can be a co-continuous form. In the case of dispersed starch, the starch is preferably in submicron form and more preferably has an average diameter of less than 0.5 μm.

[0062] Preferably, the mixture of the polyester according to the invention with the above-mentioned polymer of natural origin is characterized in that the content of said polymer of natural origin varies from 1% to 30% w / w, more preferably from 2% to 15% w / w, relative to the sum of the weight of the copolyester according to the invention and the latter, respectively.

[0063] The polyesters according to the invention can also be used in mixtures with polyolefins, non-biodegradable polyesters, polyether-urethanes, polyurethanes, polyamides, polyamino acids, polyethers, polyureas, polycarbonates and mixtures thereof.

[0064] Preferred polyolefins include polyethylene, polypropylene, copolymers thereof, polyvinyl alcohol, polyvinyl acetate, polyethylvinyl acetate, and polyethylene vinyl alcohol.

[0065] Among the non-biodegradable polyesters, PET, PBT, PTT, in particular with a renewable content of >30%, and furandicarboxylated polyalkylenes are preferred. Among the furandicarboxylated polyalkylenes, furandicarboxylated polyethylene, furandicarboxylated polypropylene, furandicarboxylated polybutylene and mixtures thereof are particularly preferred.

[0066] Examples of polyamides are polyamide 6 and 6.6, polyamide 9 and 9.9, polyamide 10 and 10.10, polyamide 11 and 11.11, polyamide 12 and 12.12 and combinations of the type 6 / 9, 6 / 10, 6 / 11, 6 / 12 as well.

[0067] The polycarbonate may be polyethylene carbonate, polypropylene carbonate, polybutylene carbonate, mixtures and copolymers thereof.

[0068] The polyether may be polyethylene glycol, polypropylene glycol, polybutylene glycol, copolymers thereof, and mixtures thereof, wherein the molecular weight is from 70,000 to 500,000.

[0069] Preferably, the mixtures of the polyester according to the invention with the aforementioned polymers (polyolefins, non-biodegradable polyesters, polyester- and polyether-urethanes, polyurethanes, polyamides, polyamino acids, polyethers, polyureas, polycarbonates and mixtures thereof) are characterized in that the content of said polymers varies from 0.5% to 99% w / w, more preferably from 5% to 50% w / w, relative to the sum of the weight of the copolyester according to the invention and of the latter, respectively.

[0070] The polyester production process according to the present invention can be carried out according to any method known in the art.

[0071] In particular, polyesters can advantageously be obtained by polycondensation. Advantageously, the polyester polymerization process can be carried out in the presence of a suitable catalyst. Suitable catalysts may, for example, include organometallic tin compounds such as stannic acid derivatives, titanium compounds such as butyl orthotitanate, aluminum compounds such as triisopropylaluminum, and antimony and zinc compounds.

[0072] The polyester according to the invention can also be obtained by a reactive extrusion process from a precursor polyester comprising units derived from at least one dicarboxylic acid and at least one substantially linear diol, said precursor polyester having an MFI at 190° C. and 2.16 kg of 5 to 30 dl / g, a weight average molecular weight Mw measured by GPC in the range of 60,000 to 120,000, and comprising active sites, such as unsaturation, in an amount of 0.1% to 1% by mole and / or terminal acid groups in an amount of 10 to 200 meq / kg polymer, preferably 10 to 100 meq / kg polymer, even more preferably 10 to 50 meq / kg polymer. The reactive extrusion process is carried out by adding a compound selected from peroxides, epoxides, carbodiimides or mixtures thereof, such as those mentioned above.

[0073] Preferably, the precursor polyester has an MFI at 190° C. and 2.16 kg of 5 to 30 g / 10 min, and more preferably 7 to 20 g / 10 min, a shear viscosity of 500 to 700 Pas and a weight average molecular weight Mw of preferably 100,000 to 130,000.

[0074] The molecular weights Mn and Mw can be measured by gel permeation chromatography (GPC). The determination can be performed using a set of two columns in series (particle sizes of 5 μm and 3 μm with mixed porosity), a refractive index detector, chloroform as the eluent (flow rate 0.5 ml / min), and polystyrene as the reference standard, while maintaining the chromatography system at 40°C.

[0075] Preferably, the unsaturation content of the precursor polyester is from 0.1 to 0.8% by mole, and more preferably from 0.2 to 0.7% by mole.

[0076] Unsaturation can be introduced in situ during polymerization or processing of the precursor polymer, or by the insertion of appropriate unsaturated monomers or unsaturated chain terminators.

[0077] Polyesters having terminal unsaturation are particularly preferred.

[0078] Among the unsaturated chain terminators, those having the following structure are preferred:

[0079] T-(CH2) n -CH=CH2

[0080] wherein "T" is a group capable of reacting with a carboxyl group and / or a hydroxyl group, such as a hydroxyl group, a carboxyl group, an amine group, an amide group, or an ester group, and "n" is an integer from 0 to 13.

[0081] These unsaturated chain terminators can also be used in mixtures.

[0082] As for "T", it is preferably a hydroxyl group or a carboxyl group.

[0083] The integer "n" is preferably 1 to 13, more preferably 3 to 13, and even more preferably 8 or 9.

[0084] Particularly preferred unsaturated chain terminators are ω-undecenoic acid, ω-undecenol and mixtures thereof.

[0085] The presence of unsaturation and / or adducts resulting from these reactions following reactive extrusion can be determined by various methods known to those skilled in the art, such as NMR spectroscopy or methanolysis of the polymer chain coupled with chromatography coupled to mass spectrometry.

[0086] One skilled in the art will readily be able to identify structures associated with the unsaturation itself or the adduct resulting from its reaction following reactive extrusion.

[0087] As far as the unsaturation content is measured by NMR, this can be done by using a 1H-NMR 300 MHz characterized by a pulse acquisition sequence with a pulse phase of 30°, spectral width = 4 kHz, a delay of 5 seconds and performing 6000 scans.

[0088] The content of terminal acid group can be measured as follows: 1.5g to 3g polyester is put into 100ml conical flask together with 60ml chloroform. After polyester is completely dissolved, add 25ml 2-propyl alcohol, and before analysis, add 1ml deionized water. The obtained solution is titrated with a solution of NaOH in ethanol previously standardized. Use a suitable indicator, for example, a glass electrode for acid-base titration in non-aqueous solvents to determine the equivalence point of titration. According to the following equation, the content of terminal acid group is calculated by the consumption of NaOH solution in ethanol:

[0089]

[0090] Where: Veq = ml of NaOH solution in ethanol at the equivalence point of the sample titration;

[0091] Vb = ml of NaOH solution in ethanol required to achieve pH = 9.5 during the blank titration;

[0092] T = concentration of NaOH solution in ethanol expressed in mol / L;

[0093] P = sample weight in grams.

[0094] The process for producing the precursor polyester may be carried out according to any of the methods known in the art as described above.

[0095] The present invention also relates to an adhesive film obtained from the biodegradable polyester and to a method for producing the film. The film has properties that make it suitable for numerous practical applications related to domestic and industrial consumption. Examples of such applications are food and non-food packaging, industrial packaging (e.g., pallets), agricultural bales, and waste packaging.

[0096] The chemical-physical properties allow the polyester according to the invention to be fed efficiently to conventional equipment for making adhesive films, usually for PE or PVC, without requiring any particular changes to the structure and operating conditions of the machines.

[0097] Due to the specific combination of rheological properties and friction coefficient of the polyester according to the invention, the film can also be advantageously produced by a blown film process, in which the bubbles can be opened, thereby allowing the collection of a single-layer film roll downstream of the film forming process. This feature is particularly advantageous in terms of the productivity of the production process.

[0098] Preferably, the bubble blown film process is characterized by a blow-up ratio (BUR (blow-up ratio or transverse stretch) of 2 to 5 and a drawdown ratio (DDR (drawdown ratio) or longitudinal stretch) in the machine direction (MD) of 5 to 60. For the purposes of the present invention, DDR means the measure of the elongation to which the melt exiting the extruder is subjected in the direction of stretch; BUR means the ratio of the bubble diameter to the die diameter. Advantageously, during bubble blowing, the process parameters are set to have a DDR / BUR ratio of 3 to 15.

[0099] The properties of the polyester according to the invention make it possible to produce very thin films in the range of 3 to 50 microns, preferably between 6 and 25 microns.

[0100] The films obtained from the biodegradable polyester according to the invention exhibit strong adhesion both to themselves and to other non-adherent surfaces such as ceramics, glass, metals and plastics such as HDPE, LDPE, PP, PET, PVC.

[0101] In a preferred embodiment according to the present invention, the stretch film comprises several layers. The multilayer film comprises at least one layer A, the at least one layer A comprising a composition according to the present invention; and at least one layer B, the at least one layer B comprising at least one polymer selected from the group consisting of diacid-diol polyesters, hydroxy acid polyesters and synthetic polymers such as polyvinyl alcohol, ethylene vinyl alcohol, polyvinyl acetate, ethyl vinyl acetate. The film is preferably characterized in that the arrangement of the layers A and B relative to each other is selected from A / B, A / B / A and B / A / B. In another particularly preferred embodiment, the layer B advantageously imparts an enhanced barrier effect. Other layers arranged in an intermediate position relative to the layers A and B may also be present (structure A / C / B / C / A, where C is an additional layer). The multilayer film can be produced according to any method known to those skilled in the art, for example by a coextrusion process, a painting / spraying process or a lamination process.

[0102] Furthermore, due to the chemical and physical properties of the polyester according to the invention, cling films obtained from said polyester can be produced without the use of plasticizers or tackifiers such as polyisobutylene or ethylene vinyl acetate. This makes it possible to understand a further significant difference between the films according to the invention and PVC and polyethylene cling films, which have significant limitations for use in the food packaging industry due to the presence of the aforementioned additives.

[0103] In a particularly preferred embodiment, the adhesive films obtained from the polyesters according to the invention are essentially free of plasticizers and tackifiers.

[0104] The adhesive films obtained from the biodegradable polyesters according to the invention also have excellent mechanical properties which, through a specific combination of tearability, strength and extensibility, make them particularly suitable for use in industrial packaging and food packaging.

[0105] Preferably, the adhesive film exhibits a tear strength value of >70 N / mm, an elongation at break of >400%, an elastic modulus of >50 MPa and <400 MPa, and a tensile strength of >25 MPa in the transverse direction relative to the film formation direction, and a tear strength value of >50 N / mm, an elongation at break of >200%, an elastic modulus of >100 MPa, and a tensile strength of >30 MPa in the longitudinal direction relative to the film formation direction.

[0106] More preferably, the adhesive film exhibits a tear strength value of >90 N / mm, an elongation at break of >450%, an elastic modulus of >70 MPa and <400 MPa, and a tensile strength of >45 MPa in the transverse direction relative to the film forming direction, and a tear strength value of >50 N / mm, an elongation at break of >300%, an elastic modulus of >90 MPa, and a tensile strength of >35 MPa in the longitudinal direction relative to the film forming direction.

[0107] As regards the mechanical properties, according to the invention, these are determined according to ASTM D882 (tear at 23° C. and 55% relative humidity and vo=50 mm / min) and ASTM D1922 (tear at 23° C. and 55% relative humidity).

[0108] Adhesive films made from the biodegradable polyesters according to the present invention advantageously possess excellent optical properties. In particular, they preferably have a haze value of less than 15%, preferably less than 10%, and a transmittance value greater than 80%, preferably greater than 90%, enabling users to identify wrapped objects without opening them. This property is particularly advantageous when used for food packaging. Optical properties are determined according to ASTM D1003.

[0109] In addition to the above characteristics, the adhesive film obtained from the biodegradable polyester according to the present invention advantageously has a water vapor permeability value much higher than that of PVC and PE adhesive films. In particular, it preferably shows a water vapor permeability of greater than 150 g / m2 measured at 23°C 50% RH on a film of 16 microns thickness. 2 / day VWTR value, preferably 300g / m 2 / day to 900g / m 2 / sky.

[0110] Permeability properties are determined according to ASTM F1249.

[0111] The adhesive films obtained from the biodegradable polyester according to the invention can be used in existing machines in the retail industry without modification. This particularly desirable property should not be considered obvious, as many adhesive films produced from biodegradable polymers do not possess these properties.

[0112] The invention will now be illustrated using an example of embodiment, which is intended as an illustration and not as a limitation of the scope of protection of this patent application. Example

[0113] Examples 1 to 2 :

[0114] Poly(1,4-butylene adipate-co-1,4-butylene terephthalate) [PBTA], wherein the terephthalic acid content is 47% by mole relative to the total dicarboxylic acid component. PBTA has an MFR of 4.8 g / 10 min (@190° C., 2.16 kg), a Poisson's ratio of 1083 (shear viscosity at 180° C. of 1083 Pas and melt strength of 1.0 g-strength), and a terminal acid group content of 34 meq / kg.

[0115] Examples 3 to 4 (comparative):

[0116] Poly(1,4-butylene sebacate-co-1,4-butylene terephthalate) [PBTSeb], wherein the terephthalic acid content is 56% by mole relative to the total dicarboxylic acid component. PBTSeb is characterized by an MFR of 2.6 g / 10 min (@190° C., 2.16 kg), a Poisson's ratio of 394 (shear viscosity of 1220 Pas at 180° C. and a melt strength of 3.1 g-strength), and a terminal acid group content of 40 meq / kg.

[0117] Characterization, membrane production, and mechanical testing

[0118] The polyesters were analyzed by gel permeation chromatography (GPC). The measurements were performed on a 1100 chromatograph at 40° C. The determinations were performed using a set of two columns in series (particle sizes of 5 μm and 3 μm with mixed porosity), a refractive index detector, chloroform as eluent (flow rate 0.5 ml / min) and polystyrene as reference standard.

[0119] Table 1 shows the properties of the prepared polymers.

[0120]

[0121] PBTA and PBTSeb pellets were fed to a Ghioldi model film blowing machine operating at 30 rpm with a 40 mm screw diameter and L / D 30. The film forming head had an air gap of 0.9 mm and L / D 12. 20 micron thick films (10+10) were obtained using the conditions described in Table 2 below:

[0122] Table 2

[0123]

[0124] Three grams of the membrane were analyzed using the method described herein to determine the weight percent ("q") of polyester oligomers having a molecular weight of ≤ 10,000 by GPC.

[0125] Table 3

[0126]

[0127] The mechanical properties were determined in accordance with ASTM D882 (pulling at 23° C. and 55% relative humidity and vo=50 mm / min) in the longitudinal direction relative to the film formation direction.

[0128] Optical properties were determined according to ASTM D1003.

[0129] The coefficient of friction (COF) is determined according to a modification of ASTM D1894, "Coefficients of Static and Dynamic Friction of Plastic Film and Sheeting," as described herein.

[0130]

Claims

1. A biodegradable aliphatic-aromatic polyester suitable for producing packaging films, said polyester having a Poisson's ratio (RVE) of 1000 to 1400 and comprising units derived from at least one dicarboxylic acid and at least one diol; and having: -Mn≥40000 -Mw / q≤90000, in: q is the weight percentage of polyester oligomers with a molecular weight of ≤10,000 as determined by GPC; Molecular weights "Mn" and "Mw" are measured by gel permeation chromatography GPC; The Poisson's ratio is calculated as the ratio of shear viscosity to melt strength MS; Shear viscosity was measured according to ASTM D3835-90 using a capillary tube with a diameter of 1 mm and L / D = 30 at γ = 103.7 s -1 The flow gradient is determined at 180 °C. Melt strength MS according to ISO 16790:2005 at 180 ° C and γ = 103.7s -l A capillary with a diameter of 1 mm and L / D = 30 was used at 6 mm / s. 2 Measured under constant acceleration and 110mm stretching length; The coefficient of friction of films of such polyesters is from 5 to 10, as measured by the following method: A sample of the polyester in the form of a flexible stretched film with a thickness ranging from 3 to 50 microns is wrapped around a glass slide covered on a support surface measuring 150 mm × 300 mm × 2 mm thick. The film sample must adhere perfectly to the glass slide and must present a smooth surface without wrinkles. The slide is placed in a horizontal position and a stainless steel slide weighing 200 ± 5 grams and measuring 63.5 mm × 5 mm thick is placed on it. A load cell is connected to one end of the slide by a nylon thread. The load cell is positioned on the moving crossbar of a dynamometer and moves at a constant speed of 10 mm / min. The coefficient of friction is defined as the ratio of the force F recorded by the dynamometer at the moment of loss of adhesion between the slide and the film to the weight Fg acting perpendicularly on the two contact surfaces, where F is the tangential friction force that hinders sliding and Fg is the weight of the steel slide. 2 . The biodegradable aliphatic-aromatic polyester according to claim 1 , wherein the shear viscosity is 800 to 1200 Pa·s. The biodegradable aliphatic-aromatic polyester according to claim 1 , wherein the shear viscosity is 900 Pa·s to 1150 Pa·s.

4. The biodegradable aliphatic-aromatic polyester according to claim 1, wherein an aliphatic polyester is added to the biodegradable aliphatic-aromatic polyester.

5. The biodegradable aliphatic-aromatic polyester according to claim 4, wherein the aliphatic polyester comprises at least one aliphatic diacid and at least one aliphatic diol.

6. The biodegradable aliphatic-aromatic polyester according to claim 1, wherein the biodegradable aliphatic-aromatic polyester has an aromatic portion comprising at least one polyfunctional aromatic acid and an aliphatic portion comprising at least one aliphatic diacid and at least one aliphatic diol.

7. The biodegradable aliphatic-aromatic polyester according to claim 6, wherein the polyfunctional aromatic acid is chosen from aromatic dicarboxylic acid compounds of the phthalic acid type and heterocyclic aromatic dicarboxylic acid compounds of renewable origin, their esters or mixtures thereof.

8. The biodegradable aliphatic-aromatic polyester according to claim 7, wherein the content of the polyfunctional aromatic acid is 30 to 70% by mole relative to the total content of the dicarboxylic acid by mole.

9. The biodegradable aliphatic-aromatic polyester according to any one of claims 6 or 7, wherein the aliphatic diacid is an aliphatic dicarboxylic acid having 2 to 22 carbon atoms in the main chain or an ester thereof.

10. The biodegradable aliphatic-aromatic polyester according to claim 9, wherein the aliphatic dicarboxylic acid is derived from a renewable source.

11. The biodegradable aliphatic-aromatic polyester according to claim 1, wherein the aliphatic dicarboxylic acid from renewable sources comprises at least 50% by mole of azelaic acid, adipic acid or a mixture thereof, relative to the total moles of aliphatic dicarboxylic acids.

12. A mixture of the biodegradable aliphatic-aromatic polyester according to any one of claims 1 to 11 with one or more polymers of synthetic or natural origin.

13. The mixture according to claim 12, wherein the polymer of synthetic or natural origin is biodegradable.

14. The mixture according to claim 13, wherein the biodegradable polymer is a biodegradable polyester of the polyester-ether type.

15. The mixture according to claim 13, wherein the biodegradable polymer is a biodegradable polyester of the hydroxy acid type or of the aliphatic or aliphatic-aromatic dicarboxylic acid-diol type.

16. The mixture according to claim 15, wherein the biodegradable polyester from hydroxy acids is selected from poly L-lactic acid, stereocomplexes of poly D-lactic acid and poly DL-lactic acid, poly-ε-caprolactone, polyhydroxybutyrate, polyhydroxybutyrate-valerate, polyhydroxybutyrate-propionate, polyhydroxybutyrate-hexanoate, polyhydroxybutyrate-decanoate, polyhydroxybutyrate-dodecanoate, polyhydroxybutyrate-octadecanoate or poly 3-hydroxybutyrate-4-hydroxybutyrate.

17. The mixture according to claim 12, wherein the natural polymer is selected from starch, cellulose, chitin, chitosan, alginate, protein, gelatin, natural gum, purified, hydrolyzed, alkalized or unprocessed lignin or its derivatives.

18. The mixture of claim 12, wherein the natural polymer is selected from gluten, zein, casein, or collagen.

19. The mixture of claim 12, wherein the polymer is selected from the group consisting of polyolefins, non-biodegradable polyesters, polyester-urethanes, polyether-urethanes, polyamides, polyamino acids, polyethers, polycarbonates, and mixtures thereof.

20. A packaging film comprising the biodegradable aliphatic-aromatic polyester according to any one of claims 1 to 11 or the mixture according to any one of claims 12 to 19.

21. Use of the packaging film according to claim 20 for producing a film having a thickness of 3 to 50 μm.

22. Use of the packaging film according to claim 20 for producing a film having a thickness of 6 to 25 μm.

23. Use of the packaging film according to claim 20 in food product packaging, industrial packaging, agricultural baling or waste wrapping.

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