Thermoplastic composition for the manufacture of transparent films

Abstract

Thermoplastic composition for the manufacture of transparent films, and the biodegradable and compostable transparent film obtained, both in monolayer and multilayer structure, comprising thermoplastic potato starch, in a proportion greater than 10% by weight with respect to the total, biodegradable biopolyesters, in a proportion greater than 50% and less than 90% by weight with respect to the total, and other biomaterials and additives, in a proportion between 0% and 10% by weight with respect to the total, the composition being biodegradable and compostable. This composition using potato starch allows, for the same dry starch content and the same production conditions, to develop films with greater transparency, less haze, less colour and odour than with corn starch or other alternatives known in the market, maintaining or improving the rest of the mechanical properties (resistance to breakage, tearing and puncture), while increasing the melt speed.

Description

(19) *EP004707334A1* (11) EP 4 707 334 A1 (12) EUROPEAN PATENT APPLICATION (43) Date of publication: 11.03.2026 Bulletin 2026 / 11 (21) Application number: 24382954.6 (22) Date of filing: 05.09.2024 (51) International Patent Classification (IPC): C08L 67 / 02 (2006.01) (52) Cooperative Patent Classification (CPC): (C-Sets available) C08L 67 / 02 (Cont.) (84) Designated Contracting States: AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR Designated Extension States: BA Designated Validation States: GE KH MA MD TN (71) Applicant: Sociedad Anónima Minera Catalano Aragonesa 50001 Zaragoza (ES) (72) Inventors: • ALFONSO ALEGRE, MARIA JOSÉ 50001 ZARAGOZA (ES) • CABALLERO LÓPEZ, MIGUEL ÁNGEL 50001 ZARAGOZA (ES) • GRACIA CASADO, ALFREDO 50001 ZARAGOZA (ES) (74) Representative: Schäfer, Matthias W. SCHAEFER Patent Trademark & Design Schwanseestrasse 43 81549 München (DE) (54) THERMOPLASTIC COMPOSITION FOR THE MANUFACTURE OF TRANSPARENT FILMS (57) Thermoplastic composition for the manufacture of transparent films, and the biodegradable and compo- stable transparent film obtained, both in monolayer and multilayer structure, comprising thermoplastic potato starch, in a proportion greater than 10% by weight with respect to the total, biodegradable biopolyesters, in a proportion greater than50%and less than 90%byweight with respect to the total, and other biomaterials and additives, in a proportion between0% and 10%by weight with respect to the total, the composition being biode- gradable and compostable. This composition using potato starch allows, for the same dry starch content and the same production con- ditions, to develop films with greater transparency, less haze, less colour and odour thanwith corn starch or other alternatives known in the market, maintaining or improv- ing the rest of the mechanical properties (resistance to breakage, tearing and puncture), while increasing the melt speed. EP 4 70 7 33 4 A 1 Processed by Luminess, 75001 PARIS (FR) (Cont. next page) (52) Cooperative Patent Classification (CPC): (Cont.) C-Sets C08L 67 / 02, C08L 3 / 02, C08K 5 / 053 2 EP 4 707 334 A1 Description

[0001] As its title indicates, the present specification relates to a thermoplastic composition for the manufacture of transparent films, and the biodegradable and compostable transparent film obtained, both in monolayer and multilayer structure, comprising thermoplastic potato starch, in a proportion greater than 10% by weight with respect to the total, biodegradable biopolyesters, in a proportion greater than 50% and less than 90% by weight with respect to the total, and other biomaterials and additives, in a proportion between 0% and 10% by weight with respect to the total, the composition being biodegradable and compostable. Field of the invention

[0002] The invention relates to the field of thermoplastic compositions for the manufacture of biodegradable and compostable transparent films. State of the art

[0003] At present, a large number of biobased and biodegradable biopolymers are known in different media, such as industrial, anaerobic, home, soil, water composting, etc., whereby films whose transparency is valued such as, for example, for the application of fruit and vegetable counter bags, can be produced. For this application, films of a thickness between 7 and 20 microns are usually used, which, in addition to good transparency, must have excellent mechanical properties of resistance to breakage, tearing and puncture.

[0004] Furthermore, an increasing number of regulations are appearing that demand that these bags must also be biodegradable in industrial composting facilities or in domestic composting equipment, even requiring a minimum biobased content of 60% in some cases.

[0005] The marketing of products with a high starch content is very interesting because of its low cost, especially that of corn. Additionally, starch is biobased and biodegradable in most media, which facilitates meeting the requirements of the regulations for counter bags. We can find a large number of films that incorporate corn or potato starch, such as, for example, that disclosed in GB2573603A "Bag for fruits and vegetables" or CN102702579A "Potato starch-based edible composite food packaging film and preparationmethod thereof’ that seek to obtain a biodegradable product at a low cost. However, by increasing thestarchcontent, theseproductsgiveus theproblem that the transparencyof thefilmsdecreases and their colour and odour increase, due to the thermal degradation of the starch during its mixture with other biomaterials andduring themanufacture of the film, giving rise to aproduct that is not very visually pleasant for use, givingasensationof lower quality. They may be valid for some applications, but they are not especially well received for counter bags for fruits and vegetables.

[0006] Currently, attempts are being made to resolve this problem by manufacturing multilayer films, with at least three layers in coextrusion equipment. The product with starch is in the core layer and for the outer layers starch-free products with greater transparency are used. This results in a film with sufficient transparency and little odour / colour, which is much more pleasant to use. The core layer product usually contains thermoplastic starch (plasticised starch) and other biopolymers that improve the processability and properties of the product.

[0007] In these multilayer films, the thermoplastic starch comprises one or more starches and one or more plasticisers, and the other biopolymers are biodegradable. The content of thermoplastic starch is usually comprised between 15% and 50% by weight with respect to the total and that of the other biodegradable biopolymers between 45% and 80% by weight with respect to the total. The core layer typically accounts for 50‑90% of the total thickness, preferably 60‑85% and more preferably 70‑80%.

[0008] In these multilayer films, the product of the outer layers are usually mixtures of biodegradable aliphatic or biodegradable aliphatic-aromatic biopolyesters, and may also contain other biopolymers and additives, preferably below 10%.Theouter layers typically account for 10‑40%of the total thickness, preferably 15‑40% andmore preferably 20‑30%.

[0009] However, this solution of multilayer films in coextrusion equipment presents several important problems, one of them being that not all film producers have coextrusion technology or do not want to dedicate it to biopolymers, which implies a significant additional economic investment for them.

[0010] Another problem of multilayer films is that the biopolymers of the outer layers are expensive, significantly increasing the final cost of the film. To try to reduce costs, producers usually minimise the thickness of the most expensive outer layers, usuallymaking a10 / 80 / 10 distributionwhich entails, for 10microns total, 1micron in theouter layers,which is very difficult to achieve in most coextrusion equipment.

[0011] Furthermore, in multilayer films the outer layers usually have a biobased content of less than 50%, since the biopolyesters normally used for their good processing and properties have a biobased content of less than 45% (for example, poly(butylene sebacate-co-butylene terephthalate) (PBTSeT)). Although the outer layer may also contain polylactic acid (PLA) having a biobased content of 100%, its concentration is usually less than 10% so as not to adversely 3 EP 4 707 334 A1 5 10 15 20 25 30 35 40 45 50 55 affect the tear strength. The limitation in the biobased content of the outer layer to less than 50% means that, although, thanks to the thermoplastic starch content, it may have 60% biobased content, the biobased content of the entire resulting film, considering all layers, is less than 60% required by some regulations for counter bags.

[0012] Wefindsomemultilayer embodiments suchas theonedisclosed inES2420830 "Polylactic acid (PLA) sheetwith goodantistatic properties",which seeks to reduce the static ofmultilayer filmwherein theouter layers are basedonPLAby adding 0.01‑20% of starch. The use of starch is to reduce the cost, but transparency is achieved with the PLA, although they do not demonstrate or intend to achieve greater transparency than other embodiments, since that is not the technical problem they aim to resolve.

[0013] A solution is also known such as that disclosed in CN110753720A "Biodegradable three-layered film" which protects a multilayer film wherein the outer layers contain biopolyesters containing sebacic acid which provides greater transparency thanotherbiopolyesters suchasPBATand the inner layerof starch, although it doesnot specifywhich typeof starch. Each outer layer is 10‑20% of the total thickness, and the inner layer contains plasticised starch and aliphatic- aromatic biopolyester, and the biopolyesters of the outer layers contain highly transparent sebacic acid, but despite everything they only achieve a haze range of 35‑60% with a multilayer structure, similar to that achieved with the composition of the invention with monolayer structure. Thus, the composition of the invention achieves a haze of 55%, within the range of 35‑60% for which CN110753720A needs a multilayer film, and with the composition of the invention, a multilayer is achievedwithpotato in the core layer andPBATin theouter layers that it obtainshasahazeof 15%, lower than the minimum value defined by CN110753720A (35%), i.e. greatly exceeding its transparency characteristic and significantly improving this state of the art, obtaining a much more transparent film with a higher starch content.

[0014] It is clear that there is a need for biodegradable and compostable compositions, with a high biobased content, whichallowachievingfilmswithmaximum transparencywithout impairing theirmechanical properties, capableofmeeting the regulations for counter bags for fruits and vegetables, and other applications. Description of the invention

[0015] In order to resolve the problem currently existing in the manufacture of biodegradable and compostable films, achieving maximum transparency, improving the current state of the art, the thermoplastic composition for the manu- facture of transparent films has been devised, which comprises: - thermoplastic potato starch, in a proportion greater than 10% by weight with respect to the total, - biodegradable biopolyesters, in a proportion greater than 50% and less than 90% by weight with respect to the total, and - other biomaterials and additives, other than a thermoplastic starch, in a proportion between 0% and 10% by weight with respect to the total, the composition being biodegradable and compostable.

[0016] The object of the invention is both the thermoplastic composition for themanufacture of transparent films and the biodegradable and compostable transparent film obtained with it.

[0017] The composition may further comprise another complementary thermoplastic starch, in a proportion of less than 30% by weight with respect to the total, containing one or more starches originating from the group formed by corn, pea, tapioca, cassava or obtained from starch-containing biomasses including waste from the agri-food industry. This addition of another complementary thermoplastic starchwould be done at the cost of reducing biodegradable biopolyesters and / or the other biomaterials and additives, if any, by the same percentage.

[0018] The thermoplastic potato starch and,whereappropriate, the complementary thermoplastic starch, comprise one ormoreplasticisers chosen from thegroup formedbywater, polyhydric alcohols, ethers, thioethers, theesters thereof, any other compound or polymer capable of transforming a starch into thermoplastic starch, or a combination thereof.

[0019] Thermoplastic potato starch preferably contains potato starch from the group consisting of biomass and waste from the food industry that contain potato starch, understanding as waste from the food industry discarded potatoes, washing water, etc.

[0020] Thestarch or starcheswill be chosen from thegroup formedby native starch,modified starch, starch derivatives, or a mixture thereof.

[0021] The biopolyesters are chosen from the group formed by poly(butylene adipate-co-butylene terephthalate) (PBAT), poly(butylene sebacate-co-butylene terephthalate) (PBTSeT), poly(butylene succinate) (PBS), poly(butylene succinate-co-adipate) (PBSA), polylactic acid (PLA), polyhydroxy acids (PHA), poly(butylene terephthalate-co-butylene succinate) PBTS or their mixtures, being preferably chosen from the group formed by poly(butylene adipate-co-butylene terephthalate) (PBAT) and poly(butylene sebacate-co-butylene terephthalate) (PBTSeT).

[0022] The other biomaterials and additives are chosen from the group formed by polyvinyl acetate (PVA), polypro- pylene carbonate) (PPC), polyglycolic acid (PGA), cellulose, modified cellulose, fibres, colouring agents, impact 4 EP 4 707 334 A1 5 10 15 20 25 30 35 40 45 50 55 modifiers, organic and inorganic fillers, heat stabilisers, hydrolysis stabilisers, UV stabilisers, lubricants, enzymes, biodegradability accelerating additives, other additives and other biodegradable polymers.

[0023] This thermoplastic composition is used for the manufacture of a transparent film, with a monolayer or multilayer structure comprising at least one layer containing a composition as described above, preferably having a thickness comprised between 7 and 100 microns.

[0024] In a preferred embodiment with multilayer structure, the film has a structure formed by an intermediate layer and two outer layers, the intermediate layer being the one containing a composition as described above. The outer layers may have different thicknesses. Likewise, the outer layers may have the same or different composition. Preferably the outer layers consist of biopolyesters chosen from the group formed by aliphatic biopolyesters and aliphatic-aromatic biopo- lyesters, and more preferably they consist of biopolyesters chosen from the group formed by poly(butylene adipate-co- butylene terephthalate) (PBAT) and poly(butylene sebacate-co-butylene terephthalate) (PBTSeT). Advantages of the invention

[0025] The main advantage of this composition using potato starch, for the same dry starch content and the same production conditions, is that it allows the development of biopolymers and films with greater transparency, less haze, less colour and odour than using corn starch or other alternatives known in the market, maintaining or improving the rest of the mechanical properties (resistance to breakage, tearing and puncture).

[0026] Anothernotableadvantageof this composition is that themelt volume-flowrate (MVR)withpotatostarch ishigher than with corn, that is, its viscosity is lower, which makes it possible to increase production in the film manufacturing lines and lower the production cost.

[0027] It is important to note that this composition makes it possible to develop with potato starch a simpler, cheaper monolayer structure, with a higher biobased content and less odour than multilayer structures based exclusively on corn starch, but with a similar or improved transparency.

[0028] Thanks to this composition, it is also a great advantage to be able to use a simpler and more accessible monolayer extruder on the market and to be able to increase the biobased content (starch) while maintaining a transparency, colour and odour similar to multilayer film.

[0029] Likewise, we cannot fail to highlight that this composition also makes it possible to develop with potato starch a multilayer structure with biopolyesters in the outer layers and the biopolymer with starch in the inner layer, much more transparent than current solutions and with a higher biobased content.

[0030] This allows the manufacture of films for all those applications wherein transparency is highly valued, such as for the application of counter bags for fruits and vegetables, being biodegradable in industrial composting facilities and in domestic composting equipment, complying with the requirements of biobased content equal to or greater than 60% in accordance with the regulations in force in some countries, such as France and Italy. Another important advantage of the invention is that it allows the reuse as thermoplastic potato starch of potato starch from waste such as biomass or waste from the food industry, which results in a significant improvement in its ecological sustainability. Description of the figures

[0031] Figure 1 shows a sectional view of an example of a monolayer film. Figure 2 shows a sectional view of an example of a multilayer film formed from three layers. Preferred embodiment of the invention

[0032] The thermoplastic composition for the manufacture of transparent films comprises - thermoplastic potato starch, in a proportion greater than 10% by weight with respect to the total, - biodegradable biopolyesters, in a proportion greater than 50% and less than 90% by weight with respect to the total, and - other biomaterials and additives, other than a thermoplastic starch, in a proportion between 0% and 10% by weight with respect to the total, the composition being biodegradable and compostable.

[0033] The composition may further comprise another complementary thermoplastic starch, in a proportion of less than 30% by weight with respect to the total, containing one or more starches originating from the group formed by corn, pea, tapioca, cassava or obtained from starch-containing biomasses including waste from the agri-food industry. This addition 5 EP 4 707 334 A1 5 10 15 20 25 30 35 40 45 50 55 of another complementary thermoplastic starchwould be done at the cost of reducing biodegradable biopolyesters and / or the other biomaterials and additives, if any, by the same percentage.

[0034] The total amount of thermoplastic starch (thermoplastic potato starch+complementary thermoplastic starch)will always be ≤40% by weight with respect to the total, since above those values the mechanical, optical and organometallic properties are not suitable for flexible film applications.

[0035] The thermoplastic potato starch and,whereappropriate, the complementary thermoplastic starch, comprise one ormoreplasticisers chosen from thegroup formedbywater, polyhydric alcohols, ethers, thioethers, theesters thereof, any other compound or polymer capable of transforming a starch into thermoplastic starch, or a combination thereof.

[0036] Thestarch or starcheswill be chosen from thegroup formedby native starch,modified starch, starch derivatives, or a mixture thereof.

[0037] The biopolyesters are chosen from the group formed by poly(butylene adipate-co-butylene terephthalate) (PBAT), poly(butylene sebacate-co-butylene terephthalate) (PBTSeT), poly(butylene succinate) (PBS), poly(butylene succinate-co-adipate) (PBSA), polylactic acid (PLA), polyhydroxy acids (PHA), poly(butylene terephthalate-co-butylene succinate (PBTS) or their mixtures, being preferably chosen from the group formed by poly(butylene adipate-co-butylene terephthalate) (PBAT) and poly(butylene sebacate-co-butylene terephthalate) (PBTSeT).

[0038] The other biomaterials and additives are chosen from the group formed by polyvinyl acetate (PVA), polypro- pylene carbonate) (PPC), polyglycolic acid (PGA), cellulose, modified cellulose, fibres, colouring agents, impact modifiers, organic and inorganic fillers, heat stabilisers, hydrolysis stabilisers, UV stabilisers, lubricants, enzymes, biodegradability accelerating additives, other additives and other biodegradable polymers.

[0039] Thermoplastic potato starch preferably contains potato starch from the group consisting of biomass and waste from the food industry that contain potato starch, understanding as waste from the food industry discarded potatoes, washing water, etc.

[0040] This thermoplastic composition is used for the manufacture of a transparent film comprising at least one layer (1) containing a composition as described in the preceding claims, preferably having a thickness comprised between 7 and 100 microns.

[0041] Thefilmmayhaveamonolayer, ormultilayer structure. In caseof havingamultilayer structure, itmayhave twoor more layers.

[0042] In a preferred embodiment with multilayer structure the film has a structure formed by an intermediate layer (1) and two outer layers (2,3), the intermediate layer (1) being the one containing a composition as described in the preceding claims 1 to 7. The outer layers (2,3) can have different thicknesses. Also, the outer layers (2,3) may have the same or different composition.

[0043] Preferably, the outer layers (2,3) consist of biopolyesters chosen from the group formed by aliphatic biopolye- sters and aliphatic-aromatic biopolyesters, and more preferably they consist of biopolyesters chosen from the group formed by poly(butylene adipate-co-butylene terephthalate) (PBAT) and poly(butylene sebacate-co-butylene terephtha- late) (PBTSeT). Examples of experimental tests and their results

[0044] This composition has been subjected to intense experimental tests to determine its components, their percen- tages and their effect on the solution of the technical problem posed, of which we show some of the results by way of example. Example 1 - Monolayer blown film

[0045] For these comparative tests,monolayer filmshavebeenmadeusingdifferent compositions. In tests 2, 4, 6 and8, native corn starch was used, and in tests 1, 3, 5, and 7, potato starch extracted from biomass waste from the agri-food industry was used. In all cases, sorbitol has been used as a plasticiser and PBAT as a biopolyester.

[0046] It is verified in Table 1 that for the same amount of dry starch, in those compositions with potato starch the haze is lower than with corn starch, therefore the transparency is greater. Table 1 ‑ Monolayer blown film TEST Starch % Dry starch % Plasticiser Thickness, microns Haze (ASTM D1003), % 1 Potato 12.00 5.00 12 45 19 44 2 Corn 12.00 5.00 11 58 20 54 6 EP 4 707 334 A1 5 10 15 20 25 30 35 40 45 50 55 (continued) TEST Starch % Dry starch % Plasticiser Thickness, microns Haze (ASTM D1003), % 3 Potato 15.00 6.20 13 57 20 53 4 Corn 15.00 6.20 13 74 19 72 5 Potato 17.00 7.00 12 54 19 55 6 Corn 17.00 7.00 10 84 20 78 7 Potato 19.00 8.00 11 55 21 56 8 Corn 19.00 8.00 10 94 20 95

[0047] Table 2 shows that the formation or compounding conditions used in the previous tests are similar in all cases: 7 EP 4 707 334 A1 5 10 15 20 25 30 35 40 45 50 55 Ta bl e 2 ‑C om po un di ng co nd iti on s of th e te st s of Ta bl e 1 TE ST C hi m ne ys kg / h B ar re lt em pe ra tu re s, °C R PM Va cu um M el tin g te m pe ra tu re ,° C To rq ue ,% SM E (s pe ci fic en er gy ), kW h / kg Pr es su re ,b ar 1 AA C 20 90 / 1 70 *2 / 1 35 *3 60 0 10 00 18 2‑ 19 0 47 ‑5 5 0. 32 ‑0 .3 6 21 ‑2 6 2 AA C 20 90 / 1 70 *2 / 1 35 *3 60 0 10 00 18 5‑ 19 4 51 ‑5 7 0. 36 2‑ 0. 38 5 21 ‑2 6 3 AA C 20 90 / 1 70 *2 / 1 35 *3 60 0 10 00 18 1‑ 18 4 45 ‑5 3 0. 32 2‑ 0. 35 1 21 ‑2 7 4 AA C 20 90 / 1 70 *2 / 1 35 *3 60 0 10 00 13 2‑ 18 8 42 ‑4 8 0. 30 3‑ 0. 32 7 22 ‑2 7 5 AA C 20 90 / 1 70 *2 / 1 35 *3 60 0 10 00 17 6‑ 18 2 47 ‑6 0 0. 29 7‑ 0. 30 8 21 ‑2 7 6 AA C 20 90 / 1 70 *2 / 1 35 *3 60 0 10 00 18 8‑ 19 4 50 ‑5 6 0. 35 8‑ 0. 38 0 23 ‑2 6 7 AA C 20 90 / 1 70 *2 / 1 35 *3 60 0 10 00 18 4‑ 19 0 49 ‑5 5 0. 32 0‑ 0. 34 0 22 ‑2 6 8 AA C 20 90 / 1 70 *2 / 1 35 *3 60 0 10 00 19 4‑ 20 0 52 ‑5 8 0. 37 0‑ 0. 39 0 24 ‑2 8 8 EP 4 707 334 A1 5 10 15 20 25 30 35 40 45 50 55

[0048] In table 3, we verify the colour of the pellets with which the films of the tests of Table 1 have been manufactured, verifying how less colour and odour is obtained with potato starch than with corn: Table 3 ‑ Colour of the pellets with which the films of the tests of Table 1 have been manufactured TEST L a b Yi 1 76 2 19 43 2 74 3 20 46 3 76 2 19 42 4 74 3 20 46 5 76 2 19 42 6 71 3 20 48 7 73 2 19 44 8 68 3 20 50

[0049] In Table 4 we have the mechanical properties of the pellets with which the films of the tests of Table 1 have been manufactured, verifying that the mechanical properties with potato starch are similar, or even better than with corn: 9 EP 4 707 334 A1 5 10 15 20 25 30 35 40 45 50 55 Ta bl e 4 ‑M ec ha ni ca lp ro pe rti es of th e pe lle ts w ith w hi ch th e fil m s of th e te st s of Ta bl e 1 ha ve be en m an uf ac tu re d TE ST M D te ns ile (IS O 52 7‑ 3) TD te ns ile (IS O 52 7‑ 3) M D El m en do rf te ar st re ng th (IS O 63 83 ‑2 ) TD El m en do rf te ar st re ng th (IS O 63 83 ‑2 ) Pu nc tu re (IS O 14 47 7) St re ss at br ea k, M Pa D ef or m at io n at br ea k, % St re ss at br ea k, M Pa D ef or m at io n at br ea k, % Te ar st re ng th m N Te ar st re ng th m N M ax im um lo ad ,N M ax im um lo ad ex te ns io n, m m En er gy at m ax im um lo ad 1 30 .3 39 0 19 .6 46 4 81 5 13 49 23 .3 43 6 25 .3 55 6 17 87 28 27 0. 8 4. 4 2. 1 2 26 48 2 17 .2 42 3 84 4 15 79 21 .5 36 7 28 .1 62 8 16 21 24 08 0. 8 4. 6 2. 3 3 23 .4 26 7 17 41 4 80 2 19 33 20 .1 44 1 21 55 0 21 90 28 23 0. 7 4. 0 1. 6 4 21 25 9 13 .5 36 6 49 6 11 48 19 .4 44 4 22 .1 53 2 19 73 27 55 0. 7 3. 9 1. 6 5 21 .5 31 2 18 .2 46 5 83 6 22 00 21 .7 46 6 23 .2 59 6 20 79 28 38 0. 7 4. 7 12 .0 6 19 32 5. 4 15 .4 37 4 90 2 13 63 17 .6 36 5 24 .6 62 3 19 57 27 20 0. 7 3. 9 17 7 20 31 5 18 38 0 81 0 21 05 19 36 0 24 .1 60 5 21 00 28 00 0. 7 4. 8 2. 1 8 18 32 0 15 36 0 85 0 12 00 17 35 0 24 61 0 19 05 26 50 0. 7 4. 2 2. 0 10 EP 4 707 334 A1 5 10 15 20 25 30 35 40 45 50 55

[0050] In the following table 5, we see the melt volume-flow rate (MVR) of the pellets with which the films of the tests of Table1havebeenmanufactured, verifyinghow themelt volume-flow rate (MVR)withpotatostarch ishigher thanwith corn, i.e. It has lower viscosity, which can increase production in the film lines and lower the production cost. Table 5 ‑ Melt volume-flow rate (MVR) of the pellets with which the films of the tests of Table 1 have been manufactured TEST MVR 190°C / 2.16 kg (humidity) 1 4.2 (0.12%) 2 3.97 (0.12%) 3 2.97 (0.15%) 4 2.41 (0.12%) 5 2.75 (0.2%) 6 2.4 (0.16%) 7 2.65 (0.15%) 8 2.38 (0.16%) Example 2 - Comparison between monolayer and multilayer film

[0051] To conduct this experimental test, two monolayer films were used, one with corn starch (test 4) and the other with potato starch (test 7), both fromexample 1, and twonewfilmswith a20 / 80 / 10multilayer structure,wherein theouter layers are made of PBAT, and the inner layer with corn starch (test 9) and potato starch (test 10). Table 6 ‑ Comparison of haze of monolayer and multilayer film with potato and corn starch. TEST Composition Film Thickness, microns Haze % 4 Test 4 biopolymer (15% dry corn starch) Monolayer 10‑15 74 7 Test 7 biopolymer (19% dried potato starch) Monolayer 10‑15 55 9 Test 4 PBAT / biopolymer (15% dry corn starch) / PBAT Multilayer 20 / 80 / 10 1.2 / 10 / 1.2 45 10 Test 7 PBAT / Biopolymer (19% dried potato starch) / PBAT Multilayer 20 / 80 / 10 1.2 / 10 / 1.2 15

[0052] In this tablewe can seehow the problem of the high hazeofmonolayer filmswith starch (test 4) is being solved by developing multilayer structures (test 9) wherein the core layer contains starch, which provides a high biobased content, biodegradability and enables lowering the price of the structure, and the outer layers a biopolyester, PBAT in this case, which lowers the haze of the final structure (45 vs 74%), but makes it more expensive and decreases its biobased content.

[0053] The multilayer film of test 9 corresponds to a film of composition already known in CN110753720A, with corn starch, wherein the outer layers contain PBTSeT instead of PBATas it is more transparent, but we verified how film 10, using potato film, far exceeds its results.

[0054] The comparison of results between test 7 and test 4 allows us to verify how a lower haze is obtained with potato starch, even with a higher percentage (19%vs15%). This implies a significant advantage in technical requirements for the application, thanks to its greater transparency.

[0055] The comparison of results between test 7 and test 9 indicates that the haze and the rest of the properties are very similar with monolayer with potato (with 19% dry starch) and with multilayer with corn (with 15% dry starch), obtaining a haze of 55% compared to 45%. This implies a great advantage in being able to use a simpler monolayer extruder, accessible on the market, and in being able to increase the biobased content (starch) while maintaining a transparency, colour and odour similar to multilayer film.

[0056] Thecomparisonof results between test 10and test 9 shows that lesshaze is obtained in coextrusionusingpotato starch (19% dry starch) versus corn starch (15% dry starch). This gives us the advantage of obtaining a much more transparent film with a higher starch content, with the additional advantage of a higher biobased content, due to a higher starch content, with very good transparency. 11 EP 4 707 334 A1 5 10 15 20 25 30 35 40 45 50 55

[0057] In the case of test 10, the haze values of 15% obtained are much lower than the range achieved in already known solutions, with corn starch, wherein the outer layers contain PBTSeT instead of PBATas it is more transparent, such as CN110753720A, wherein a haze of 35‑60% is obtained. Example 3 - Comparison of mechanical properties between multilayer films

[0058] In this experimental test, themechanical properties of the twomultilayer films, onewith corn starch, and the other withpotatostarch, previouslyused inexample2,havebeencompared.Thecomparisonof results shows that, although the mechanical properties are similar, or even better, with potato starch (19% dry starch - test 10) than with corn starch (15% dry starch - test 9), the transparency obtained in the case of test 10 is much higher, as we saw earlier. Table 7 ‑ Comparison of multilayer properties with potato and corn starch TEST MD tensile strength (IS0527‑3) MD Elmendorf tear strength (ISO6383‑2) TD Elmendorf tear strength (ISO6383‑2) Thickness, microns Module, MPa Creep stress, MPa Creep deformation, % Stress at break, MPa Deformation at break, % Tear strength mN Tear strength mN 9 13 190 7 7 22 299 881 1859 10 12 180 8 8 22 276 1018 2648

[0059] Personsskilled in theartwill easilyunderstand that thecharacteristicsof different embodimentscanbecombined with characteristics of other possible embodiments whenever such a combination is technically possible.

[0060] All the information referring to examples or modes of embodiment, form part of the description of the invention. Claims 1. - Thermoplastic composition for the manufacture of transparent films, characterised in that it comprises - thermoplastic potato starch, in a proportion greater than 10% by weight with respect to the total, - biodegradable biopolyesters, in a proportion greater than 50% and less than 90% by weight with respect to the total, and - other biomaterials and additives, other than a thermoplastic starch, in a proportion between 0% and 10% by weight with respect to the total, the composition being biodegradable and compostable. 2. - Thermoplastic composition for the manufacture of transparent films, according to the preceding claim, charac- terised in that the biodegradable biopolyesters are chosen from the group formed by poly(butylene adipate-co- butylene terephthalate) (PBAT), poly(butylene sebacate-co-butylene terephthalate) (PBTSeT), poly(butylene succi- nate) (PBS), poly(butylene succinate-co-adipate) (PBSA), polylactic acid (PLA), polyhydroxy acids (PHA), poly(bu- tylene-co-tetrahydrofurandimethylene succinate) PBTS or their mixtures. 3. - Thermoplastic composition for the manufacture of transparent films, according to claim 1, characterised in that the biodegradable biopolyesters are chosen from the group formed by poly(butylene adipate-co-butylene terephthalate) (PBAT) and poly(butylene sebacate-co-butylene terephthalate) (PBTSeT). 4. - Thermoplastic composition for the manufacture of transparent films, according to any of the preceding claims, characterised in that the other biomaterials and additives are chosen from the group formed by PVA (polyvinyl alcohol), PPC (polypropylene carbonate), PGA (polyglycolic acid), cellulose, modified cellulose, fibres, colouring agents, impact modifiers, organic and inorganic fillers, heat stabilisers, hydrolysis stabilisers, UV stabilisers, lubricants, enzymes, biodegradability accelerating additives, other additives and other biodegradable polymers. 12 EP 4 707 334 A1 5 10 15 20 25 30 35 40 45 50 55 5. - Thermoplastic composition for the manufacture of transparent films, according to any of the preceding claims, characterised in that the thermoplastic potato starch contains potato starch from the group formed by biomass and waste from the food industry containing potato starch. 6. - Thermoplastic composition for the manufacture of transparent films, according to any of the preceding claims, characterised in that it additionally comprisesanother complementary thermoplastic starch, inaproportion less than 30% by weight with respect to the total, containing one or more starches originating from the group formed by corn, pea, tapioca, cassava or obtained from starch-containing biomasses including waste from the agri-food industry. 7. - Thermoplastic composition for the manufacture of transparent films, according to any of the preceding claims, characterised in that the thermoplastic potato starch and, where appropriate, the complementary thermoplastic starch, comprise one or more plasticisers chosen from the group formed by water, polyhydric alcohols, ethers, thioethers, the esters thereof, any other compound or polymer capable of transforming a starch into thermoplastic starch, or a combination thereof. 8. - Thermoplastic composition for the manufacture of transparent films, according to any of the preceding claims, characterised in that the starch or starches are chosen from the group formed by native starch, modified starch, starch derivatives, or a mixture thereof. 9. - Transparent film characterised in that it comprises at least one layer (1) containing a composition as described in the preceding claims. 10. - Transparent film, according to claim 9, characterised in that the thickness of the film is between 7 and 100 microns. 11. - Transparent film according to any of claims 9 and 10, characterised in that it has a monolayer structure. 12. - Transparent film according to any of claims 9 and 10, characterised in that it has a multilayer structure. 13. - Transparent film, according to claim 12, characterised in that it has a structure formed by an intermediate layer (1) and two outer layers (2,3), the intermediate layer (1) being the one containing a composition as described in the preceding claims 1 to 7. 14. - Transparent film, according to claim 13, characterised in that the outer layers (2,3) consist of biopolyesters chosen from the group formed by aliphatic biopolyesters and aliphatic-aromatic biopolyesters. 15. - Transparent film, according to claim 14, characterised in that the outer layers consist of biopolyesters chosen from the group formed by poly(butylene adipate-co-butylene terephthalate) (PBAT) and poly(butylene sebacate-co- butylene terephthalate) (PBTSeT). 13 EP 4 707 334 A1 5 10 15 20 25 30 35 40 45 50 55 14 EP 4 707 334 A1 15 EP 4 707 334 A1 5 10 15 20 25 30 35 40 45 50 55 16 EP 4 707 334 A1 5 10 15 20 25 30 35 40 45 50 55 17 EP 4 707 334 A1 REFERENCES CITED IN THE DESCRIPTION This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard. Patent documents cited in the description • GB 2573603 A

[0005] • CN 102702579 A

[0005] • ES 2420830

[0012] • CN 110753720 A

[0013]

[0053]

[0057] 摘 要 一种用于制造透明薄膜的热塑性组合物，以及由该组合物获得的单层或多 层结构的可生物降解、可堆肥透明薄膜，该热塑性组合物包含：按总重量计大 于 10 重量%的热塑性马铃薯淀粉、按总重量计大于 50 重量%且小于 90 重量 %的可生物降解生物聚酯，以及按总重量计在 0 重量%至 10 重量%之间的其他 生物材料和添加剂，该组合物是可生物降解和可堆肥的。 该组合物采用马铃薯淀粉，在相同的干淀粉含量和相同的生产条件下，能 够制得比使用玉米淀粉或市场上其他已知替代品更透明、雾度更低、颜色较浅 且气味较轻的薄膜，同时保持或改善其余力学性能（抗断裂性、抗撕裂性和抗 穿刺性），并提高熔融速度。

Claims

1. - Thermoplastic composition for the manufacture of transparent films, characterised in that it comprises - thermoplastic potato starch, in a proportion greater than 10% by weight with respect to the total, - biodegradable biopolyesters, in a proportion greater than 50% and less than 90% by weight with respect to the total, and - other biomaterials and additives, other than a thermoplastic starch, in a proportion between 0% and 10% by weight with respect to the total, the composition being biodegradable and compostable.

2. - Thermoplastic composition for the manufacture of transparent films, according to the preceding claim, characterised in that the biodegradable biopolyesters are chosen from the group formed by poly(butylene adipate-co-butylene terephthalate) (PBAT), poly(butylene sebacate-co-butylene terephthalate) (PBTSeT), poly(butylene succinate) (PBS), poly(butylene succinate-co-adipate) (PBSA), polylactic acid (PLA), polyhydroxy acids (PHA), poly(butylene-co-tetrahydrofurandimethylene succinate) PBTS or their mixtures.

3. - Thermoplastic composition for the manufacture of transparent films, according to claim 1, characterised in that the biodegradable biopolyesters are chosen from the group formed by poly(butylene adipate-co-butylene terephthalate) (PBAT) and poly(butylene sebacate-co-butylene terephthalate) (PBTSeT).

4. - Thermoplastic composition for the manufacture of transparent films, according to any of the preceding claims, characterised in that the other biomaterials and additives are chosen from the group formed by PVA (polyvinyl alcohol), PPC (polypropylene carbonate), PGA (polyglycolic acid), cellulose, modified cellulose, fibres, colouring agents, impact modifiers, organic and inorganic fillers, heat stabilisers, hydrolysis stabilisers, UV stabilisers, lubricants, enzymes, biodegradability accelerating additives, other additives and other biodegradable polymers.

5. - Thermoplastic composition for the manufacture of transparent films, according to any of the preceding claims, characterised in that the thermoplastic potato starch contains potato starch from the group formed by biomass and waste from the food industry containing potato starch.

6. - Thermoplastic composition for the manufacture of transparent films, according to any of the preceding claims, characterised in that it additionally comprises another complementary thermoplastic starch, in a proportion less than 30% by weight with respect to the total, containing one or more starches originating from the group formed by corn, pea, tapioca, cassava or obtained from starch-containing biomasses including waste from the agri-food industry.

7. - Thermoplastic composition for the manufacture of transparent films, according to any of the preceding claims, characterised in that the thermoplastic potato starch and, where appropriate, the complementary thermoplastic starch, comprise one or more plasticisers chosen from the group formed by water, polyhydric alcohols, ethers, thioethers, the esters thereof, any other compound or polymer capable of transforming a starch into thermoplastic starch, or a combination thereof.

8. - Thermoplastic composition for the manufacture of transparent films, according to any of the preceding claims, characterised in that the starch or starches are chosen from the group formed by native starch, modified starch, starch derivatives, or a mixture thereof.

9. - Transparent film characterised in that it comprises at least one layer (1) containing a composition as described in the preceding claims.

10. - Transparent film, according to claim 9, characterised in that the thickness of the film is between 7 and 100 microns.

11. - Transparent film according to any of claims 9 and 10, characterised in that it has a monolayer structure.

12. - Transparent film according to any of claims 9 and 10, characterised in that it has a multilayer structure.

13. - Transparent film, according to claim 12, characterised in that it has a structure formed by an intermediate layer (1) and two outer layers (2,3), the intermediate layer (1) being the one containing a composition as described in the preceding claims 1 to 7.

14. - Transparent film, according to claim 13, characterised in that the outer layers (2,3) consist of biopolyesters chosen from the group formed by aliphatic biopolyesters and aliphatic-aromatic biopolyesters.

15. - Transparent film, according to claim 14, characterised in that the outer layers consist of biopolyesters chosen from the group formed by poly(butylene adipate-co-butylene terephthalate) (PBAT) and poly(butylene sebacate-co-butylene terephthalate) (PBTSeT).

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