Biodegradable polymer compositions for producing molded articles

Abstract

A biodegradable polymer composition for producing a molded article, the biodegradable polymer composition comprising: i. 5% to 70% by weight of a polyester comprising a hydroxyl group derived from an aromatic dicarboxylic acid, succinic acid and C5-C 24 saturated dicarboxylic acid units; and units derived from saturated aliphatic diols and unsaturated aliphatic diols; ii. 0 wt % to 40 wt % of a polyester comprising units derived from succinic acid and units derived from saturated aliphatic diols and unsaturated aliphatic diols; iii. 23 wt % to 43 wt % of a polyhydroxyalkanoate; iv. 10 wt % to 20 wt % of a filler; v. 0 wt % to 0.5 wt % of a crosslinker and / or a chain extender.

Description

[0001] The present invention relates to polymer compositions which are biodegradable in industrial composting and which are particularly suitable for the production of mouldings, in particular by injection moulding.

[0002] The invention also relates to a product obtained from said composition, and to a process for obtaining said product.

[0003] As is known, thermoforming techniques of plastics, such as injection molding, are mainly used to produce articles with high resistance to deformation, such as disposable cutlery, containers, dishes, trays or capsules for dispensing beverages, with a wall thickness usually exceeding 200 microns.

[0004] While the manufacture of thick articles imparts the necessary property of resistance to deformation, it also creates difficulties in ensuring that articles made from inherently biodegradable polymers can decompose in a manner that allows them to be efficiently transported to industrial composting plants.

[0005] In view of the above, it would therefore be desirable to have a composition that could be economically and productively processed into thick-walled moldings without compromising its decomposition in industrial composting.

[0006] Polymer blends currently on the market are usually made of aliphatic and / or aliphatic-aromatic polyesters and lactic acid polymers, such as those described in U.S. Patent No. 6,573,340 and patent application WO 2005 / 063883. However, the injection molded products made of these compositions cannot fully meet the requirements of high temperature deformation resistance, elastic modulus and decomposability. A solution can be to use fillers that improve the dimensional stability of molded products. EP 3 328 940 B1 of the applicant describes a polymer composition comprising poly (1,4-butylene succinate) (PBS), polylactic acid (PLA), a crosslinking agent and talcum (filler). Although the physical properties and mechanical properties of these compositions make them suitable for molding applications, these compositions do not meet the decomposition requirements according to European standard EN13432 when the parts are more than 500 microns thick.

[0007] Patent application US 2013 / 0004759 describes injection molded articles comprising a biodegradable polyester (PBS copolymer), PLA and a mineral filler. If the filler is talc, the composition has a high elastic modulus but is characterized by biodegradation kinetics that do not comply with the harmonized standard EN 13432. If the filler is replaced by gypsum, it is biodegradable according to EN 13432 but shows a decrease in the elastic modulus.

[0008] Starting from the need to find a balance between high deformation resistance at high temperatures, elastic modulus and high decomposition in industrial composting, it has now been found that, surprisingly, this problem can be solved by a composition comprising a biodegradable polyester, an inorganic filler and a polyhydroxyalkanoate having specific properties.

[0009] The moldings comprising the composition according to the invention are characterized by a heat resistance level in accordance with the requirements of the application and therefore do not require a thermal annealing treatment at a temperature of 60 to 120° C. to ensure functionality.

[0010] The present invention relates in particular to a biodegradable polymer composition for producing a molded article, said biodegradable polymer composition comprising, relative to the total composition:

[0011] i) 5 to 70 wt. %, relative to the sum of components i. to v., of at least one polyester comprising:

[0012] a. a dicarboxylic acid component, relative to the total dicarboxylic acid component comprising:

[0013] (a1) 0 to 20 mol %, preferably 0 to 10 mol %, of units derived from at least one aromatic dicarboxylic acid

[0014] (a2) 53 mol % to 95 mol % of succinic acid units,

[0015] (a3) 5 to 27 mol% of a saturated C5-C 24 Dicarboxylic acid unit

[0016] b. a diol component, comprising, compared to the total diol component:

[0017] (b1) 95 to 100 mol %, preferably 97 to 100 mol %, of units derived from at least one saturated aliphatic diol;

[0018] (b2) 0 to 5 mol %, preferably 0 to 3 mol %, of units derived from at least one unsaturated aliphatic diol;

[0019] ii) 0% to 40% by weight, relative to the sum of components i. to v., of at least one polyester comprising:

[0020] c. A dicarboxylic acid component having 100 mol % succinic acid

[0021] d. a diol component, comprising, compared to the total diol component:

[0022] (d1) 95 to 100 mol %, preferably 97 to 100 mol %, of units derived from at least one saturated aliphatic diol;

[0023] (d2) 0 to 5 mol %, preferably 0 to 3 mol %, of units derived from at least one unsaturated aliphatic diol;

[0024] iii) 23% to 43% by weight of at least one polyhydroxyalkanoate, based on the sum of components i. to v.;

[0025] iv) 10 to 20 wt. % of at least one filler, relative to the sum of components i. to v.;

[0026] v) 0% to 0.5% by weight, relative to the sum of components i. to v., of at least one crosslinker and / or chain extender;

[0027] Wherein component iii. has a melting point (Tm2) ≥ 160°C and a (ΔHm) ≥ 10 J / g.

[0028] Component i. is present in the final composition at 5 to 70 wt. % relative to the sum of component iv. In a preferred aspect of the invention, component i. is present in the final composition at 15 to 65 wt. % relative to the sum of component iv; even more preferably at 25 to 60 wt. % relative to the sum of component iv.

[0029] As regards the polyester i) of the composition according to the invention, it comprises a dicarboxylic acid component comprising, relative to the total dicarboxylic acid component: 0 to 20 mol %, preferably 0 to 10 mol %, of units derived from at least one aromatic dicarboxylic acid (component a1) and 53 to 95 mol % of succinic acid units (component a2), 5 to 27 mol % of one or more C5-C 24 Saturated dicarboxylic acid units other than succinic acid among dicarboxylic acids (component a3).

[0030] The aromatic dicarboxylic acid is preferably selected from phthalic acid type aromatic dicarboxylic acids, preferably terephthalic acid or isophthalic acid, more preferably terephthalic acid; and heterocyclic aromatic dicarboxylic acid compounds, preferably 2,5-furandicarboxylic acid, 2,4-furandicarboxylic acid, 2,3-furandicarboxylic acid, 3,4-furandicarboxylic acid, more preferably 2,5-furandicarboxylic acid; esters, salts thereof and mixtures thereof.

[0031] In a preferred embodiment, the aromatic dicarboxylic acids comprise:

[0032] 1 to 99 mol %, preferably 5 to 95 %, more preferably 10 to 80 % of terephthalic acid, its esters or salts.

[0033] 99 to 1 mol %, preferably 95 to 5 %, more preferably 90 to 20 % of 2,5-furandicarboxylic acid, an ester or a salt thereof.

[0034] Preferably, the saturated aliphatic dicarboxylic acid other than succinic acid (component a3) is selected from C5-C 24 Saturated dicarboxylic acid, preferably C5-C 13 Saturated dicarboxylic acid, more preferably C7-C 11 Saturated dicarboxylic acids, C1-C 24 Preferably, the saturated aliphatic dicarboxylic acid is selected from the group consisting of succinic acid (component a2), 2-ethylsuccinic acid, glutaric acid, 2-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and C1-C4 alkyl esters, salts thereof, and mixtures thereof. 1-24 Alkyl esters.

[0035] Unsaturated aliphatic dicarboxylic acids may also be optionally present in an amount of 0 to 5 mol %, preferably 0.1 to 1 mol %. They are preferably selected from itaconic acid, maleic acid, fumaric acid, 4-methylene-pimelic acid, 3,4-bis(methylene)azelaic acid, 5-methylene-azelaic acid; 24 Alkyl esters, preferably C1-C4 alkyl esters; salts thereof and mixtures thereof.

[0036] Even more preferably, the dicarboxylic acid component of the polyester i. in the composition according to the invention consists of saturated aliphatic dicarboxylic acids.

[0037] In an even more preferred embodiment of the present invention, the saturated aliphatic dicarboxylic acid other than succinic acid is azelaic acid.

[0038] The diol component of the polyester of the composition according to the present invention comprises 95 mol % to 100 mol %, preferably 97 mol % to 100 mol %, relative to the total diol component, of units derived from at least one saturated aliphatic diol (component b1), and 0 mol % to 5 mol %, preferably 0 mol % to 3 mol %, relative to the total diol component, of units derived from at least one unsaturated aliphatic diol (component b2).

[0039] In a preferred embodiment, the diol component of the polyester of the composition according to the invention consists of saturated aliphatic diols.

[0040] As for the saturated aliphatic diol, it is preferably selected from 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, dianhydrosorbitan, dianhydromannitol, dianhydroiditol, cyclohexanediol, cyclohexanemethanediol, dialkylene glycol and polyalkylene glycol having a molecular weight of 100 to 4000 (e.g. polyethylene glycol, polypropylene glycol), and mixtures thereof. Preferably, the diol component comprises at least 50 mol% of one or more diols selected from 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butanediol. In a preferred embodiment of the present invention, the saturated aliphatic diol is 1,4-butanediol.

[0041] The unsaturated aliphatic diol of the polyester i. in the composition according to the invention is preferably selected from cis-2-butene-1,4-diol, trans-2-butene-1,4-diol, 2-butyne-1,4-diol, cis-2-pentene-1,5-diol, trans-2-pentene-1,5-diol, 2-pentyne-1,5-diol, cis-2-hexene-1,6-diol, trans-2-hexene-1,6-diol, 2-hexyne-1,6-diol, cis-3-hexene-1,6-diol, trans-3-hexene-1,6-diol, 3-hexyne-1,6-diol.

[0042] As regards the polyester i. in the composition, it is preferably selected from aliphatic polyesters (AP) and aliphatic-aromatic polyesters (AAPE).

[0043] Within the meaning of the present invention, an aliphatic polyester (AP) is understood to mean a polyester comprising a dicarboxylic acid component and a diol component, the dicarboxylic acid component consisting of from 53 to 95 mol % of succinic acid units, from 5 to 27 mol % of saturated dicarboxylic acid units of one or more “C5-C24-dicarboxylic acids” other than succinic acid, and from 0 to 5 mol % of at least one unsaturated aliphatic dicarboxylic acid, relative to the total moles of the diol component; the diol component comprising from 95 to 100 mol % of units derived from at least one saturated aliphatic diol, and from 0 to 5 mol % of units derived from at least one unsaturated aliphatic diol, relative to the total moles of the diol component.

[0044] In the present invention, aliphatic-aromatic polyester (AAPE) is defined as a polyester comprising a dicarboxylic acid component and a diol component, wherein the dicarboxylic acid component is composed of at least one aromatic dicarboxylic acid compound, in particular 0 mol% to 20 mol%, preferably 0 mol% to 10 mol% of units derived from at least one aromatic dicarboxylic acid, succinic acid, optionally saturated C5-C 24 dicarboxylic acid, and 0 mol % to 5 mol % of at least one unsaturated aliphatic dicarboxylic acid; the diol component comprises 95 mol % to 100 mol % of units derived from at least one saturated aliphatic diol, and 0 mol % to 5 mol % of units derived from at least one unsaturated aliphatic diol, relative to the total moles of the diol component.

[0045] In a preferred embodiment of the present invention, the polyester i. in the composition comprises at least one aliphatic polyester (AP), preferably poly(butylene 1,4-adipate-co-butylene 1,4-succinate), poly(butylene 1,4-azelaate-co-butylene 1,4-succinate), poly(butylene 1,4-sebacate-co-butylene 1,4-succinate), poly(butylene 1,4-succinate-co-butylene 1,4-adipate-co-butylene 1,4-azelaate), poly(butylene 1,4-succinate-co-butylene 1,4-adipate-co-butylene 1,4-azelaate), poly(butylene 1,4-succinate-co-butylene 1,4-adipate-co-butylene 1,4-sebacate), poly(butylene 1,4-succinate-co-butylene 1,4-azelaate-co-butylene 1,4-sebacate).

[0046] In a particularly preferred embodiment, the aliphatic polyester is poly(butylene 1,4-succinate-co-butylene 1,4-azelaate).

[0047] In addition to the dicarboxylic acid component and the diol component, the polyester i. in the composition according to the invention may also contain repeating units derived from at least one hydroxy acid in an amount of 0 mol % to 49 mol %, preferably 0 mol % to 30 mol %, relative to the total moles of the dicarboxylic acid component. Examples of suitable hydroxy acids are glycolic acid, hydroxybutyric acid, hydroxycaproic acid, hydroxyvaleric acid, 7-hydroxyheptanoic acid, 8-hydroxycaproic acid, 9-hydroxynonanoic acid, lactic acid or lactide. The hydroxy acids can be inserted into the chain as such or as prepolymers / oligomers, or they can also be reacted beforehand with diacids or diols.

[0048] Long molecules with two functional groups not in terminal position may also be added in an amount not exceeding 10 mol % relative to the total moles of the dicarboxylic acid component. Examples are dimer acid, ricinoleic acid and acids with epoxy groups and polyoxyethylenes with a molecular weight of 200 to 10,000.

[0049] Diamines, amino acids or amino alcohols may also be present in percentages up to 30% of the total moles of the dicarboxylic acid component.

[0050] During the preparation of the polyester i. in the composition according to the invention, it is also advantageous to add one or more molecules with multiple functional groups in an amount of 0.05 to 3 mol % relative to the total moles of the dicarboxylic acid component (and any hydroxy acids) to obtain branched products. Examples of such molecules are glycerol, pentaerythritol, trimethylolpropane, citric acid, dipentaerythritol, monosorbitan, monohydromannitol, triglycerides, polyglycerols, etc.

[0051] The molecular weight Mn of the polyester i. is preferably ≥ 20 000, more preferably ≥ 40 000. As regards the polydispersity index Mw / Mn of the molecular weight, it is preferably from 1.5 to 10, more preferably from 1.6 to 5, even more preferably from 1.8 to 2.7.

[0052] The molecular weights Mn and Mw can be measured by gel permeation chromatography (GPC). The determination can be carried out using a set of two columns in series (particle size 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, while the chromatography system is maintained at 40°C.

[0053] The polyester of the composition according to the invention preferably has a terminal acid group content of 30 to 160 milliequivalents / kg.

[0054] The terminal acid content can be measured as follows: 1.5 g to 3 g of polyester is placed in a 100 ml conical flask together with 60 ml of chloroform. After the polyester is completely dissolved, 25 ml of 2-propanol is added, and immediately before analysis, 1 ml of deionized water is added. The resulting solution is titrated with a pre-standardized solution of NaOH in ethanol. The equivalence point of the titration is determined using an appropriate indicator, such as a glass electrode for acid-base titration in non-aqueous solvents. The terminal acid content is calculated from the consumption of NaOH solution in ethanol according to the following equation:

[0055]

[0056] Where: Veq = ml of NaOH solution in ethanol at the equivalence point of the sample titration;

[0057] Vb = ml of NaOH solution in ethanol required to reach pH = 9.5 during the blank titration;

[0058] T = concentration of NaOH solution in ethanol expressed in mol / L;

[0059] P = sample weight in grams.

[0060] Preferably, the polyester i. has an intrinsic viscosity (measured at 25°C using an Ubbelohde viscometer on a solution in CHCl3 having a concentration of 0.2 g / dl) greater than 0.3 dl / g, preferably 0.3 dl / g to 2 dl / g, more preferably 0.4 dl / g to 1.4 dl / g.

[0061] Preferably, the polyester i. is biodegradable. For the purposes of the present invention, a biodegradable polymer is understood to be a polymer which is biodegradable according to EN 13432.

[0062] The polyester i. can be synthesized by any method known in the prior art. In particular, it can be advantageously obtained by polycondensation.

[0063] The synthesis process may advantageously be carried out in the presence of a suitable catalyst. Suitable catalysts include organometallic tin compounds such as stannic acid derivatives, titanium compounds such as ortho-butyl titanate, aluminum compounds, antimony compounds, zinc compounds and zirconium compounds.

[0064] As regards the polyester ii. of the composition according to the invention, it comprises a dicarboxylic acid component (component c) which is 100% succinic acid.

[0065] Component (c) of the polyester ii is present in an amount of 0% to 40% by weight, relative to the sum of components i. to v.

[0066] In a preferred aspect of the present invention, polyester ii. is present in an amount of 0% to 30% relative to the sum of components i. to v.

[0067] In a particularly preferred embodiment of the present invention, the biodegradable polymer composition comprises a mixture of poly(butylene 1,4-succinate-co-butylene 1,4-azelaate) (polyester i.)) and poly(butylene 1,4-succinate) (polyester ii.)), wherein the amount of poly(butylene 1,4-succinate) is 0% to 40% by weight, preferably 0% to 30% by weight, and the poly(butylene 1,4-succinate-co-butylene 1,4-azelaate) is present in an amount of 5% to 70% by weight, preferably 15% to 65% by weight, even more preferably 25% to 60% by weight, relative to the sum of the two polymers.

[0068] The diol component (component d) of the polyester ii. of the composition according to the present invention comprises 95 mol % to 100 mol %, preferably 97 mol % to 100 mol %, relative to the total diol component, of units derived from at least one saturated aliphatic diol (component d1) and 0 mol % to 5 mol %, preferably 0 mol % to 3 mol %, relative to the total diol component, of units derived from at least one unsaturated aliphatic diol (component d2).

[0069] In a preferred embodiment, the diol component of the polyester of the composition according to the invention consists of saturated aliphatic diols.

[0070] As for the saturated aliphatic diol, it is preferably selected from 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, dianhydrosorbitan, dianhydromannitol, dianhydroiditol, cyclohexanediol, cyclohexanemethanediol, dialkylene glycol and polyalkylene glycol having a molecular weight of 100 to 4000 (e.g. polyethylene glycol, polypropylene glycol), and mixtures thereof. Preferably, the diol component comprises at least 50 mol% of one or more diols selected from 1,2-ethylene glycol, 1,3-propylene glycol, 1,4-butanediol. In a preferred embodiment of the present invention, the saturated aliphatic diol is 1,4-butanediol.

[0071] The unsaturated aliphatic diol of the polyester ii. in the composition according to the invention is preferably selected from cis-2-butene-1,4-diol, trans-2-butene-1,4-diol, 2-butyne-1,4-diol, cis-2-pentene-1,5-diol, trans-2-pentene-1,5-diol, 2-pentyne-1,5-diol, cis-2-hexene-1,6-diol, trans-2-hexene-1,6-diol, 2-hexyne-1,6-diol, cis-3-hexene-1,6-diol, trans-3-hexene-1,6-diol, 3-hexyne-1,6-diol.

[0072] In order to provide the molded article with high high temperature deformation resistance and elastic modulus, the composition according to the present invention comprises at least one polyhydroxyalkanoate (component iii.), which is preferably selected from lactic acid polyesters, polyhydroxybutyrates, polyhydroxybutyrate-valerates, polyhydroxybutyrate-propionates, polyhydroxybutyrate-hexanoates, polyhydroxybutyrate-decanoates, polyhydroxybutyrate-dodecanoates, polyhydroxybutyrate-hexadecanoates, polyhydroxybutyrate-octadecanoates, poly3-hydroxybutyrate-4-hydroxybutyrate. Preferably, the polyhydroxyalkanoates of the composition comprise at least 70% by weight of one or more lactic acid polyesters.

[0073] In a particularly preferred embodiment of the present invention, the lactic acid polyester comprises at least 97% w / w of units derived from L-lactic acid, ≤3% w / w of repeating units derived from D-lactic acid, has a melting point (Tm2) in the range of 160° C. to 200° C., more preferably 160° C. to 180° C., a glass transition temperature (Tg) in the range of 55° C. to 65° C. and an MFR in the range of 20 g / 10 min to 100 g / 10 min (measured according to standard ASTM-D1238 at 210° C. and 2.16 kg). Commercial examples of lactic acid polyesters having these characteristics include Ingeo TM Biopolymer 3251D trademark products and L130 trademark product.

[0074] The polyhydroxyalkanoate iii. is present in the composition at 23% to 43% relative to component i. to component v. In a particularly preferred aspect of the present invention, the polyhydroxyalkanoate iii. is present at 25% to 35% relative to the sum of component i. to component v.

[0075] The polyhydroxyalkanoates iii. are characterized by a melting enthalpy (ΔHm) greater than 10 J / g. The melting enthalpy (ΔHm) is advantageously determined by differential scanning calorimetry (DSC) using a Perkin Elmer Pyris Diamond calorimeter under the conditions given below:

[0076] - Isothermal at -20°C for 60 seconds

[0077] -1st scan from -20°C to 200°C at 20°C / min

[0078] - Isothermal at 200°C for 60 seconds

[0079] - Perform the second scan from 200°C to -20°C at 10°C / min

[0080] - Isothermal at -20°C for 60 seconds

[0081] - Perform the third scan from -20°C to 200°C at 20°C / min

[0082] The melting enthalpy (ΔHm) was measured as the area of ​​the endothermic peak corresponding to the polyhydroxyalkanoate melt found in the third scan using PyrisTM software from Perkin Elmer specifically designed for processing DSC graphs. The melting point (Tm2) was the maximum of the endothermic peak corresponding to the polyhydroxyalkanoate melt found in the third scan.

[0083] More preferably, the melting enthalpy (ΔHm) is from 10 J / g to 93 J / g, more preferably from 10 J / g to 50 J / g.

[0084] Particularly preferred are polymer compositions comprising a mixture of an aliphatic polyester having dicarboxylic acid units comprising succinic acid (component ii.) and an aliphatic polyester having dicarboxylic acid units comprising succinic acid and one or more C5-C 24 Aliphatic copolyesters of dicarboxylic acid units of a saturated dicarboxylic acid other than succinic acid (component i). This composition results in articles having improved heat resistance.

[0085] This means that the composition of the invention allows obtaining articles which do not require annealing.

[0086] In the composition according to the invention, fillers (component iv.) contribute to improving the dimensional stability of the molded articles according to the invention and are preferably selected from kaolin, wollastonite, barite, clay, talc, calcium and magnesium carbonates, iron and lead carbonates, aluminum hydroxide, diatomaceous earth, aluminum sulfate, barium sulfate, silicon dioxide, mica, titanium dioxide, starch, chitin, chitosan, alginates, proteins such as gluten, zein, casein, collagen, gelatin and natural gums.

[0087] The term starch is understood here to mean all types of starch, i.e. flour, native starch, hydrolyzed starch, destructured starch, gelatinized starch, plasticized starch, thermoplastic starch, complex starch containing biological fillers or mixtures thereof. According to the invention, starches such as potato starch, corn starch, tapioca starch and pea starch are particularly suitable.

[0088] Starches which can be easily destructured and have a high initial molecular weight, such as potato starch or corn starch, are particularly advantageous.

[0089] In a preferred embodiment of the invention, the filler comprises talc, calcium carbonate, silicon dioxide, kaolin, wollastonite or a mixture thereof in the form of particles having an arithmetic mean diameter measured on the major axis of the particles of less than 10 micrometers. The concentration of the filler (component iv.) is particularly relevant and should be from 10% to 20%, more preferably from 10.1% to 18%, even more preferably from 12% to 18% relative to components i. to v.

[0090] The composition according to the invention may also comprise 0% to 5% of at least one crosslinker and / or chain extender (component v.) in order to improve the stability towards hydrolysis.

[0091] The crosslinking agent and / or chain extender is selected from isocyanate group, peroxide group, carbodiimide group, isocyanurate group, Compounds having two or more functional groups, such as oxazoline group, epoxide group, acid anhydride group, divinyl ether group, and mixtures thereof.

[0092] The compound having two or more functional groups and having an isocyanate group is preferably selected from p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,3-phenylene-4-chlorodiisocyanate, 1,5-naphthalene diisocyanate, 4,4-diphenylene diisocyanate, 3,3'-dimethyl-4,4-diphenylmethane diisocyanate, 3-methyl-4,4'-diphenylmethane diisocyanate, diphenyl ester diisocyanate, 2,4-cyclohexane diisocyanate, 2,3-cyclohexane diisocyanate. , 1-methyl-2,4-cyclohexyl diisocyanate, 2,6-cyclohexyl diisocyanate, bis(cyclohexyl isocyanate)methane, 2,4,6-toluene triisocyanate, 2,4,4-diphenyl ether triisocyanate, polymethylene-polyphenyl-polyisocyanate, methylene diphenyl diisocyanate, triphenylmethane triisocyanate, 3,3'-tolyl-4,4-diisocyanate, 4,4'-methylenebis(2-methylphenyl isocyanate), hexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,2-cyclohexylene diisocyanate, and mixtures thereof.

[0093] In a preferred embodiment, the compound having an isocyanate group is 4,4-diphenylmethane diisocyanate.

[0094] As for the peroxide-based compound having two or more functional groups, it is preferably selected from 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, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, di(2-ethylhexyl)peroxydicarbonate, and mixtures thereof.

[0095] The compound having two or more functional groups having a carbodiimide group preferably used in the composition according to the present invention is selected from poly(cyclooctylenecarbodiimide), poly(1,4-dimethylcyclohexylenecarbodiimide), poly(cyclohexylenecarbodiimide), poly(ethylenecarbodiimide), poly(butylenecarbodiimide), poly(isobutylenecarbodiimide), poly(nonylenecarbodiimide), poly(dodecylenecarbodiimide), poly(neopentylenecarbodiimide), poly(1,4-dimethylphenylenecarbodiimide), poly(2,2',6,6-tetraisopropyldiphenylenecarbodiimide) ( D), poly (2,4,6-triisopropyl-1,3-phenylenecarbodiimide) ( P-100), poly (2,6-diisopropyl-1,3-phenylenecarbodiimide) ( P), 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.

[0096] Examples of compounds with two or more functional groups having epoxide groups that can be advantageously used in the composition according to the invention are all polyepoxides from epoxidized oils and / or styrene-glycidyl ether-methyl methacrylate, glycidyl ether methyl methacrylate having a molecular weight in the range of 1000 to 10,000 and an epoxide value per molecule in the range of 1 to 30 and preferably 5 to 25, the epoxide being 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 propoxy triglycidyl ether, 1,4-butanediol diglycidyl ether, sorbitol polyglycidyl ether, glycerol diglycidyl ether, tetraglycidyl ether of meta-xylene diamine and diglycidyl ether of bisphenol A and mixtures thereof.

[0097] Together with the above-mentioned ones having isocyanate groups, peroxide groups, carbodiimide groups, isocyanurate groups, Compounds having two or more functional groups such as oxazoline, epoxide, anhydride or divinyl ether may also use a catalyst to increase the reactivity of the reactive groups. In the case of polyepoxides, fatty acid salts are preferably used, and calcium stearate and zinc stearate are even more preferred.

[0098] In addition to the above-mentioned components i to v., the composition according to the present invention preferably further comprises at least one other component (component vi.) selected from the following: plasticizers, UV stabilizers, lubricants, nucleating agents, surfactants, antistatic agents, pigments, flame retardants, compatibilizers, lignin, organic acids, antioxidants, antifungal agents, waxes, processing aids and polymer components, wherein the polymer component is preferably selected from vinyl polymers, glycol diacid polyesters other than the above-mentioned polyesters i. and polyesters ii., polyamides, polyurethanes, polyethers, polyureas or polycarbonates.

[0099] As regards plasticizers, the composition according to the invention preferably comprises one or more plasticizers selected from the group consisting of water and polyols having 2 to 22 carbon atoms; phthalates, such as diisononyl phthalate; trimellitic acid esters, such as diisononyl phthalate; 20 Trimellitate esters of monoalcohols (preferably selected from n-octanol and n-decanol); and aliphatic esters having the structure:

[0100] R1-OC(O)-R4-C(O)-[-O-R2-OC(O)-R5-C(O)-] m -O-R3

[0101] in:

[0102] R1 is selected from one or more of the following groups: H, C1 to C 24 Linear and branched saturated and unsaturated hydrocarbon residues of various types, from C1 to C 24 Monocarboxylic acid esterified polyol residues;

[0103] R2 comprises -CH2-C(CH3)2-CH2- and alkylene C2 to C8 groups, and comprises at least 50 mol% of said -CH2-C(CH3)2-CH2- groups;

[0104] R3 is selected from one or more of the following groups: H, C1 to C 24 Linear and branched saturated and unsaturated hydrocarbon residues of various types, from C1 to C 24 Monocarboxylic acid esterified polyol residues;

[0105] R4 and R5 are the same or different and contain one or more C2 to C 22 Olefins, preferably C2 to C 11 Olefins, more preferably C4 to C9 olefins, and comprising at least 50 mol% C7 olefins;

[0106] m is an integer of 1-20, preferably 2-10, more preferably 3-7.

[0107] Preferably, in the ester, at least one of the groups R1 and / or R3 comprises, relative to the total amount of R1 and / or R3 groups, an amount of preferably ≥10 mol %, more preferably ≥20 mol %, even more preferably ≥25 mol % of at least one C1 to C2-containing amino group selected from stearic acid, palmitic acid, 9-keto stearic acid, 10-keto stearic acid, 24 Polyol residues esterified with monocarboxylic acids and mixtures thereof. Examples of such aliphatic esters are described in Italian patent application MI2014A000030 and in international patent applications WO 2015 / 104375 and WO 2015 / 104377.

[0108] When present, preferably up to 10 wt. % of the selected plasticizer is present relative to the total weight of the composition.

[0109] Preferably, the lubricant is chosen from esters and metal salts of fatty acids, such as zinc stearate, calcium stearate, aluminum stearate and glyceryl stearate. Preferably, the composition according to the invention comprises up to 1% by weight, more preferably up to 0.5% by weight of lubricant relative to the total weight of the composition.

[0110] Examples of nucleating agents include saccharin sodium salt, calcium silicate, sodium benzoate, calcium titanate, boron nitride, isotactic polypropylene, low molecular weight PLA. These additives are preferably added in an amount of up to 10 wt %, and more preferably 2 wt % to 6 wt %, relative to the total weight of the composition.

[0111] If necessary, pigments such as titanium dioxide, clay, copper phthalocyanine, titanium dioxide, silicates, iron oxides and hydroxides, carbon black and magnesium oxide may also be added. These additives are preferably added up to 10% by weight.

[0112] The processing aid is preferably a fatty acid amide such as stearamide, behenamide, erucamide, oleamide, ethylenebisstearamide, ethylenebisoleamide and derivatives.

[0113] The polymer composition of the present invention may contain vinyl polymers, polyamides, polycarbonates, polyethers and glycolic polyesters other than polyester i. and polyester ii. as further additives.

[0114] Preferred vinyl polymers include polyethylene, polypropylene, copolymers thereof, polyvinyl alcohol, polyvinyl acetate, polyethylvinyl acetate and polyethylene vinyl alcohol, polystyrene, chlorinated vinyl polymers, polyacrylates.

[0115] In addition to polyvinyl chloride, chlorinated ethylene-based polymers include polyvinylidene chloride, polyvinyl chloride, poly(vinyl chloride-vinyl acetate), poly(vinyl chloride-ethylene), poly(vinyl chloride-propylene), poly(vinyl chloride-styrene), poly(vinyl chloride-isobutylene), and copolymers in which polyvinyl chloride accounts for more than 50 mole percent. The copolymers may be random, block or alternating.

[0116] As regards the polyamide of the composition according to the invention, it is preferably chosen from 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 types 6 / 9, 6 / 10, 6 / 11, 6 / 12, blends and copolymers (both random and block) thereof.

[0117] Preferably, the polycarbonate of the composition according to the invention is chosen from polyalkylene carbonates, more preferably polyethylene carbonate, polypropylene carbonate, polybutylene carbonate, mixtures thereof and random and block copolymers.

[0118] Among the polyethers, preferred are those having a molecular weight of 70,000 to 500,000 selected from polyethylene glycol, polypropylene glycol, polybutylene glycol, copolymers thereof and mixtures thereof.

[0119] As regards the diacid diol polyester other than the polyester i., it preferably comprises:

[0120] e. a dicarboxylic acid component, relative to the total dicarboxylic acid component, comprising:

[0121] (e1) 20 to 100 mol % of units derived from at least one aromatic dicarboxylic acid,

[0122] (e2) 0 to 80 mol % of units derived from at least one saturated aliphatic dicarboxylic acid,

[0123] (e3) 0 to 5 mol % of units derived from at least one unsaturated aliphatic dicarboxylic acid;

[0124] f. a diol component, comprising, compared to the total diol component:

[0125] (f1) 95 mol % to 100 mol % of units derived from at least one saturated aliphatic diol;

[0126] (f2) 0 to 5 mol% of units derived from at least one unsaturated aliphatic diol.

[0127] Preferably, the aromatic dicarboxylic acids e1, saturated aliphatic dicarboxylic acids e2, unsaturated aliphatic dicarboxylic acids e3, saturated aliphatic diols d1 and unsaturated aliphatic diols f2 used in the polyester are chosen from those mentioned above for the polyester i. of the composition according to the invention.

[0128] More preferably, the diacid-diol polyester other than polyester i) is chosen from block or random copolymers of the poly(ethylene terephthalate), poly(propylene terephthalate), poly(butylene terephthalate), poly(ethylene 2,5-furandicarboxylate), poly(propylene 2,5-furandicarboxylate), poly(butylene 2,5-furandicarboxylate) and poly(alkylene 2,5-furandicarboxylate-co-alkylene terephthalate) type.

[0129] The process for producing the polymer composition according to the present invention may be carried out according to any method known in the art.

[0130] Advantageously, the polymer composition according to the invention is produced by an extrusion process, wherein the polymer components are mixed in the molten state. When the composition is extruded, the components may be fed together, or one or more components may be fed separately along the extruder.

[0131] The invention also relates to high thickness (≥500 μm) moldings comprising said polymer composition, which have processing and performance characteristics that make them particularly suitable for this use. Its properties allow the production of moldings with good resistance to deformation at high temperatures, high dimensional stability, high deflection temperature under load and the ability to decompose in industrial composting processes.

[0132] For example, the polymer composition according to the invention is particularly suitable for making mouldings such as disposable cutlery, plates and cups, rigid containers, covers, covers and lids for dispensing beverages, preferably hot beverages, packaging materials for foods which can be heated in conventional ovens and microwave ovens.

[0133] The composition according to the invention and the molded articles comprising it are preferably characterized by a THF content of less than 30 mg / kg, preferably less than 10 mg / kg and more preferably <5 mg / kg, so as to be able to be used in contact with foods, such as in disposable tableware.

[0134] Compared to other conventional polymers such as polyethylene, polypropylene, polystyrene and ABS, the polymer composition according to the invention has the additional advantage that it can be processed in conventional machinery without requiring substantial changes to the usual processing conditions. For example, an object having dimensions such as a maximum thickness of about 1 mm, a width of 70 mm and a length of 80 mm can be molded using a melt temperature of 210° C., a filling pressure of 1400 bar, a cooling time of 6 seconds and a cycle time of 12 seconds.

[0135] Compared to the moldings known in the art, the composition according to the invention unexpectedly makes it possible to obtain articles which do not require an annealing heat treatment to become heat-resistant. This feature is particularly desirable since it has significant advantages from a production point of view. In particular, in order to produce articles with a thickness of ≥500 microns, preferably ≥800 microns, it is necessary to use temperatures even higher than 120° C. for several minutes.

[0136] Preferably, the injection molded article is characterized in that: the conservative elastic modulus (G') value at 70°C measured by dynamic mechanical analysis (DMTA) according to ASTM D5279-13 on a 30×6×1 mm rectangular specimen obtained from a 70×80×1 mm injection molded plate (temperature sweep test in torsion mode, frequency = 1 Hz, oscillation amplitude = 0.1% strain. Heating rate = 3°C / min from 30°C to 120°C) is greater than 100 MPa, more preferably greater than 120 MPa, even more preferably greater than 130 MPa.

[0137] According to the present invention, a "heat-resistant article that does not require annealing" means a product characterized by a conservative elastic modulus (G') at 70°C greater than 100 MPa.

[0138] Preferably, injection molded articles and thermoformed articles comprising the biodegradable composition according to the invention are considered to be decomposable according to EN 13432 at a thickness of up to 1 mm.

[0139] The compositions according to the invention may also be used in articles produced by thermoforming, such as containers, dishes, trays, beverage dispensing capsules and printed circuit boards for electronic devices.

[0140] The invention will now be illustrated by means of several examples of embodiments, which are intended to illustrate but not to limit the scope of protection of the present patent application.

[0141] illustrate

[0142] In an embodiment, the different components present in the polymer composition of the present invention are as follows:

[0143] i-1 = poly(1,4-butylene succinate-co-azelaate) ("PBSAz10")

[0144] i-2 = poly(1,4-butylene succinate-co-azelaate) ("PBSAz20")

[0145] ii-1 = poly(butylene 1,4-succinate) ("PBS").

[0146] iii-1 = polylactic acid ("PLA") MFR (210°C, 2.16 kg) = 35 g / 10 min, ΔH = 45 J / g, Tm2 = 167°C;

[0147] iii-2 = polyhydroxybutyrate-valerate ("PHBHV") MFR (210°C, 2.16 kg) = 28 g / 10 min, ΔH = 88 J / g, Tm2 = 170°C;

[0148] iii-3 = polylactic acid ("PLA") MFR (210°C, 2.16 kg) = 3.5 g / 10 min, ΔH = 0.7 J / g, Tm2 = 165°C;

[0149] iii-4 = polylactic acid ("PLA") MFR (210°C, 2.16 kg) = 80 g / 10 min, ΔH = 31 J / g, Tm2 = 164°C;

[0150] iv-1 = micronized talc with a mean diameter of 1.1 μm (particle distribution measured by Sedigraph according to ISO 13317-3), commercial grade Jetfine 3CA from Imerys;

[0151] iv-2 = micronized talc with a mean diameter of 1.9 μm (particle distribution measured by Sedigraph according to ISO 13317-3), commercial grade Mistron R10C from Imerys;

[0152] iv-3 = Aktifit VM, vinylsilane-modified kaolin from the Hoffmann Group,

[0153] v-1 = Carbodilite HMV15CA from Nisshinbo Chemical Inc;

[0154] v-2=a masterbatch comprising 10 wt% Joncryl ADR4368CS (styrene-glycidyl ether-methyl methacrylate copolymer) and 90 wt% of component ii-1;

[0155] vi-1 = Oleamide from plant sources (processing adjuvant)

[0156] vi-2 = poly(1,4-butylene adipate-co-1,4-butylene terephthalate) ("PBTA", glycol acid polyester other than polyester i. and polyester ii.) Example:

[0157] Examples of components i. to v.

[0158] ·i-1 = poly(1,4-butylene succinate-co-azelaate) ("PBSAz10")

[0159] 11655 g of 1,4-butanediol, 11865 g of succinic acid, 2100 g of azelaic acid, 20.5 g of glycerol and 2.0 g of an 80 wt % ethanolic solution of diisopropyltriethanolamino titanate (containing 8.2 wt % of titanium) were charged to a steel reactor with a geometric capacity of 60 liters, the steel reactor being equipped with a mechanical stirring system, a nitrogen inlet, a distillation column, an abatement system for high boiling distillates and a connection to a high vacuum system. Over a period of 120 minutes, the temperature of the substance was gradually raised to 230° C. When 95% of the theoretical water had been distilled, 20 g of tetra-n-butyl titanate (corresponding to 140 ppm of metal compared to the amount of poly(1,4-butylene succinate) theoretically obtainable by converting all the succinic acid fed into the reactor) was added. The reactor temperature was then raised to 235° C. to 240° C., and the pressure was gradually reduced to below 2 mbar over 60 minutes. The reaction was allowed to proceed for the required time to obtain poly(butylene succinate-co-butylene azelate) having an MFR of about 6 g / 10 min (at 190° C. and 2.16 kg), and the material was then discharged in the form of strands into a water bath and pelletized.

[0160] *i-2 = poly(1,4-butylene succinate-co-azelaate) ("PBSAz20")

[0161] 11130 g of 1,4-butanediol, 10150 g of succinic acid, 4045 g of azelaic acid, 19.8 g of glycerol and 2.0 g of an 80% by weight ethanolic solution of diisopropyltriethanolamino titanate (containing 8.2% by weight of titanium) are charged to a steel reactor with a geometric capacity of 60 liters, equipped with a mechanical stirring system, a nitrogen inlet, a distillation column, a system for eliminating high-boiling distillates and a connection to a high vacuum system, at a diol / dicarboxylic acid molar ratio (MGR) of 1.15. Over a period of 120 minutes, the temperature of the mass is gradually raised to 230° C. When 95% of the theoretical water has been distilled off, 20 g of tetra-n-butyl titanate are added (corresponding to 140 ppm of metal compared to the amount of poly(1,4-butylene succinate) theoretically obtainable by converting all the succinic acid fed to the reactor). The reactor temperature was then raised to 235° C. to 240° C., and the pressure was gradually reduced to below 2 mbar over 60 minutes. The reaction was allowed to proceed for the required time to obtain poly(butylene succinate-co-butylene azelate) having an MFR of about 8 g / 10 min (at 190° C. and 2.16 kg), and the material was then discharged in the form of strands into a water bath and pelletized.

[0162] • ii-1 = poly(butylene 1,4-succinate) ("PBS").

[0163] 14000 g of 1,4-butanediol, 17150 g of succinic acid, 26.75 g of glycerol and 2.0 g of an 80 wt % ethanolic solution of diisopropyltriethanolamino titanate (containing 8.2 wt % of titanium) were charged to a steel reactor with a geometric capacity of 60 liters, the steel reactor being equipped with a mechanical stirring system, a nitrogen inlet, a distillation column, a system for eliminating high boiling distillates and a connection to a high vacuum system. Over a period of 120 minutes, the temperature of the substance was gradually raised to 230° C. When 95% of theoretical water had been distilled off, 21.25 g of tetra-n-butyl titanate (corresponding to 119 ppm of metal compared to the amount of poly(1,4-butylene succinate) theoretically obtainable by converting all the succinic acid fed into the reactor) was added. The reactor temperature was then raised to 235° C. to 240° C., and the pressure was gradually reduced to less than 2 mbar over 60 minutes. The reaction was allowed to proceed for the required time to obtain poly(butylene 1,4-succinate) having an MFR (at 190°C and 2.16 kg) of about 7 g / 10 min, and the material was then discharged in the form of strands into a water bath and pelletized.

[0164] ·vi-2=Poly(1,4-butylene adipate-co-1,4-butylene terephthalate) ("PBAT")

[0165] 7453 g of terephthalic acid, 7388 g of adipic acid, 12033 g of 1,4-butanediol, 4.4 g of glycerol and 3.4 g of an 80 wt. % ethanolic solution of diisopropyltriethanolamine titanate (Tyzor TE containing 8.2 wt. % of titanium) were added at a diol / dicarboxylic acid molar ratio (MGR) of 1.40 to a steel reactor with a geometric capacity of 60 liters, which was equipped with a mechanical stirring system, a nitrogen inlet, a distillation column, a dismantling system for high-boiling distillates and a connection to a high vacuum system. The temperature of the mass was gradually increased to 230° C. over a period of 120 minutes. When 95% of the theoretical water has been distilled off, 17.0 g of tetra-n-butyl titanate are added (corresponding to 119 ppm of metal relative to the amount of poly(1,4-adipate-co-1,4-terephthalate) that can theoretically be obtained by converting all the adipic acid and terephthalic acid fed to the reactor). The reactor temperature is then raised to 235° C. to 240° C., and the pressure is gradually reduced over a period of 60 minutes to a value reaching less than 2 mbar. The reaction is allowed to proceed for the time required to obtain poly(1,4-adipate-co-1,4-terephthalate) having an MFR of about 6 g / 10 min (measured at 190° C. and 2.16 kg), and the material is then discharged in the form of strands into a water bath and pelletized.

[0166] Examples of the production of injection-moulded articles comprising the composition according to the invention; (1 to 2 Invention, 3 to 4 Comparative).

[0167] Table 1 - Composition Examples 1 to 5

[0168]

[0169] The composition in Table 1 was fed into a co-rotating twin-screw extruder (model Icma San Giorgio MCM 25HT) operating under the following conditions:

[0170] Screw diameter (D) = 25 mm;

[0171] L / D=52;

[0172] Screw rotation = 200 rpm;

[0173] Thermal profile = 110-150-190-200×5-190×3-170×3;

[0174] Flow rate 10.1kg / hour;

[0175] Vacuum degassing.

[0176] The pellets obtained from the extrusion process were fed into an injection molding machine (model Engel Victory 120) for the production of sheets conforming to standard ISO 294-3 type D1 (width 70 mm, length 80 mm, thickness 1 mm)

[0177] The operating conditions used to obtain 1 mm thick plates are described below:

[0178] Injection T°C = 200°C (Examples 1, 2 and 4), 190°C (Example 3), 210°C (Example 5);

[0179] Approximate filling pressure = 1400 bar (Examples 1, 2 and 4); 1300 bar (Example 3), 1600 bar (Example 5);

[0180] Approximate fill time = 1 second (Examples 1, 2, 3, 4 and 5);

[0181] Holding or packing pressure = 600 bar (Examples 1, 2, 4 and 5); 400 bar (Example 3);

[0182] Holding time at holding pressure = 5 seconds (Examples 1, 2, 4 and 5); 6 seconds (Example 3);

[0183] Cooling time = 9 seconds (Examples 1, 2, 4 and 5); 14 seconds (Example 3);

[0184] Approximate cycle time = 18 seconds (Examples 1, 2, 4 and 5); 24 seconds (Example 3);

[0185] rpm = 95 rpm (Examples 1, 2, 3, 4 and 5);

[0186] Flakes with a width of 70 mm, a length of 80 mm and a thickness of 0.6 mm conforming to standard ISO 294-3 type D1 were also produced by feeding the pellets into an Engel Victory 120 injection molding machine. The operating conditions for obtaining 0.6 mm thick flakes are described as follows:

[0187] Injection T℃=220℃ (Examples 1, 2 and 4), 210℃ (Example 3), 240℃ (Example 5);

[0188] Approximate filling pressure = 1200 bar (Examples 1, 2 and 4); 900 bar (Example 3), 1400 bar (Example 5);

[0189] Approximate filling time = 0.5 seconds (Examples 1, 2, 3, 4 and 5);

[0190] Holding pressure or dwell pressure = 800 bar (Examples 1, 2, 4 and 5); 500 bar (Example 3);

[0191] Holding time at holding pressure = 4 seconds (Examples 1, 2, 4 and 5); 5 seconds (Example 3);

[0192] Cooling time = 10 seconds (Examples 1, 2, 4 and 5); 15 seconds (Example 3);

[0193] Approximate cycle time = 20 seconds (Examples 1, 2, 4 and 5); 25 seconds (Example 3);

[0194] rpm = 95 rpm (Examples 1, 2, 3, 4 and 5).

[0195] Strips (length 30 mm, width 6 mm) with thicknesses of 1 mm and 0.6 mm were obtained from plates (length 80 mm, width 70 mm) obtained by injection. They were then subjected to dynamic mechanical analysis (DMTA) in torsion mode using an Ares G2 rotational rheometer from TA Instrument. The samples were heated from 25°C to 120°C at 3°C / min, applying a strain of 0.1% and a frequency of 1 Hz. The injection molded compositions were characterized at 70°C.

[0196] Table 2 - DMTA Characterization

[0197]

[0198] 0.6 mm thick boards were tested to determine their decomposition under industrial composting conditions. The test was carried out according to ISO 20200:2004 over a period of 91 days. The samples were cut into squares with a side length of about 2.5 cm, mixed with synthetic waste and incubated at 58°C. At the end of the test, the composting material was sieved and the residue was recovered, washed as much as possible and weighed. The weight difference (start-end test) was considered as the decomposition of the sample.

[0199] Table 3 - Decomposition Test

[0200] Example Weight loss after 90 days at 58°C 1 >90％ 2 >90％ 3 (Comparison) >90％ 4 (Comparison) <90％

Claims

1. A biodegradable polymer composition for producing a molded article, comprising, relative to the total composition: i) 5 to 70 wt. %, relative to the sum of components i. to v., of at least one polyester comprising: a. a dicarboxylic acid component, relative to the total dicarboxylic acid component comprising: (a1) 0 to 20 mol% of units derived from at least one aromatic dicarboxylic acid (a2) 53 mol % to 95 mol % of succinic acid units, (a3) 5 to 27 mol % of units derived from at least one saturated aliphatic C5-C24 dicarboxylic acid b. a diol component, comprising, compared to the total diol component: (b1) 95 to 100 mol % of units derived from at least one saturated aliphatic diol; (b2) 0 to 5 mol% of units derived from at least one unsaturated aliphatic diol; ii) 0% to 40% by weight, relative to the sum of components i. to v., of at least one polyester comprising: c. A dicarboxylic acid component having 100 mol % succinic acid d. a diol component, comprising, compared to the total diol component: (d1) 95 to 100 mol % of units derived from at least one saturated aliphatic diol; (d2) 0 to 5 mol% of units derived from at least one unsaturated aliphatic diol; iii) 23% to 43% by weight, based on the sum of components i. to v., of at least one polyhydroxyalkanoate, wherein the polyhydroxyalkanoate is a lactic acid polyester comprising at least 97% w / w of units derived from L-lactic acid, ≤3% w / w of repeating units derived from D-lactic acid, having a melting point (Tm2) in the range of 160°C to 200°C, a glass transition temperature (Tg) in the range of 55°C to 65°C and an MFR in the range of 20 g / 10 min to 100 g / 10 min, the MFR being measured according to standard ASTM-D1238 at 210°C and 2.16 kg; iv) 10 to 20 wt. % of at least one filler, relative to the sum of components i. to v.; v) 0% to 0.5% by weight, relative to the sum of components i. to v., of at least one crosslinker and / or chain extender; Wherein component iii. has a melting enthalpy (ΔHm) ≥ 10 J / g.

2. The biodegradable polymer composition for producing a molded article according to claim 1, wherein the polyester i) comprises: a. a dicarboxylic acid component, relative to the total dicarboxylic acid component comprising: (a1) 0 to 10 mol % of units derived from at least one aromatic dicarboxylic acid, (a2) 53 mol % to 95 mol % of succinic acid units, (a3) 5 to 27 mol % of units derived from at least one saturated aliphatic C5-C24 dicarboxylic acid.

3. The biodegradable polymer composition for producing a molded article according to claim 1, wherein the polyester i) comprises: b. a diol component, comprising, compared to the total diol component: (b1) 97 mol % to 100 mol % of units derived from at least one saturated aliphatic diol; (b2) 0 to 3 mol% of units derived from at least one unsaturated aliphatic diol.

4. The biodegradable polymer composition for producing a molded article according to claim 1, wherein the polyester ii) comprises: d. a diol component, comprising, compared to the total diol component: (d1) 97 to 100 mol % of units derived from at least one saturated aliphatic diol; (d2) 0 to 3 mol % of units derived from at least one unsaturated aliphatic diol.

5. The biodegradable polymer composition for producing molded articles according to claim 1, wherein the polyester i) comprises one or more molecules having multiple functional groups in an amount of 0.05 mol% to 3 mol% based on the total moles of the dicarboxylic acid component to obtain a branched product.

6. The biodegradable polymer composition for producing molded articles according to claim 5, wherein the one or more molecules having multiple functional groups are selected from glycerol, pentaerythritol, trimethylolpropane, citric acid, dipentaerythritol, monoanhydrosorbitol, monoanhydromannitol or polyglycerol.

7. The biodegradable polymer composition for producing molded articles according to claim 1, wherein the saturated aliphatic C5-C24 dicarboxylic acid is selected from C5-C 13 Saturated aliphatic dicarboxylic acids.

8. The biodegradable polymer composition for producing molded articles according to claim 1, wherein the saturated aliphatic C5-C24 dicarboxylic acid is selected from C7-C 11 Saturated aliphatic dicarboxylic acids.

9. The biodegradable polymer composition for producing molded articles according to claim 1, wherein the saturated aliphatic C5-C24 dicarboxylic acid is selected from the group consisting of 2-ethylsuccinic acid, glutaric acid, 2-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and tridecanedioic acid.

10. The biodegradable polymer composition for producing a molded article according to claim 1, wherein the polyester i) comprises at least one aliphatic polyester.

11. The biodegradable polymer composition for producing a molded article according to claim 1, wherein the polyester i) comprises poly(butylene 1,4-adipate-co-butylene 1,4-succinate), poly(butylene 1,4-azelaate-co-butylene 1,4-succinate), poly(butylene 1,4-sebacate-co-butylene 1,4-succinate), poly(butylene 1,4-succinate-co-butylene 1,4-adipate-co-butylene 1,4-azelaate), poly(butylene 1,4-succinate-co-butylene 1,4-adipate-co-butylene 1,4-azelaate), poly(butylene 1,4-succinate-co-butylene 1,4-adipate-co-butylene 1,4-sebacate), poly(butylene 1,4-succinate-co-butylene 1,4-azelaate-co-butylene 1,4-sebacate).

12. The biodegradable polymer composition for producing molded articles according to claim 1, wherein the polyester i) is poly(butylene 1,4-succinate-co-butylene 1,4-azelaate), and the polyester ii) is poly(butylene 1,4-succinate). 13 . The biodegradable polymer composition for producing a molded article according to claim 1 , wherein the polyhydroxyalkanoate has a melting enthalpy (ΔHm) in the range of 10 J / g to 93 J / g. 14 . The biodegradable polymer composition for producing a molded article according to claim 13 , wherein the polyhydroxyalkanoate has a melting enthalpy (ΔHm) in the range of 10 J / g to 50 J / g.

15. The biodegradable polymer composition for producing a molded article according to claim 13, wherein the polyhydroxyalkanoate has a melting point in the range of 160°C to 180°C.

16. A biodegradable polymer composition for producing a molded article according to any one of claims 1 to 12, wherein the filler is selected from wollastonite, barite, clay, talc, calcium and magnesium carbonates, iron and lead carbonates, aluminum hydroxide, diatomaceous earth, aluminum sulfate, barium sulfate, silicon dioxide, mica, titanium dioxide, starch, chitin, chitosan, alginates, proteins and natural gums.

17. The biodegradable polymer composition for producing a molded article according to any one of claims 1 to 12, wherein the filler is selected from kaolin, gluten, zein, casein, collagen and gelatin.

18. The biodegradable polymer composition for producing a molded article according to any one of claims 1 to 12, wherein the filler is selected from talc, calcium carbonate, silicon dioxide, kaolin, wollastonite and mixtures thereof in the form of particles having an arithmetic mean diameter measured on the major axis of the particles of less than 10 micrometers.

19. The biodegradable polymer composition for producing a molded article according to any one of claims 1 to 12, wherein the crosslinking agent and / or chain extender is selected from the group consisting of a polymer having an isocyanate group, a peroxide group, a carbodiimide group, an isocyanurate group, Compounds having two or more functional groups, such as oxazoline group, epoxide group, acid anhydride group, divinyl ether group, and mixtures thereof.

20. A moulding comprising the polymer composition of claim 1, said moulding having the properties of resistance to deformation at high temperatures and capable of being decomposed according to EN 13432 at a thickness of up to 1 mm.

21. A molded article comprising the polymer composition of claim 1, characterized in that The THF content is less than 30 mg / kg, so it can be used in contact with food.

22. The molded article according to claim 21, wherein the THF content is less than 30 mg / kg, thereby being usable in disposable tableware.

23. The molded article according to claim 21, wherein the THF content is less than 10 mg / kg.

24. The molded article according to claim 21, wherein the THF content is <5 mg / kg.

25. An article molded by injection molding comprising the polymer composition of claim 1, the article being selected from disposable cutlery, plates and cups, rigid containers, capsules for dispensing beverages, covers and lids, packaging for food that can be heated in conventional ovens and microwave ovens.

26. The article of claim 25, wherein the article is selected from capsules for dispensing hot beverages.

27. A thermoformed article comprising the polymer composition of claim 1, wherein the thermoformed article is selected from the group consisting of a container and a printed circuit board for an electronic device.

28. The thermoformed article of claim 27, wherein the thermoformed article is selected from the group consisting of a dish, a tray, and a beverage dispensing capsule.

29. A method for injection molding of a molded article according to any one of claims 20 to 24 or an article according to claim 25 or 26, said method being carried out without an annealing heat treatment, wherein said molded article or said article is characterized by a conservative elastic modulus (G') at 70°C exceeding 100 MPa.

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