Biodegradable polymeric compositions comprising starch and a thermoplastic polymer

Abstract: Polymeric compositions comprising thermoplastic starch and a thermoplastic polymer incompatible with starch, in which the starch constitutes the dispersed phase and the thermoplastic polymer constitutes the continuous phase, selected: A) from compositions comprising an agent with an interfacial effect selected from esters of polyols with mono- or polycarboxylic acids with dissociation constants within certain limits, the esters having specific values of the hydrophillic/lipophilic balance index HLB or being amongst the non-ionic surfactants which are soluble in water but cannot significantly be extracted by water from the compositions which contain them, B) from compositions wherein the thermoplastic polymer is an aliphatic or aliphatic-aromatic copolyester wherein the ratio R between the average viscometric molecular weight and the melt index is greater than 25,000 and C) from compositions wherein the thermoplastic polymer is selected from aliphatic-aromatic copolyesters, polyester-amides, polyester-ethers, polyester-ether-amides, polyester-urethanes and polyester-ureas and wherein the compositions are obtained by extrusion of the component maintaining a water content during the mixing stage from 1 to 5% by weight.

Description: The present invention relates to biodegradable polymeric compositions with good resistance to ageing and to low humidities, comprising thermoplastic starch and a thermoplastic polymer incompatible with starch. In these compositions, starch constitutes the dispersed phase and the thermoplastic polymer constitutes the continuous phase. The invention relates in particular to biodegradable compositions which can maintain a high tear strength in conditions of low humidity. It is known that the mechanical properties, particularly the tear strength, of products (films) produced from compositions comprising thermoplastic starch and a thermoplastic polymer incompatible with starch in which the starch constitutes the dispersed phase undergo considerable deterioration because the starch gives up or absorbs water until it achieves equilibrium with the ambient humidity. In conditions of relatively low humidity, for example 20% humidity, the material tends to become fragile since the dispersed phase becomes insufficiently plasticized because of the loss of water which raises the glass transition point above the ambient temperature. In these conditions, when the starch particles constituting the dispersed phase are stressed they cannot deform and absorb the stress but remain rigid, thus initiating tearing. Water is a very effective plasticizer of the starchy phase; however, it has the disadvantage that it is volatile and that its concentration fluctuates in order to achieve equilibrium with the ambient humidity. High-boiling plasticizers such as glycerol, sorbitol, etherified or esterified sorbitol, ethylene glycol, trimethylol propane, pentaerythritol and polyols in general are therefore preferred. Some of the water present during the plasticizing of the starch is supplied by the starch itself and some may be added. Upon completion of the plasticizing and the mixing of the components, the water is removed by degassing to give a final content of about 1-3% by weight. Water, like high-boiling plasticizers, modifies the viscosity of the starch phase and affects the rheological properties of the starch/polymer system, helping to determine the dimensions of the dispersed particles. The most effective high-boiling plasticizers (glycerol in particular) tend to be lost from the system either because of evaporation in a ventilated atmosphere, particularly if the humidity undergoes cyclic variations, or by migration in contact with other hydrophilic materials such as cellulose. In both cases, the concentration of plasticizer is no longer sufficient to keep the Tg of the dispersed phase below the temperature of use and the material becomes fragile. To prevent this problem, plasticizers such as, for example, sorbitol, sorbitol mono-ethoxylate and trimethylol propane, which do not migrate and do not evaporate, have been used. The effectiveness of these plasticizers, however, is quite low and the final characteristics of the material are worse than those obtained with the use of more effective plasticizers such as glycerol, particularly in conditions of low humidity. To prevent the problems which arise in dry conditions, it has also been attempted to bring the Tg of the dispersed phase back to values below the temperature of use by increasing the quantity of high-boiling plasticizer. This gives rise to too soft a "feel" of the material when it is in the 50% relative humidity conditions in which the material is normally calibrated to achieve the maximum performance. WO-A-9524447 relates to compositions containing starch, a thermoplastic polymer, a stretching agent such as decaglycerol tetraoleate and a further plasticizer such as glycerol acetate. According to the patent application of the present application, the problem of providing biodegradable heterophase compositions comprising thermoplastic starch and a thermoplastic polymer incompatible with starch in which starch constitutes the dispersed phase and the polymer constitutes the continuous phase capable of maintaining high mechanical properties even in conditions of low relative humidity can be solved by using a composition selected from the following ones: A) Compositions prepared by extrusion of the components in the presence of an interfacial agent selected from the group consisting of: a) esters which hove hydrophilic/lipophilic balance index values (HLB) greater than 8 and which are obtained from polyols and from mono- or polycarboxylic acids with dissociation constants pK lower than 4.5 (the value relates to the pK of the first carboxyl group in the case of polycarboxylic acids); b) esters with HLB values of between 5.5 and 8, obtained from polyols and from mono- or polycarboxylic acids with less than 12 carbon atoms and with pK values greater than 4.5 (this value relating to the pK of the dissociation of the first carboxyl group in the case of polycarboxylic acids); c) esters with HLB values lower than 5.5, obtained from polyols and from fatty acids with 12-22 carbon atoms, used in quantities of from 10 to 40% by weight relative to the starch; d) non-ionic, water-soluble surfactants which, when added to the starch/thermoplastic polymer heterophase compositions indicated above, migrate in water by no more than 30% of their concentration after the material containing them has been immersed in water for 100 hours at ambient temperature; e) reaction products of an aliphatic or aromatic diisocyanate with a polymer containing terminal groups reactive with the diisocyanates; B) Compositions wherein the thermoplastic polymer incompatible with starch is a polyester comprising repeating units deriving from an aliphatic dicarboxylic acid and/or from a hydroxyacid with more than 2 carbon atoms and wherein the ratio R between the average viscosimetric molecular weight and the melt index of the polyester (measured at 180°C under a load of 5 kg) is greater than 25,000; C) Compositions wherein the thermoplastic polymer incompatible with starch is a copolyester selected from the aliphatic-aromatic copolyesters, polyester-amides, polyester-ethers, polyester-ether-amides, polyester-ureas, and polyester-urethanes, said compositions being obtained by extrusion of the components under conditions wherein the content of water during the extrusion mixing is maintained from 1 to 5% by weight as measured at the exit of the extruder, prior to conditioning. The subject matter of the present invention, as defined in the appended claims, relates to those compositions identified in the parent application as compositions A)sub b); consistently, the esters used as interfacial agents in the compositions of the present invention are identified in the following as esters b). The HLB index of the ester a) - c) of the A) compositions is given by the ratio between the molecular mass of the hydrophilic fraction of the molecule (Mh) and the total molecular mass (M) multiplied by 20: HLB = 20 x (Mh/M). In the case of monoglycerides, the empirical formula normally adopted is the following: HLB = 20 (1 - S/A) in which S is the saponification number of the ester and A is the acidity number of the acid. The hydrophilic/lipophilic balance of the esters is controlled by the length of the acid chain and by the number of hydroxyl groups which remain free after esterification. The effect of the esters in bringing about compatibility in the case of starch/polyester systems is due to the interaction between the free alcohol groups of the ester and those of the starch and between the ester groups of the ester which brings about compatibility, and the polyester phase. The esters of class a) are soluble in water; their effectiveness varies in dependence on the pK value of the acid and generally increases as the pK value decreases. The best results are achieved with the esters of oxalic acid (pK = 1.23), maleic acid (pK1 = 1.83), malonic acid (pK1 - 2.83), and mono-, di- and tri-chloroacetic acids (pK 2.83, 1.48 and 0.70, respectively). Mono- and di-esters of polyols containing 3 or more alcohol groups are preferred; mono- and di-glycerides, particularly of oxalic acid, are particularly preferred. Mono- and di-esters of sorbitol, trimethylol propane, pentaerythritol and similar polyols are also examples of compounds which can advantageously be used. The esterification of the hydroxyl groups of the polyol is generally partial, affecting between 10 and 90% of the hydroxyl groups, preferably between 20 and 70%, and most preferably between 25 and 50%. The partial esterification condition applies both to the esters a) and to the esters b) and c). The esters a) are generally used in a ratio to the starch of from 1:30 to 1:2.5 by weight. The quantities of the esters a) used are preferably from 5 - 40% relative to the starch, or from 0.5 to 20% by weight relative to the total composition. However, the compatibility effect starts to appear even at levels of 1-3% of the total weight of the composition. The esters are generally used to replace 30-35% of the plasticizer; however, they may also be used without plasticizers. The HLB values of some monoglycerides of class a) and the pK1 and pK2 constants of the corresponding acids are given by way of illustration: Acid pK1 pK2 HLB of the ester Oxalic 1.23 4.19 12.4 Malonic 2.83 5.69 11.7 Succinic 4.16 5.61 11.1 Adipic 4.43 4.41 9.9 Pivalic 4.78 - 8.4 The effect of the esters of type a) in bringing about compatibility is such as to achieve a fine microstructure of the starch with a mean particle size at least one order of magnitude smaller than that of the particles of the compositions prepared, even in very favourable rheological conditions, in the absence of type a) agents for bringing about compatibility. The average numeral size of the starch particles is between 0.1 and 0.5 microns and more than 80% of the particles have a size of less than 1 micron. The water content of the compositions during the mixing of the components is preferably kept between 1 and 15% by weight. It is, however, also possible to operate with a content of less than 1% by weight, in this case, starting with predried and pre-plasticized starch. The fine niicrcstructure of the starch permits the production of a film which still retains good tensile and tear-strength properties after washing with water in order to remove the plasticizers. In these films, the small dimensions of the starch particles no longer enable tearing to be initiated. The esters of clas b) of the present invention are insoluble in water and are therefore not removed by washing. Unlike the esters which are soluble in water and which, as well as acting as interfacial agents, also have a fairly good plasticizing effect, the insoluble esters, by virtue of the size of their hydrophobic aliphatic components, act mainly as interfacial agents, facilitating the slippage of the surfaces during stressing, thus minimizing the capacity of the particles, which have become rigid and no longer deformable as a result of loss of plasticizer, to initiate tearing. Examples of esters of class b) of the present invention are monoglycerides of caproic acid (pK = 4.85; HLB = 7.3), of suberic acid (pK1 = 4.52 and HLB = 6) and of azelaic acid (pK1 = 4.55 and HLB = 5.8). Esters of caproic acid, particularly monoglycerides (HLB = 7.3), are preferred since they can maintain a high tear strength of the films without detracting from their quality. Esters b) of the present invention are generally used in a ratio to the starch of from 1:30 to 1:2.5 or from 0.5 to 20% by weight relative to the total composition. Examples of esters of class c) are monoglycerides of lauric acid (HLB 5.4) and of oleic acid (HLB = 4.2). Examples of other monoglycerides which can be used are those of myristic, palmitic, stearic, erucic and linoleic acids. The esters of class c), since materials of these types act as interfacial agents and not as lubricants, are used in high concentrations in comparison with those of the lubricants used in the prior art, that is, in concentrations of from 3 to 10%, preferably from 5 to 10% by weight, which is equal to about 10-40% by weight relative to the starch. Examples of non-ionic surfactants of class d) are alkoxylated alkylphenols with HLB indices greater than 10, such as nonylphenol ethoxylate, with the degree of ethoxylation regulated in a manner such that the HLB is greater than 10. The alkoxylated alkylphenols are used in concentrations within a fairly narrow range, generally of from 3-7% of the weight of the composition. Concentrations outside this critical range have no effect. Other examples of surfactants of class d) are the ethoxylation products of sorbitol, starch, fatty acids, rosinic acid, tall oil, amides of fatty acids and ethanolamides. The acids usable in the preparation of the esters a) to c) comprise saturated and unsaturated, linear or branched aliphatic and aromatic, mono- to polycarboxylic acids, possibly containing substituents selected, for example, from halogen atoms, hydroxyl groups, alkoxyl groups, nitro groups, and ester groups, for example, acetyl citric acid. Representative acids are: formic acid, mono-, di- and tri-chloroacetic acid, propionic acid, butyric and isobutyric acids, amylic acid, isoamylic acid, pivalic acid and caproic acid, and fatty acids from lauric acid to docosanoic acid; di-carboxylic acids such as oxalic, malonic, succinic, glutaric, adipic, suberic and azelaic acids; hydroxy-acids such as glycolic, glyceric, lactic, citric, tartaric, malic, and benzoic acids, substituted benzoic acid and salicylic acid. The interfacial agents of class e) are preferably obtained by reaction of a diisocyanate such as hexamethylenediisocyanate with an aliphatic-aromatic polyester, such as poly-epsilon-caprolactone. The agents e) are used in the amount of 1 to 10% by weight of the composition. The polyols used for the preparation of esters a) to c) contain 3 or more carbon atoms and 2 or more alcohol groups, for example, glycerol, di- and polyglycerols, ethylene or propylene glycol, ethylene or propylene diglycol, polyethylene glycol, polypropylene glycol, 1,2-propandiol, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitol, erythritol, xylitol, sucrose, 1,3-propandiol, 1,2-, 1,3-, 1,4-butandiol, 1,5-pentandiol, 1,6-, 1,5-hexandiol, 1,2,6-, 1,3,5-hexantriol, neopentyl glycol, and polyvinyl alcohol prepolymers. These polyols as such or esterified with acids other than those used in the esters of classes a) and b) constitute an effective class of plasticizers usable in the compositions of the invention. Polyols usable as plasticizers, in addition to those indicated above, comprise polyol acetates, ethoxylates and propoxylates, particularly sorbitol ethoxylate, glycerol ethoxylate, sorbitol acetate, and pentaerythritol acetate. These and other polyols which may be used are described in USP 5,292,782. The quantities of plasticizers used are generally from 1 to 100%, preferably from 10-30% by weight, relative to the starch. The thermoplastic polymers incompatible with starch usable in the compositions of the invention are preferably selected from following groups of polymers: a) aliphatic polyesters obtained by polycondensation of hydroxy-acids with 2 or more carbon atoms or of the corresponding lactones or lactides. Examples of these polyesters and their derivatives are described in USP 5,412,005; polycaprolactones, hydroxy-butyric and hydroxyvaleric polymers and copolymers, polyalkylene tartrate, and glycolic and lactic acid polymers and copolymers are preferred; b) aliphatic polyesters obtained by polycondensation of diols with 2-10 carbon atoms with aliphatic dicarboxylic acids; polyalkylene succinate, polyalkylene adipate are preferred; c) aliphatic polycarbonates such as polyethylene carbonate and polypropylene carbonate, polyester-carbonates, polyamides-carbonates, polyesters amides-carbonates; d) esters of cellulose such as cellulose acetate, cellulose propionate, cellulose butyrate and mixed esters thereof; e) esters of starch such as starch acetate, propionate, and butyrate and starches esterified with acids up to C18; the degree of substitution of the starch is between 0.5 and 3; f) carboxymethyl cellulose, alkyl ethers and hydroxyalkyl ethers of cellulose, polysaccharides, chitin and chitosan, alginic acid and alginates; g) vinyl esters and copolyesters both as such and partially hydrolyzed, such as polyvinyl acetate, polyvinyl acetate/polyvinyl alcohol up to 50% hydrolysis, polyethylenevinyl acetate, polyethylene-acrylic acid and mixtures of polymers from a) to g). The polyesters, particularly those obtained from hydroxy-acids, may be modified to form block copolymers or graft copolymers with polymers or copolymers which can react with the carboxyl and/or hydroxyl groups present in the polyesters. The polymers and copolymers listed may be upgraded with chain extenders such as di- or polyisocynates, di- or polyepoxides, or with polyfunctional compounds such as pyromellitic acid, pyromellitic anhydride. The homopolymers and copolymers of epsilon-hydroxy-acids, particularly 6-hydroxy-caproic acid and the corresponding lactone are preferred. The polyesters and their derivatives generally have melting points of between 40° and 175°C and molecular weights (weighted average) greater than 20000, preferably greater than 40000. The polyesters and their derivatives can advantageously be used in mixtures with one or more polymers or copolymers obtained from ethylenically unsatured monomers containing polar groups, preferably hydroxyl and carboxyl groups, such as ethylene/vinyl acetate, ethylene/vinyl alcohol and polyvinyl alcohol copolymers (the latter obtained by hydrolysis of polyvinyl acetate and ethylene vinyl acetate copolymers with degrees of hydrolysis of from 50 to 100%) and ethylene/acrylic acid copolymers. The ethylene/vinyl alcohol copolymers preferably contain from 10 to 50% by weight of ethylene. The alcohol groups of the polymers mentioned above may be converted into ether, ester, acetal or ketal groups. Preferred mixtures contain poly-epsilon-caprolactone and ethylene/vinyl alcohol or ethylene/vinyl acetate or polyvinyl alcohol copolymers. The ratio by weight between the polyesters and the polymers or copolymers containing alcohol groups is preferably between 1:30 and 30:1, more preferably between 1:15 and 15:1 and even more preferably between 1:6 and 6:1. The ratio by weight between thermoplastic starch and e) - g) polymer is generally between 1:20 and 20:1 and preferably from 1:10 to 10:1, more preferably from 1:4 to 4:1 and is selected in a manner such that the polyester constitutes the continuous phase and the starch the dispersed phase. Other preferred mixtures, used particularly in injection moulding, contain cellulose or starch esters with a degree of substitution of between 1 and 3, particularly cellulose acetate and starch acetate. The thermoplastic starch present in the compositions is obtained from native starch extracted from vegetables such as potatoes, rice, tapioca, maize and/or from chemically or physically modified starch. The compositions of the invention may include quantities of from 0.5 to 20% by weight of urea or hydroxides of alkaline-earth metals, between 0.1 and 5% of inorganic salts of alkali-metals or alkaline-earth metals, particularly LiCl, NaCl, Na 2 SO 4 , and also compounds containing boron, particularly boric acid, proteins and salts of proteins such as casein, gluten, caseinates, etc., abietic acid and derivatives thereof, rosinic acids, and natural gums. Other hydrophobic polymers such as polyethylene, polypropylene and polystyrene and additives such as anti-oxidants, lubricants, flame-proofing agents, fungicides, herbicides, fertilizers and opacifiers, compounds with rodent-repellent effects, waxes and lubricants may be present. The compositions are preferably prepared by mixing the components in an extruder heated to a temperature of between 100° and 220°C. Instead of an extruder, the components may be mixed in any apparatus which can ensure temperature and shear stress conditions appropriate for the viscosity values of the thermoplastic starch and of the polymer incompatible with starch. The starch may be treated to render it thermoplastic before being mixed with the other components of the composition or during the mixing of the components of the composition. In both cases, known methods are used, with operating temperatures of between about 100° and 220°C, in the presence of plasticizers and possibly water. The water content at the output of the extruder (that is, before any conditioning treatments) is preferably less than 5% by weight. The content is regulated by degassing during extrusion or with the use of dehydrated starch with a low water content. The compositions of the invention are usable particularly in the preparation of films, sheets, fibres, in injection-moulding, thermoforming, coextrusion, and in the preparation of expanded materials. Fields of use of particular interest are those of nappies and sanitary towels, of films for agriculture particularly for mulching, of bags, of films for cellophaning, of disposable articles, of expanded packaging elements, and of articles for nurserymen. The films may be used in laminates with layers formed by polyesters, polyester-amides, polyamides, aliphatic polycarbonates, aromatic/aliphatic polycarbonates, soluble polymers such as polyvinyl alcohol or other polymers, with paper, and with layers of inorganic materials such as silica, aluminium, etc. The compositions may be supplemented with fillers, preferably of natural origin, and with natural or modified resins such as abietic acid. The following examples 1-40 are provided. Example 1 is a comparative example; among examples 2 to 40, the compositions according to the invention are marked with an asterisc in Table 1; the remaining examples relate to compositions described in the parent application. The esters used in the examples 1-40 were prepared in accordance with conventional methods. In the case of the stronger carboxylic acids, the use of acid catalysts was not necessary but it sufficed to remove the water produced by the reaction. For the weaker acids, particularly the fatty acids, the reaction was catalyzed with small amounts of toluene sulphonic acid. Since the esterification did not affect all of the hydroxyl groups of the polyol (so that both ester functions and alcohol functions were present simultaneously in the reaction product) but only a fraction of between 10 and 90% of the hydroxyl groups, preferably between 20 and 70%, and more preferably between 25 and 50%, it was possible to continue the reaction until the acid was used up. Any traces of unreacted acid could be neutralized with organic or inorganic bases, preferably triethanolamine. The product of these partial esterifications was constituted predominantly by the polyol with the desired degree of esterification; the second largest fraction was constituted by unsubstituted polyol, and the remainder was constituted by polyol with higher degrees of substitution or, in the case of dicarboxylic acids, by oligomeric forms. The inherent viscosity, when measured in the examples, is expressed by the equation: [η] inh = [η]t/t° c where: t° = time taken by a known volume of pure solvent tc pass through the capillary of the viscosimeter; t = time taken by an identical volume of the solution containing the polymer to pass through the capillary, c = concentration of the polymer in the solution, expressed in g/dl. The instrument used for the measurements was a Bischoff viscosimeter. The measurement was carried out in tetrahydrofuran at 25° with the use of 1g of polymer in 100ml of solvent. In the following examples all "parts" are intended by weight, unless otherwise stated. EXAMPLE 1 (comparison) A composition containing 55 parts of PCL TONE 787 (Union Carbide), 31 parts of Globe maize starch 03401 (Cerestar), 0.25 parts of erucamide, 12 parts of glycerol, and 1.75 parts of water was mixed in an OMC single-screw extruder D = 20 mm and L/D = 30 with an operating temperature profile of 80/180/150/130°C at 70 rpm. The pellets obtained were then supplied to a Haake single-screw extruder, D = 19 mm and L/D = 20, with a film-forming head. The heating profile during the blow-moulding was 115/120/125/130°C at 30 rpm. The film obtained constituted the reference material. EXAMPLES 2-40 The compositions given in the following table were mixed and filmed with the use of the method of Example 1 and with the PCL, starch, water and erucamide parts remaining the same but with all or some of the glycerol replaced by the esters indicated below: EVALUATION OF THE MATERIAL SAMPLES The films were conditioned at 20°C and 15% RH for 48 hours and were then subjected to preliminary tear-strength screening. The evaluation was carried out manually and the appraisal was as follows: Example very good good poor very poor 1 x 2 x 3 x 4 x 5 x 6 x 7 x 8 x 9 x 10 x 11 x 12 x 13 x 14 x 15 x 16 x 17 x 18 x 19 x 20 x 21 x 22 x 23 x 24 x 25 x 26 x 27 x 28 x 29 x 30 x 31 x 32 x 33 x 34 x 35 x 36 x 37 x 38 x 39 x 40 x PAPER CONTACT TEST The formulations which gave good or very good responses in the preliminary screening were tested in terms of tear strength after the corresponding films had been placed between sheets of pure cellulose paper at 50°C and RH < 10% for two months. In this case, preliminary manual screening was again carried out. The test was quite severe since the paper was able to take plasticizers such as glycerol from the films. The results were as follows: Example very good good poor very poor 1 x 2 x 3 x 5 x 7 x 8 x 9 x 10 x 11 x 12 x 13 x 14 x 15 x 16 x 17 x 18 x 19 x 20 x 21 x 22 x 23 x 24 x 25 x 26 x 27 x 28 x 30 x 31 x 32 x 33 x 34 x 37 x 38 x 40 x TEAR STRENGTH AFTER THE FILMS HAD BEEN WASHED IN WATER This was the most severe test since the conventional plasticizers (glycerol and sorbilene in this case) as well as the water-soluble esters were completely removed. In practice, the film was immersed in distilled water for 24 hours, after which it was left to dry for 25 hours at ambient temperature. The films which were good or very good in the paper contact test were subjected to this test; evaluation was again manual. Example very good good poor very poor 1 x 2 x 3 x 5 x 7 x 8 x 9 x 10 x 11 x 12 x 13 x 14 x 15 x 16 x 17 x 18 x 19 x 20 x 21 x 22 x 23 x 24 x 25 x 26 x 27 x 28 x 30 x 31 x 33 x 34 x 37 x 38 x 40 x MECHANICAL PROPERTIES The mechanical properties of some films subjected to washing with water are given in comparison with the untreated films. Example No. Sigma b MPa Ext. % Modulus MPa Breaking energy KJ/m 2 1 untr. 33 849 200 6837 1 washed 19 3 1179 16 7 untr. 12 684 156 3958 7 washed 8 314 752 1790 12 untr. 22 969 271 6409 12 washed 12 8 751 45 13 untr. 23 946 161 6340 13 washed 11 326 573 1768 17 untr. 33 923 170 7515 17 washed 19 490 885 4750 18 untr. 33 849 200 6837 18 washed 19 420 996 4970 19 untr. 26 741 170 5042 19 washed 17 393 1007 3339 36 untr. 25 1076 156 7582 36 washed 10 9 804 38 37 untr. 23 946 161 6349 37 washed 6 326 546 1768

Claims: Biodegradable heterophase polymeric compositions having good resistance to ageing and to low humidity conditions, comprising thermoplastic starch and a thermoplastic polymer incompatible with starch, in which starch constitutes the dispersed phase and the thermoplastic polymer constitutes the continuous phase, containing an interfacial agent selected from esters of polyols with mono- or polycarboxylic acids with less than 12 carbon atoms and with pK values greater than 4.5 and having HLB indices between 5.5 and 8. Compositions according to claim 1, in which the said esters are obtained from caproic, suberic, or azelaic acid. A composition according to claim 2, in which the ester comprises the monoglyceride. Compositions according to any of the preceding claims 1 to 3, in which the ratio by weight between the thermoplastic starch and the thermoplastic polymer incompatible with starch is such that the starch constitutes the dispersed phase and the thermoplastic polymer constituted the continuous phase. Compositions according to any of the preceding claims 1 to 3, in which the quantities of the esters used are from 0.5 to 20% by weight relative to the total composition. Compositions according to any of the preceding claims 1 to 5, comprising a plasticizer. Compositions according to claim 6, in which the plasticizer is selected from polyols with 3 or more carbon atoms and with 2 or more alcohol groups, the polyols optionally being etherified or esterified Compositions according to claim 7, in which the polyol is selected from glycerol, sorbitol, etherified or esterified sorbitol, ethylene glycol and trimethylol propane. Compositions according to any of claims 5 to 8, in which a quantity of plasticizer of from 1 to 100% by weight relative to the starch is used. Compositions according to claim 9, in which the ester is used in a ratio of from 1:30 to 1:2.5 by weight to the starch. Compositions and materials according to any of the preceding claims, in which the thermoplastic polymer is selected from aliphatic or aliphatic-aromatic polyesters obtained by polycondensation of hydroxy-acids with 2 or more carbon atoms, or from the corresponding lactones or lactides, or by polycondensation of a diol with 1-12 carbon atoms with a dicarboxylic aliphatic acid or with mixtures thereof with dicarboxylic aromatic acids. Compositions according to claim 11, in which the polymer is a poly-ε-caprolactone. A film obtained from the compositions according to any of claims 1 to 12. Use of the films according to claim 13 in the manufacture of nappies, of sanitary towels, of bags and of laminated paper. Use of the films according to claim 14 in the agricultural field for mulching application. Use of the compositions according to any of claims 1 to 12 for the manufacture of expanded moulded articles usable in packaging, and of disposable articles.

Inventors: BASTIOLI CATIA, BELLOTTI VITTORIO, CELLA GIAN DOMENICO, DEL GIUDICE LUCIANO, MONTINO SANDRO, PEREGO GABRIELE, BASTIOLI, CATIA, BELLOTTI, VITTORIO, CELLA, GIAN DOMENICO, DEL GIUDICE, LUCIANO, MONTINO, SANDRO, PEREGO, GABRIELE
Applicants: NOVAMONT SPA, NOVAMONT S.P.A.
Application year: 1997
Main classification: C08L67
IPC codes: C08L77, C08G18, C08J5, C08L75, C08L101, C08L67, C08L3