US20190330430A1 - Biodegradable film - Google Patents
Biodegradable film Download PDFInfo
- Publication number
- US20190330430A1 US20190330430A1 US16/309,576 US201716309576A US2019330430A1 US 20190330430 A1 US20190330430 A1 US 20190330430A1 US 201716309576 A US201716309576 A US 201716309576A US 2019330430 A1 US2019330430 A1 US 2019330430A1
- Authority
- US
- United States
- Prior art keywords
- acid
- film according
- moles
- component
- mixtures
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000004806 packaging method and process Methods 0.000 claims abstract description 11
- -1 aromatic dicarboxylic acids Chemical class 0.000 claims description 69
- 239000000203 mixture Substances 0.000 claims description 54
- 229920000728 polyester Polymers 0.000 claims description 37
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 36
- 229920002472 Starch Polymers 0.000 claims description 31
- 235000019698 starch Nutrition 0.000 claims description 31
- 239000008107 starch Substances 0.000 claims description 29
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 22
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 18
- 150000002009 diols Chemical class 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
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- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
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- 235000012055 fruits and vegetables Nutrition 0.000 claims description 3
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
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- 230000000052 comparative effect Effects 0.000 description 8
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 8
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- 239000004310 lactic acid Substances 0.000 description 7
- 235000014655 lactic acid Nutrition 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
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- 235000011187 glycerol Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical group O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 5
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- 239000004952 Polyamide Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 239000000600 sorbitol Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-Lactic acid Natural products C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000009264 composting Methods 0.000 description 4
- FEKRFYZGYUTGRY-UHFFFAOYSA-N n'-ethylmethanediimine Chemical compound CCN=C=N FEKRFYZGYUTGRY-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
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- 239000003054 catalyst Substances 0.000 description 3
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
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- 238000001125 extrusion Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
Definitions
- This invention relates to a biodegradable film that is particularly suitable for use in the manufacture of packaging of various kinds, in particular bags for the carrying of goods and bags for food packaging, characterized by high level mechanical properties, in particular high tear resistance.
- the production of packaging, in particular bags for the carrying of goods requires the use of films with good mechanical properties.
- this invention addresses this problem and presents a solution to it that is capable of suitably balancing these different requirements.
- this invention relates to a film made by a composition comprising
- the film according to this invention structurally comprises a continuous phase and a dispersed phase capable of rendering the film rapidly biodegradable under industrial composting conditions and more preferably in home composting according to standard UNI11355.
- the said film also has high level mechanical properties, in particular a tear resistance in the machine direction of >100 N/mm, determined according to ASTM D1922 (at 23° C. and 55% relative humidity).
- the aromatic dicarboxylic acids in component a1 are preferably selected from aromatic dicarboxylic acids of the phthalic acid type, preferably terephthalic acid or isophthalic acid, more preferably terephthalic acid, and heterocyclic dicarboxylic aromatic compounds, preferably 2,5-furandicarboxylic acid, 2,4-furandicarboxylic acid, 2,3-furandicarboxylic acid, 3,4-furandicarboxylic acid, more preferably 2,5-furandicarboxylic acid, their esters, salts and mixtures.
- the said aromatic dicarboxylic acids comprise:
- the saturated aliphatic dicarboxylic acids in component a2 of polyester i. are preferably selected from saturated C 2 -C 24 , preferably C 4 -C 13 , more preferably C 4 -C 11 dicarboxylic acids, their C 1 -C 24 , preferably C 1 -C 4 , alkyl esters, their salts and mixtures thereof.
- the saturated aliphatic dicarboxylic acids are selected from succinic acid, 2-ethylsuccinic acid, glutaric acid, 2-methylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, hexadecanedioic acid, octadecanedioic acid and their C 1-24 alkyl esters.
- the saturated aliphatic dicarboxylic acid comprise mixtures comprising at least 50% by moles, preferably more than 60% by moles, more preferably more than 65% by moles, of succinic acid, adipic acid, azelaic acid, sebacic acid, brassylic acid, their C 1 -C 24 , preferably C 1 -C 4 , esters, and mixtures thereof.
- the said mixtures comprise or consist of adipic acid and azelaic acid and contain azelaic acid in a quantity of between 5 and 40% by moles, more preferably between 10 and 35% by moles of azelaic acid with respect to the sum of adipic acid and azelaic acid.
- the unsaturated aliphatic dicarboxylic acids in component a3 of polyester i. are preferably selected from itaconic acid, fumaric acid, 4-methylene-pimelic acid, 3,4-bis(methylene)nonandioic acid, 5-methylene-nonandioic acid, their C 1 -C 24 , preferably C 1 -C 4 , alkyl esters, their salts and mixtures thereof.
- the unsaturated aliphatic dicarboxylic acids comprise mixtures comprising at least 50% by moles, preferably more than 60% by moles, more preferably more than 65% by moles, of itaconic acid and its C 1 -C 24 , preferably C 1 -C 4 , esters. More preferably the unsaturated aliphatic dicarboxylic acid comprise itaconic acid.
- saturated aliphatic diols in component b1 of polyester i. are preferably selected from 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 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-cyclohaxanedimethanol, neopentylglycol, 2-methyl-1,3-propanediol, dianhydrosorbitol, dianhydromannitol, dianhydroiditol, cyclohexane
- the diol component comprises at least 50% by moles of one or more diols selected from 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol. More preferably the diol component comprises or consists of 1,4-butanediol.
- the unsaturated aliphatic diols in component b2 of polyester i. are preferably selected from cis 2-buten-1,4-diol, trans 2-buten-1,4-diol, 2-butyn-1,4-diol, cis 2-penten 1,5 diol, trans 2-penten 1,5 diol, 2-pentyn 1,5 diol, cis 2-hexen-1,6-diol, trans 2-hexen-1,6-diol, 2-hexyn-1,6-diol, cis 3-hexen-1,6-diol, trans 3-hexen-1,6-diol, 3-hexyn-1,6-diol.
- the polyester i. comprises at least 10% by moles, more preferably at least 20% by moles, even more preferably at least 30% by moles, of aromatic dicarboxylic acids and/or aliphatic dicarboxylic acids and/or diols of renewable origin.
- the products that can be considered of renewable origin are those obtained from sources that, by their very nature, are regenerable and inexhaustible on the time scale of human life and the use of which consequently does not negatively affect the availability of natural resources for future generations.
- monomers of renewable origin are sebacic acid, succinic acid, 2,5-furandicarboxylic acid, azelaic acid, 1,4-butanediol.
- the Mn molecular weight of the said polyester i. is preferably ⁇ 20000, more preferably ⁇ 40000. As far as the polydispersity index of the molecular weights, Mw/Mn, is concerned, this is instead preferably between 1.5 and 10, more preferably between 1.6 and 5, and even more preferably between 1.8 and 2.7.
- the M n and M w molecular weights may be measured using Gel Permeation Chromatography (GPC). The determination may be performed with the chromatography system held at 40° C., using a set of two columns in series (particle diameters 5 ⁇ m and 3 ⁇ m with mixed porosity), a refractive index detector, chloroform as eluent (flow 0.5 ml/min) and using polystyrene as the reference standard.
- GPC Gel Permeation Chromatography
- the terminal acid groups content of the said polyester i. is preferably below 100 meq/kg, preferably below 60 meq/kg, and even more preferably below 40 meq/kg.
- the terminal acid groups content may be measured as follows: 1.5-3 g of polyester are placed in a 100 ml flask together with 60 ml of chloroform. After the polyester has completely dissolved 25 ml of 2-propanol are added, and then 1 ml of deionised water immediately before analysis. The solution so obtained is titrated against a previously standardised solution of NaOH in ethanol. An appropriate indicator is used to determine the end point of the titration, such as for example a glass electrode for acid-base titrations in non-aqueous solvents.
- the terminal acid groups content is calculated on the basis of the consumption of NaOH solution in ethanol using the following equation:
- Terminal ⁇ ⁇ acid ⁇ ⁇ groups ⁇ ⁇ content ⁇ ⁇ ( meq ⁇ / ⁇ kg ⁇ ⁇ polymer ) ⁇ ( V eq - V b ) ⁇ T ⁇ ⁇ 1000 P
- V eq ml of NaOH in ethanol at the end point of the titration of the sample
- the polyester i. has an inherent viscosity (measured using an Ubbelohde viscosimeter for solutions of concentration 0.2 g/dl in CHCl 3 at 25° C.) of over 0.3 dl/g, preferably between 0.3 and 2 dl/g, more preferably between 0.4 and 1.1 dl/g.
- polyester i. is biodegradable.
- biodegradable polymer is meant a polymer which is biodegradable in accordance with standard EN 13432.
- the said polyester i. can be synthesised according to any of the processes known in the state of the art. In particular it may advantageously be obtained through a polycondensation reaction.
- the synthesis process may be performed in the presence of a suitable catalyst.
- suitable catalysts mention may for example be made of organometallic compounds of tin, for example stannoic acid derivatives, titanium compounds, for example orthobutyl titanate, aluminium compounds, for example triisopropyl aluminium, compounds of antimony and zinc and zirconium and mixtures thereof.
- the composition of the film according to the present invention comprises 0.1-50% by weight, preferably 5-40%, with respect to the sum of components i.-v., of at least one polymer of natural origin.
- the polymer of natural origin (component ii.) is advantageously selected from starch, chitin, chitosan, alginates, proteins such as gluten, zein, casein, collagen, gelatin, natural rubbers, rosinic acid and their derivatives.
- the polymer of natural origin is starch.
- starch all types of starch, that is flour, native starch, hydrolysed starch, destructured starch, gelatinised starch, plasticised starch, thermoplastic starch, biofiller comprising complexed starch or mixtures thereof.
- starches such as those from potato, maize, tapioca and peas.
- Starches which are capable of easily being destructured or which have high initial molecular weights such as for example potato or maize starch, have proved to be particularly advantageous.
- the starch may be present as such or in a chemically modified form, such as for example in the form of starch esters having a degree of substitution of between 0.2 and 2.5, starch hydroxypropylate or starch modified with fatty chains.
- the starch is destructured by means of an extrusion process at temperatures of between 110 and 250° C., preferably 130-180° C., preferably at pressures between 0.1 and 7 MPa, preferably 0.3-6 MPa, preferably providing a specific energy of more than 0.1 kWh/kg during the said extrusion.
- Destructuring of the starch preferably takes place in the presence of 1-40% by weight with respect to the weight of the starch of one or more plasticisers selected from water and polyols having from 2 to 22 carbon atoms. As far as the water is concerned, this may also be that which is naturally present in the starch.
- plasticisers selected from water and polyols having from 2 to 22 carbon atoms.
- the polyols those preferred are polyols having from 1 to 20 hydroxyl groups containing 2 to 6 carbon atoms, their ethers, thioethers and organic and inorganic esters.
- polyols examples include glycerine, diglycerol, polyglycerol, pentaerythritol, polyglycerol ethoxylate, ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentylglycol, sorbitol monoacetate, sorbitol diacetate, sorbitol monoethoxylate, sorbitol diethoxylate, and mixtures thereof.
- the starch is destructured in the presence of glycerol or a mixture of plasticisers comprising glycerol, more preferably containing between 2 and 90% by weight of glycerol.
- the destructured and cross-linked starch according to this invention comprises between 1 and 40% by weight of plasticisers with respect to the weight of the starch.
- the starch is preferably in the form of particles having a circular or elliptical cross section or in any event a cross-section similar to an ellipse having a mean arithmetic diameter less than 1 micron, and more preferably of less than 0.5 ⁇ m mean diameter, measured using the major axis of the particle.
- the composition of the film according to the present invention comprises 1-40% by weight, preferably 2-30%, with respect to the sum of components i.-v., of at least one polyhydroxyalkanoate (component iii.), preferably selected from the group consisting of polyesters of lactic acid, poly- ⁇ -caprolactone, polyhydroxybutyrate, polyhydroxybutyrate-valerate, polyhydroxybutyrate propanoate, polyhydroxybutyrate-hexanoate, polyhydroxybutyrate-decanoate, polyhydroxybutyrate-dodecanoate, polyhydroxybutyrate-hexadecanoate, polyhydroxybutyrate-octadecanoate, poly-3-hydroxybutyrate-4-hydroxybutyrate.
- the said polyhydroxyalkanoate comprises at least 80% by weight of one or more polyesters of lactic acid.
- the lactic acid polyesters are selected from the group comprising poly-L-lactic acid, poly-D-lactic acid, the poly-D-L-lactic acid stereo complex, copolymers comprising more than 50% by moles of the said lactic acid polyesters, or mixtures thereof.
- the lactic acid polyester comprises at least 95% by weight of units deriving from L-lactic acid, ⁇ 5% of repetitive units deriving from D-lactic acid, has a melting point within the range 135-180° C., a glass transition temperature (Tg) in the range 55-65° C. and an MFR (measured in accordance with standard ISO 1133-1 at 190° C. and 2.16 kg) within the range 1-50 g/10 min.
- Tg glass transition temperature
- MFR measured in accordance with standard ISO 1133-1 at 190° C. and 2.16 kg
- the composition of the film according to the present invention comprises 0-15% by weight, with respect to the sum of components i.-v., of at least one inorganic filler (component iv.), which is preferably selected from kaolin, barytes, clay, talc, calcium and magnesium, iron and lead carbonates, aluminium hydroxide, diatomaceous earth, aluminium sulfate, barium sulfate, silica, mica, titanium dioxide, wollastonite.
- component iv. inorganic filler
- the inorganic filler comprises talc, calcium carbonate or their mixtures, present in the form of particles having a mean arithmetic diameter of less than 10 microns measured in relation to the major axis of the particles. It has in fact been discovered that fillers of the abovementioned type which are not characterised by the said mean arithmetic diameter prove the disintegratability characteristics significantly less during the industrial composting of objects containing them.
- the composition of the film of the present invention comprises 0-5% by weight, preferably 0-0.5%, with respect to the sum of components i.-v., of at least one cross-linking agent and/or chain extender (component v.) in order to improve stability to hydrolysis.
- the said cross-linking agent and/or chain extender is selected from compounds having two and/or multiple functional groups including isocyanate, peroxide, carbodiimide, isocyanurate, oxazoline, epoxy, anhydride or divinylether groups or mixtures thereof.
- the cross-linking agent and/or chain extender comprises at least one compound having two and/or multiple functional groups including isocyanate groups. More preferably the cross-linking agent and/or chain extender comprises at least 25% by weight of one or more compounds having two and/or multiple functional groups including isocyanate groups.
- the compounds having two and multifunctional groups including isocyanate groups are preferably selected from p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4-diphenylmethane-diisocyanate, 1,3-phenylene-4-chloro diisocyanate, 1,5-naphthalene diisocyanate, 4,4-diphenylene diisocyanate, 3,3′-dimethyl-4,4-diphenylmethane diisocyanate, 3-methyl-4,4′-diphenylmethane diisocyanate, diphenylester diisocyanate, 2,4-cyclohexane diisocyanate, 2,3-cyclohexane diisocyanate, 1-methyl 2,4-cyclohexyl diisocyanate, 1-methyl 2,6-cyclohexyl diisocyanate, bis-(isocyanate cyclohexyl)
- these are preferably selected from benzoyl peroxide, lauroyl peroxide, isononanoyl peroxide, di-(t-butylperoxyisopropyl)benzene, t-butyl peroxide, dicumyl peroxide, alpha, alpha-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butyl cumyl peroxide, di-t-butylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hex-3-yne, di(4-t-butylcyclohexyl)peroxy dicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, 3,6,9-triethyl-3
- the compounds having two and/or multiple functional groups including carbodiimide groups which are preferably used in the composition according to this invention are selected from poly(cyclooctylene carbodiimide), poly(1,4-dimethylencyclohexylene carbodiimide), poly(cyclohexylene carbodiimide), poly(ethylene carbodiimide), poly(butylene carbodiimide), poly(isobutylene carbodiimide), poly(nonylene carbodiimide), poly(dodecylene carbodiimide), poly(neopentylene carbodiimide), poly(1,4-dimethylene phenylene carbodiimide), poly(2,2′,6,6′-tetraisopropyldiphenylene carbodiimide) (Stabaxol® D), poly(2,4,6-triisopropyl-1,3-phenylene carbodiimide) (Stabaxol® P-100), poly(2,6 diiso
- Examples of compounds having two and multiple functional groups including epoxy groups which may advantageously be used in the composition according to this invention are all the polyepoxides from epoxidated oils and/or from styrene-glycidylether-methylmethacrylate or glycidylether-methylmethacrylate, included within a range of molecular weights between 1000 and 10000 and having an epoxide number per molecule within the range 1 to 30 and preferably between 5 and 25, the selected epoxides in the group comprising: diethyleneglycol diglycidylether, polyethyleneglycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, 1,2-epoxybutane, polyglycerol polyglycidyl ether, isoprene diepoxide, and cycloaliphatic diepoxides, 1,4-cyclohaxanedimethanol diglycidyl ether, g
- catalysts may also be used to raise the reactivity of the reactive groups.
- salts of fatty acids even more preferably calcium and zinc stearates, may preferably be used.
- the cross-linking agent and/or chain extender for the composition comprises compounds including isocyanate groups, preferably 4,4-diphenylmethane-diisocyanate, and/or containing carbodiimide groups, and/or containing epoxy groups, preferably of the styrene-glycidylether-methylmethacrylate type.
- the film according to the present invention comprises a composition comprising the components i.-v. and preferably one or more polymers which are not the same as components i., ii. and iii., of synthetic or natural origin, which may or may not be biodegradable, together with possibly one or more other components.
- polymers which are not the same as components i., ii. and iii., of synthetic or natural origin, which may or may not be biodegradable, are concerned, these are advantageously selected from the group comprising vinyl polymers, diacid diol polyesters which are not the same as polyester i., polyamides, polyurethanes, polyethers, polyureas, polycarbonates and mixtures thereof.
- vinyl polymers those preferred are polyethylene, polypropylene, their copolymers, polyvinyl alcohol, polyvinyl acetate, polyethylvinyl acetate and polyethylene vinyl alcohol, polystyrene, chlorinated vinyl polymers, polyacrylates.
- chlorinated vinyl polymers those which are intended to be included here, in addition to polyvinyl chloride are polyvinylidene chloride, polyethylene 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 represents more than 50% by moles.
- the said polymers may be random, block or alternating copolymers.
- polyamides in the composition according to this invention are preferably selected from the group comprising 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 their combinations of the 6/9, 6/10, 6/11 and 6/12 type, their mixtures and both random and block copolymers.
- the polycarbonates of the composition according to this invention are selected from the group comprising polyalkylene carbonates, more preferably polyethylene carbonates, polypropylene carbonates, polybutylene carbonates, their mixtures and random and block copolymers.
- polyethers those preferred are those selected from the group consisting of polyethylene glycols, polypropylene glycols, polybutylene glycols, their copolymers and their mixtures having molecular weights from 70000 to 500000.
- diacid diol polyesters which are not the same as polyester i. are concerned, these preferably comprise:
- aromatic dicarboxylic acids c1, saturated aliphatic dicarboxylic acids c2, unsaturated aliphatic dicarboxylic acids c3, saturated aliphatic diols d1 and unsaturated aliphatic diols d2 for the said polyesters are selected from those described above for the polyester i according to this invention.
- composition preferably also comprises at least one other component selected from the group consisting of plasticisers, UV stabilisers, lubricants, nucleating agents, surfactants, antistatic agents, pigments, flame-retardant agents, compatibilising agents, lignin, organic acids, antioxidants, anti-mould agents, waxes, process coadjuvants and polymer components preferably selected from the group consisting of vinyl polymers, diacid diol polyesters which are not the aliphatic-aromatic polyesters described above, polyamides, polyurethanes, polyethers, polyureas or polycarbonates.
- plasticisers in addition to the plasticisers preferably used for preparation of the destructured starch described above, one or more plasticisers selected from the group consisting of phthalates, such as for example diisononyl phthalate, trimellitates, such as for example esters of trimellitic acid with C 4 -C 20 monoalcohols preferably selected from the group consisting of n-octanol and n-decanol, and aliphatic esters having the following structure:
- R 1 O—C(O)—R 4 —C(O)—[—O—R 2 —O—C(O)—R 5 —C(O)—] m —O—R 3
- the selected plasticisers are preferably present up to 10% by weight with respect to the total weight of the composition of the film according to the present invention.
- the lubricants are preferably selected from esters and metal salts of fatty acids such as for example zinc stearate, calcium stearate, aluminium stearate and acetyl stearate.
- the composition of the film according to the present invention comprises up to 1% by weight of lubricants, more preferably up to 0.5% by weight with respect to the total weight of the composition of the film according to the present invention.
- nucleating agents examples include the sodium salt of saccharine, calcium silicate, sodium benzoate, calcium titanate, boron nitride, isotactic polypropylene, or low molecular weight PLA. These additives are preferably added in quantities up to 10% by weight and more preferably between 2 and 6% by weight with respect to the total weight of the composition.
- Pigments may also be added if necessary, for example titanium dioxide, clays, copper phthalocyanine, silicates, iron oxide and hydroxides, carbon black and magnesium oxide.
- additives are preferably added up to 10% by weight.
- the film according to this invention advantageously has a thickness of less than 40 ⁇ m, preferably less than 30 ⁇ m.
- the film according to the present invention is characterized by a tear resistance in the machine direction of >100 N/mm, determined according to ASTM D1922 (at 23° C. and 55% relative humidity).
- the film according to the present invention is characterized by a tear resistance in the transversal direction of >150 N/mm, determined according to ASTM D1922 (at 23° C. and 55% relative humidity).
- the film according to the present invention is biodegradable in accordance with standard EN 13432.
- the film according to the present invention is biodegradable in home composting according to standard UNI11355.
- the film according to the present invention is particularly suitable for the production of an extensive range of articles such as for example packaging of various kinds, in particular bags for carrying of goods and bags for food packaging such as bags for fruit and vegetables.
- said bags for fruit and vegetables comprising the film of this invention are characterized by a thickness of less than 20 ⁇ m, more preferably less than 17 ⁇ m, even more preferably less than 15 ⁇ m.
- the film according to the present invention can be advantageously be used as a single layer or in multilayer films.
- Said multilayer films may be produced according to any of those processes known in the art, through for example a coextrusion, coating/spreading or lamination process.
- HMV-15CA Carbodilite from Nisshinbo Chemical Inc.
- the extrusion parameters are as follows:
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Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| ITUA2016A004319A ITUA20164319A1 (it) | 2016-06-13 | 2016-06-13 | Film biodegradabile multistrato. |
| IT102016000060486 | 2016-06-13 | ||
| PCT/EP2017/064408 WO2017216158A1 (en) | 2016-06-13 | 2017-06-13 | Biodegradable film |
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| PCT/EP2017/064408 A-371-Of-International WO2017216158A1 (en) | 2016-06-13 | 2017-06-13 | Biodegradable film |
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| US20190330430A1 true US20190330430A1 (en) | 2019-10-31 |
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| US16/309,560 Abandoned US20190160796A1 (en) | 2016-06-13 | 2017-06-13 | Multilayer biodegradable film |
| US16/309,576 Abandoned US20190330430A1 (en) | 2016-06-13 | 2017-06-13 | Biodegradable film |
| US17/665,039 Pending US20220402249A1 (en) | 2016-06-13 | 2022-02-04 | Biodegradable film |
| US18/047,307 Active US12138890B2 (en) | 2016-06-13 | 2022-10-18 | Multilayer biodegradable film |
| US18/907,747 Pending US20250033333A1 (en) | 2016-06-13 | 2024-10-07 | Multilayer biodegradable film |
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| US17/665,039 Pending US20220402249A1 (en) | 2016-06-13 | 2022-02-04 | Biodegradable film |
| US18/047,307 Active US12138890B2 (en) | 2016-06-13 | 2022-10-18 | Multilayer biodegradable film |
| US18/907,747 Pending US20250033333A1 (en) | 2016-06-13 | 2024-10-07 | Multilayer biodegradable film |
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| US (5) | US20190160796A1 (OSRAM) |
| EP (5) | EP4617059A1 (OSRAM) |
| JP (3) | JP7001623B2 (OSRAM) |
| CN (5) | CN115491001A (OSRAM) |
| CA (2) | CA3027266A1 (OSRAM) |
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| ES (3) | ES3031958T3 (OSRAM) |
| FI (1) | FI3778236T3 (OSRAM) |
| HR (2) | HRP20201942T1 (OSRAM) |
| HU (3) | HUE053160T2 (OSRAM) |
| IT (1) | ITUA20164319A1 (OSRAM) |
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| TN (1) | TN2018000421A1 (OSRAM) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US12108711B2 (en) | 2014-09-23 | 2024-10-08 | Hologenix Llc | Active polymer materials for growing more vigorous, larger and healthier plants |
| DE102017003341A1 (de) * | 2017-04-05 | 2018-10-11 | Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg | Biologisch abbaubare Folie |
| ES2968304T3 (es) | 2019-01-30 | 2024-05-08 | Basf Se | Procedimiento para la preparación de mezclas de almidón |
| IT201900006282A1 (it) * | 2019-04-23 | 2020-10-23 | Novamont Spa | Film biodegradabili aventi migliorate proprietà meccaniche |
| IT201900014154A1 (it) * | 2019-08-06 | 2021-02-06 | Novamont Spa | Film per imballaggio |
| WO2021107000A1 (ja) * | 2019-11-29 | 2021-06-03 | 大日本印刷株式会社 | 積層体、積層体の製造方法、積層用フィルム、画像表示装置 |
| IT202000012184A1 (it) * | 2020-05-25 | 2021-11-25 | Novamont Spa | Poliestere biodegradabile e pellicole aderenti per l’imballaggio con esso realizzate |
| US11584110B2 (en) * | 2020-07-30 | 2023-02-21 | Pepsico, Inc. | Multi-layered packaging films |
| IT202000032663A1 (it) * | 2020-12-29 | 2022-06-29 | Novamont Spa | Film biodegradabile multistrato ad alta disintegrazione |
| CN113172975A (zh) * | 2021-04-06 | 2021-07-27 | 温州银润包装有限公司 | 一种多层复合共挤膜及其制作工艺 |
| CN113912879A (zh) * | 2021-08-20 | 2022-01-11 | 山东亿隆薄膜材料有限责任公司 | 一种环保热收缩膜 |
| DE102022000533A1 (de) | 2022-02-11 | 2023-08-17 | proStruktur Management GmbH | Verfahren für das Verpacken von Einzelteilen |
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