ZA200102221B - Use of polyester resins for the production of articles having good properties as barries to water vapour. - Google Patents
Use of polyester resins for the production of articles having good properties as barries to water vapour. Download PDFInfo
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- ZA200102221B ZA200102221B ZA200102221A ZA200102221A ZA200102221B ZA 200102221 B ZA200102221 B ZA 200102221B ZA 200102221 A ZA200102221 A ZA 200102221A ZA 200102221 A ZA200102221 A ZA 200102221A ZA 200102221 B ZA200102221 B ZA 200102221B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 27
- 229920001225 polyester resin Polymers 0.000 title claims description 24
- 239000004645 polyester resin Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000010408 film Substances 0.000 claims description 21
- 230000035699 permeability Effects 0.000 claims description 20
- -1 polyethylene Polymers 0.000 claims description 19
- 230000004888 barrier function Effects 0.000 claims description 15
- 235000013305 food Nutrition 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 238000006068 polycondensation reaction Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 150000002009 diols Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000004806 packaging method and process Methods 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 7
- 235000013410 fast food Nutrition 0.000 claims description 7
- 239000008107 starch Substances 0.000 claims description 7
- 235000019698 starch Nutrition 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 229920002988 biodegradable polymer Polymers 0.000 claims description 6
- 239000004621 biodegradable polymer Substances 0.000 claims description 6
- 238000009264 composting Methods 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 6
- 229940116351 sebacate Drugs 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 claims description 6
- 235000013311 vegetables Nutrition 0.000 claims description 6
- 241000196324 Embryophyta Species 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 235000013372 meat Nutrition 0.000 claims description 5
- 235000013336 milk Nutrition 0.000 claims description 5
- 239000008267 milk Substances 0.000 claims description 5
- 210000004080 milk Anatomy 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 claims description 5
- 229920003232 aliphatic polyester Polymers 0.000 claims description 4
- 229940067597 azelate Drugs 0.000 claims description 4
- 235000013361 beverage Nutrition 0.000 claims description 4
- 238000009933 burial Methods 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 239000000123 paper Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 240000002129 Malva sylvestris Species 0.000 claims description 3
- 235000006770 Malva sylvestris Nutrition 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 235000013351 cheese Nutrition 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 150000001261 hydroxy acids Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 230000002262 irrigation Effects 0.000 claims description 3
- 238000003973 irrigation Methods 0.000 claims description 3
- 150000002596 lactones Chemical class 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005054 agglomeration Methods 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002537 cosmetic Substances 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 229940079593 drug Drugs 0.000 claims description 2
- 235000012055 fruits and vegetables Nutrition 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000011104 metalized film Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 235000013618 yogurt Nutrition 0.000 claims description 2
- 101100505320 Caenorhabditis elegans gpa-16 gene Proteins 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 239000003963 antioxidant agent Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 235000013365 dairy product Nutrition 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 239000000796 flavoring agent Substances 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 239000000314 lubricant Substances 0.000 claims 1
- 239000002304 perfume Substances 0.000 claims 1
- 239000004014 plasticizer Substances 0.000 claims 1
- 230000008569 process Effects 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 claims 1
- 229920000728 polyester Polymers 0.000 description 7
- 229920001634 Copolyester Polymers 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 230000035622 drinking Effects 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000010902 straw Substances 0.000 description 4
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 229920001748 polybutylene Polymers 0.000 description 3
- 239000004631 polybutylene succinate Substances 0.000 description 3
- 229920002961 polybutylene succinate Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 239000011785 micronutrient Substances 0.000 description 2
- 235000013369 micronutrients Nutrition 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- 229940070710 valerate Drugs 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- JOSXCARTDOQGLV-UHFFFAOYSA-N 14-hydroxymyristic acid Chemical class OCCCCCCCCCCCCCC(O)=O JOSXCARTDOQGLV-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000021056 liquid food Nutrition 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000005068 transpiration Effects 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Biological Depolymerization Polymers (AREA)
Description
Use of polyester resins for the production of articles having good properties as barriers to water vapour
The present invention relates to the use of biodegradable polyester resins in the production of formed articles having good properties as barriers to water vapour.
The water-vapour barrier properties of biodegradable polymers develcped in recent years are guite poor.
For example, polyesters such as polyvhydroxybutyrate- valerate, polylactic acid, polyglycolic acid, polycaprolactone, polybutylene succinate, copolymers such as polybutylene adipate-co-terephthalate, polyester-amides such as polybutylene adipate-co-caprolactam, polyvinyl alcohol, ethylene-vinyl alcchol copolymers, polyesters-urethanes, and esters of cellulose and regenerated cellulose have permeabilities to water vapour greater than 300 gx30um/m’ per day at 38°C and 90% relative humidity (RH) (Lyssy method).
The poor barrier properties can be related to the fact that these polymers have good biodegradability which, in order for the bacterial action to be performed advantageously, means that the polymer should be wettable and hence contains polar groups in its structure with a consequent reduction in its water-vapour barrier properties since the polar groups increase the solubility of water in the polymer and hence its permeability to water vapour.
High permeability to water vapour considerably limits the fields of use of biodegradable polymers such as the above- mentioned aliphatic polyesters or copolyesters, particularly where good biodegradability and low permeability to water would be very desirable.
CONFIRMATION COPY
~.
Fields of use in which there 1s a particular need for biodegradable materials having good water-vapour barrier properties are, for example, the hygiene field (so-called non-breathable nappies, that is to say, nappies with a low transpiration value, similar to the nappies which are in use with a backsheet of polyethylene and non-woven polypropylene fabric), multi-layer and non-multi-layer food packaging pased on laminated milk cartons, mulching of soils where the evaporation of water through materials is to be as limited as possible, containers for soil for growing plants in greenhouses, sacks for collecting grass cuttings which require reduced biodegradation rates by virtue of a lower wettability of the biodegradable film of which the sack is made, non-woven, fabric which can provide a dry feel for nappies, fishing nets which must not undergo significant alterations due to water during the period of use, expanded products for packaging which requires moisture protection whilst remaining biodegradable, irrigation pipes for agriculture, products in contact with liquid foodstuffs, such as fast-food cups, plates and drinking straws, expanded 's trays for foodstuffs, blister packs for pharmaceutical products, nursery plant-pots through which moisture must not be able to pass and which must have a degradation process which does not interfere with the growth of the plants, hygiene products such as colostomy bags and the like, or blood containers, fibres for disposable products which can withstand water and a few washings, for disposable hosiery and garments, etc.
Tt has now been found, unexpectedly - in view of the outstanding permeability of aliphatic polyesters such as polybutylene adipate, polybutylene succinate, polyhexamethylene adipate and polybutylene adipate-co- terephthalate to water vapour - that the polyester resins defined below have good water-vapour barrier properties and,
at the same time, are sufficiently biodegradable in normal composting conditions and are therefore usable in applications in which such properties are required.
The polyester resins usable in the applications of the invention are formed by recurring units X = [O- (CHz) n—0CO- (CH) -CO] and/or Y = [0- (Ci) x—CO], where the na_f-sum of n + m is equal to or greater than 6 and k is a number equal to or greater than 6, or Dy copolymers comprising units and/or sequences having the fermula x. [0- (CHy) ni —OCO~ (CHz) niCO} 7 Yi (0- (CH) x3—CO] where: i,J = 1-5; ny = 2-22; my = 0-20; ks = 1=21; 5
Sx y= ist i=) and x: and y; vary between 0 and 1 and are molar fractions of the various units such that 5 5
IRC FEY } . ,=) 2 =) , or by recurring units
Z= [O- (CH) ,-0CO- (CHz),—CO} where a=2-3 and b=7-11, present in sufficient quantity to ensure good barrier properties and biodegradability of the resins in the production of products in which a permeability to water vapour of less than 350 gx30pm/m’ per day at 38°C and 90% RH and biodegradability in composting or burial cenditions are required.
The products which can be produced from the polyesters as defined above can ensure permeability to water vapour of less than 350, more particularly less than 300, gx30pm/m? per day at 38°C and 90% RH.
The biodegradability of the products during composting or burial is sufficient to bring about their decomposition within the required periods of time.
PCT/EP99/06333 . > 4
More particularly, in the case of the products produced from the preferred polyester resins, the biodegradability is less than 30% in one month and more than 60% in six months, in accordance with DIN 54900, part II, or decomposition on 30pm film of less than 10% in 14 days and more than 90% in 6 months, in accordance with the method described in "Journal of Environmental Polymer Degradation”, Vol. 4, No. 1, 1996, p. 55-63, or in accordance with the burial test described in "Biodegradable Plastics, Practices and Test Methods" ASTM
Subsection D-20.96.1 of mnvironmental Degradable Plastics,
Version 4.0 Dec. 6 1890.
The polyester resins usable according to the invention have a mean numeral ‘molecular weight greater than 10000 and a melting point (acceptable for industrial applications) of between 60 and 110°C.
Polyester resins with a mean numeral molecular weight of between 45000 and 70000 have been found particularly advantageous for use according to the invention.
There is not the slightest reference in the literature either to the barrier properties, particularly to water vapour, of the polyester resins falling within the general formula given above, Or to their good biodegradability by decomposition.
The use of the above-mentioned polyester resins in applications which require a low permeability to water vapour (below the value indicated above) combined with a biodegradability during composting compatible with the standards in use is novel and constitutes the subject of the rresent invention.
Examples of applications in which the polyester resins according to the invention are particularly useful are: - coatings produced by extrusion-coating with good water- barrier properties, particularly for the packaging of fresh milk and diary products, of meat, and of foods with high water content, - multi-layer laminates with layers cf paper, plastics material or paper/plastics material, aluminium and metallized films in general, - films as such, and multi-layer films with other polymer materials, - sacks for organic refuse and for grass cuttings with periods of use longer than 1 week, - single-layer and multi-layer food packaging, particularly containers for milk, yoghurt, cheeses, meat and beverages, in which the layer in contact with the food or beverage is formed by the polyester, - composites with gelatinized starch, destructured starch, native starch in the form of a filler, or complexed starch, - mono-directional or bi-directional films, - semi-expanded and expanded products produced by physical and/or chemical means, by extrusion, injection, or agglomeration of pre-expanded particles, from materials constituted by the polyester as such, from blends, or from filled materials, - expanded sheet and expanded containers for foods, (fruit, vegetables, meat, cheeses) for drugs, and for fast-food, - fibres, fabrics and non-woven fabrics in the hygiene, sanitary and clothing fields, - outer non-woven fabric and/or film, front tapes for increasing the thickness of the backsheet in critical points, and adhesive strips, for the production of nappies, - composites with mineral and vegetable fillers with various form ratios,
PCT/EP99/06333 . 6 ~ —- extruded or thermoformed sheets and profiles in the field of food and fast-food packaging (drinking straws, cups, trays, etc.), - pottles for the food, cosmetics and pharmaceutical fields, - fishing nets, - containers for fruit and vegetables, - irrigation pipes in the agricultural field, - products precduced from plends with other biodegradable polymers (for example, polybutylene succinate, polycaprolactone, polyhydroxybutyrate-co-valerate, polyesters-amides, aliphatic-aromatic polyesters), for correcting the piodegradation rate, the processability, and/or the permeability to water of these latter polymers and the superficial properties such as migration phenomena of low molecular weight molecules, - products produced from blends with non-biodegradable polymers.
Polyesters falling within the general formula given above can be produced by the polycondensation, in accordance with ' known methods, of a bicarboxylic aliphatic acid with 2-22 carbon atoms with a diol with 2-22 carbon atoms, selected in a manner such that the hal f-sum of the carbon atoms relating to the acid and to the diol is egual to OIL: preferably greater than 6, more preferably equal to 7, or by polycondensation of hydroxy-acids with 7-22, preferably 8-22 carbon atoms, or by ring-opening of the corresponding lactones or lactides; or by polycondensation of ethylen glycol with azelaic and sebacic acid.
Aliphatic-aromatic copolyesters, aliphatic-polyamide copolyesters, aliphatic-ether copolyesters, aliphatic-urea copolyesters or linear or pranched urethanes in which the fraction of the aliphatic polyesters of the copolymers have the structure given above, and also blends of these v PCT/EP99/06333 ; polyester resins with unmodified or modified polysaccharides, with water-vapour barrier properties of the type defined above, also fall within the scope of the invention.
Examples of picarboxylic acids usable are succinic, adipic, pimelic, suberic, azelalic, sepacic, brassilic, urdecandioic and dodecandioic acids, and dimeric acids; examples of hydroxy-acids which may be used are glycolic, hydroxybutyric, hydroxypropionic, hydroxycaproic, nhydroxyvaleric, 7-hyroxyheptanoic, g§-hydroxyoctanoic, 9- hydroxynonoic, 10-hydroxydecanoic and 13-hydroxy- tridecancarboxylic acids.
Examples of diols which may be used are 1,2-ethandiol, 1,4- butandiol, 1, 6-hexandiol, 1, 7-heptandiol, 1, 8-octandiol, 1,9-nonandiol, 1,10~decandiol, 1,12-dodecandiol, 1,4- cyclohexandimethylol and 1,4-cyclohexandiol.
Diacids and dialcohols which come from renewable sources and which can be produced from fatty acids such as cleic and ricinoleic acids are preferred.
When the diol has less than 7 carbon atoms, the acid has a number of carbon atoms such that the half-sum of the carbon atoms of the diol and of the acid is equal to or greater than 6, more preferably equal or higher than 7. The same criterion applies when the bicarboxylic acid has less than 7 carbon atoms.
The polycondensation is performed at temperatures of between 180° and 230°C in the presence of known catalysts based on transition and rare-earth metals such as tin, titanium, antimony, zinc, etc.
~.
In the case of copolymers formed by or containing units or sequences of units X and Y, the preparation is performed in accordance with known methods by polycondensation of the diacid and the diol in the presence of the preselected lactone or lactide.
The mean numeral molecular welght obtainable by polycondensation may go up to values of the order of 100000 put it is preferably kept between 45000 and 70000.
Mean numeral molecular weights of less than 10000 do not permit the production of products having mechanical properties of practical interest.
The molecular weight can be increased by post-condensation reactions, operating either in the fused state or in the solid state, in the presence of pelyfunctional compounds having groups reactive with the terminal -OH groups of the polyester, such as aliphatic or aromatic diisocyanates.
For post-condensation reactions (upgrades) in the solid state, the reaction is carried out by placing the solid resin in granular form in contact with the polyfunctional compound at ambient temperature or at a temperature slightly below the melting point of the resin for a period of time sufficient to bring about the desired increase in molecular weight.
The polyfunctional compound is used in the molten state, or dispersed homogeneously On the solid resin. preferably, however, it is mixed with the resin in the fused state, for example, in an extruder, with periods of less than 5 minutes spent in the extruder to prevent undesired cross-linking reactions.
J PCT/EP99/06333
The intrinsic viscosity (measured in chloroform at 25°C) is increased even beyond 1 dl/g. preferably, it 1s brought to values greater than 0.7 dl/g and most preferably between 0.8 and 2.5 dl/g. The viscosity of the resin in the fused state after upgrading is generally between 2000 and 30000
Pas measured at 180°C and with a "shear rate" of 1C0 sec”.
Diisocyanates are the preferred polyfunctional compounds acting as chain extenders; they are used in sufficient guantity to react with the terminal -OH groups of the resin.
The quantity 1s between 0.2 and 1 equivalent of -NCO isocyanic groups per -0H group cf the resin.
The quantity, expressed by weight, is generally between 0.01 and 3% of the resin, preferably between ¢.1 and 2%.
The preferred diisccyanates are hexamethylene diisocyanate, diphenylmethane diisocyanate and isophorone diisocyanate.
Examples of other polyfunctional compounds which may be used are epoxides such as epoxy ethane, and the dianhydrides of tetracarboxylic aromatic acids sucn as pyromellitic anhydride.
The dianhydrides and the epoxides are also generally used in quantities of petween 0.01 and 2% by weight of the resin.
The following examples are provided by way of non-limiting illustration of the invention.
Example 1
A polybutylene sebacate film having an intrinsic viscosity of 1.26 measured at 0.2 g/dl in chloroform at 25°C (produced by polycondensation of cebacic acid with 1,4-butandiol) was
~~ used for the production of organic refuse sacks, bags for growing plants in greenhouses with metering of micro- nutrients, mulching films, bags for vegetables and tubers which do not sweat, or for other specific applications in which a low permeability to water vapour 1s required. The permeability to water vapour of this film was 250 gx30pm/m’ per day at 38°C and 90% RH.
The film for the different applications has been produced using a Ghioldi machine for film-blowing of 40mm of diameter and L/D= 30, a temperature of 125C and 60 rpm. The head of 100mm was cooled with air at 10C.
The polymer was also found particularly suitable for the production of products which are to come into contact with liquid foods, such as thermoformed cups, drinking straws and plates for fast-food.
In case of thermoformed sheets the sheets have been produced with a mono screw extruder of 30 mm of diameter and L./D=30, using a flat head of 20cm of width. The extrusion \ temperature was of 130C, the thickness was of 700 microns.
The sheet has been thermoformed at g0C in a round cup. In case of drinking straws a MAI machine was used of 60mm of diameter and L/D=25. The productivity at 150C was comparable with the one of polyethylene.
Example 2
A polyhexamethylene sepacate film having an intrinsic viscosity of 0.7 dl/g (produced by polycondensation of sebacic acid with 1, 6-hexandiol and subsequent upgrading with 1,6-hexamethylene diisocyanate at 60°C to give an intrinsic viscosity of 1.3 d1/g) was used for the production of organic refuse sacks, bags for growing plants in
” WO bon2627 PCT/EP99/06333 greenhouses with metering of micro-nutrients, mulching films, bags for vegetables and tubers which do not sweat, Or for other specific applications in which a low permeability to water vapour is required as in example 1.
The permeability to water vapour of this film was 180 gx30pum/m? per day at 38°C and 90% RH.
Example 3
Polyhexamethylene sebacate having an intrinsic viscosity of 1.3 dl/g was used for the production of single-layer and multi-layer films and sheets and for the production of containers for foods and drinks. An HAAKE RHEOCORD machine was used with a diameter of 19mm and L/D=25. The flat head had a width of 10cm. The molten film was calandered on cardboard in order to obtain an extrusion coated product fer food containers.
Comparison Example 1
Polyhexamethylene adipate was used for the production of films the permeability of which was 700 gx30um/m? per day at 38°C and 90% RH.
Example 4
The barrier properties of the following polymers were measured: polyethylenesebacate polynonandiol sebacate, polydecandiol sebacate, polyoctandiol azelate, polyoctandiol brassilate.
The barrier properties, expressed as permeability to vapour in gx30um/m? per day (measured with a Lissy 180-4000 vapour
PCT/EP99/06333 . bY 12 permeability tester at 38°C and 90% RH) were 300, 109, 10GC, 168, and 98, respectively.
The biodegradation pehaviour according to the method described in “Journal of Environmental Polymer Degradation” vol. 4, N1, 1996, p55-63 for all the polymers fell inside the range of less than 10% of biodegradation in 14 days and more than 90% in 6 months.
Claims (1)
- SR ———— 50-10-2000 EP 009906333 ¢ Pa Co CLATMS1. Use of compositions comprising, in quantities sufficient to ensure the required performance, polyester resins with mean numeral molecular weights greater than 10000 formed by recurring units X = [0-(CH,),-0CO-(CH,),-CO] and/or Y = [0-(CH,),-CO], where the half-sum of n + m is equal to or greater than 6 and k is a number equal to or greater than 6, or by copolymers comprising units and/or sequences having the formula x,[0- (CH,),-0CO-(CH,),;~-COl; vy; [O-{(CH,)4-COl] where: 1,7 - 1-5; n, = 2-22; my = 0-20; ky = 1-21; s 5 PIEEDIWES! 1=1 =! and x; and y; vary between 0 and 1 and are molar fractions of the various units such that IEE Ca BS SPN 1=1 “ = ’ or by recurring units 32=[0- (CH,),-OCO- (CH,)b-CO] where a=2-3, b=7-11, present in sufficient quantity to ensure good barrier prop- erties and biodegradability of the resins for the manufac- ture of articles having a permeability to water vapour of ’ less than 350 gx30um/m* per day at 38°C and 90% RH, said ar- : ticles showing decomposition in composting conditions on 30pm £ilm of less than 10% in 14 days and more than $0% in six months.2. Use according to Claim 1, in which the polyester resins : have a melting point of between 60 and 110°C.3. Use according to Claim 1, in which the polyester resin AMENDED SHEETBE mm EE — T_T, 20-10-2000 EP 0089906333 F) 14 : is produced by polycondensation of bicarboxylic aliphatic acids with from 2 to 22 carbon atoms and of diols with from 2 to 22 carbon atoms, selected in a manner such that the half-sum of the number of carbon atoms relating tc the acid and to the diol is greater than 6, or by polycondensation of hydroxy-acids, or by ring-opening of corresponding lac- tones or lactides having from 7 to 22 carbon atoms.4. Use according to Claim 1, in which the diacids and the dialcohols are obtained from renewable sources.5. Use according to any one of the preceding claims, in which the polyester resin is selected from polyethylene se- bacate, polybutandiol sebacate, polyhexandicl azelate, po- lvhexandiol sebacate, polynonandiol azelate, polynonandiol sebacate, polyoctandiocl azelate, polyoctandicl brassilate, : polydecandiol sebacate and polydecandiol brassilate.6. Use according to any one of the preceding claims, in : which the polyester resin has an intrinsic viscosity greater than 0.7 dl1/g in chloroform at 25°C. .7. Use according to any one of the preceding claims, in which the polyester resin is subjected to an upgrading pro- cess.8. Use according to any one of the preceding claims, in which the polyester resin is a component of a blend of un- modified or modified polysaccharides.9. Use according to any one of the preceding claims, in AMENDED SHEET20-10-2000 Co } EP 009906333 : which the polyester resin contains mineral or vegetable fillers and/or additives selected from lubricants, plasti- cizers, cclourings, flavourings, perfumes, flame-proofing agents,. stabilizers with regard to hydrolysis and to ther- mal degradation, and antioxidants.10. Use according to any one of the preceding claims, in which the mean numeral molecular weight of the polyester resin is between 45000 and 70000.11. Use according to Claim 1 wherein said articles are se- lected from: - coatings which are produced by extrusicn-coating, with water-vapour barrier properties, and which are usable for the packaging of fresh milk and dairy products, of meat, and of foods having high water content, - multi-layer laminates with layers of paper, plastics material or paper/plastics material, aluminium and metal- lized films, - films as such and multi-layer films with other poly- mer materials, - sacks for organic refuse and for grass cuttings with periods of use longer than 1 week, - single-layer and multi-layer food packaging compris- ing containers for milk, yoghurt, cheeses, meat and bever- ages, in which the layer in contact with the food or bever- age is formed by the aliphatic polyester, } - composites with gelatinized or destructured starch, and/or complexed starch or natural starch as a filler, - mono-directional and bi-directional £ilms, - semi-expanded and expanded products produced by AMENDED SHEET20-10-2000 bo EP 009206333 v physical and/or chemical means, by extrusion, injection, or agglomeration of pre-expanded particles, - expanded sheet and expanded containers for foods, for drugs, and for fast food, ~ fibres, fabrics and non-woven fabrics in the hy- giene, sanitary and clothing fields, - composites with mineral and vegetable fillers, - thermoformed sheets for the food or fast-food pack- aging fields, . - bottles for the food, cosmetics and pharmaceutical fields, - fishing nets, - containers for fruit and vegetables, - extruded sections usable in the fast-food field and irrigation pipes in the agricultural field.12. Use of polyester resins as defined in Claim 1 in blends : with other biodegradable polymers having a permeability to water vapour greater than 300 gx30um/m’ per day at 38°C and 90% RH.13. Use of polyester resins as defined in Claim 1 in blends ' with polylactic acid.14. Use of polyester resins as defined in Claim 1 in blends with other non-biodegradable polymers, the said polymers having a permeability to water vapour of less than 300 gx30um/m* per day at 38°C and 90% RH. AMENDED SHEET18. Products according to Claim 16 in the form of extruded films and non-woven fabrics for nappies, films for agricultural mulching, bags for special soil for plants to be grown in greenhouses, coextruded products formed by one or more layers, thermoformed and blown products for holding foodstuffs, and expanded products.19. Products which are used in uses in wnich a permeability to water vapour of less than 350 gx30um/m® per day at 38°C and 90% RH and biodegradability in composting and/or burial conditions are required, and which are produced from polyester resins in blends with other polymers as defined in Claim 13 or Claim 14 or 15.20. Products according to claim 19, in film, fibre, or sheet form, or in the form of extruded sections, or injection- moulded, moulded, or expanded products, Or of non-woven fabrics.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT98TO000729 IT1303548B1 (en) | 1998-08-28 | 1998-08-28 | Use of compositions with polyester resins formed by specified recurring units, sequences or specified copolymers in making articles having excellent water barrier properties |
Publications (1)
Publication Number | Publication Date |
---|---|
ZA200102221B true ZA200102221B (en) | 2001-09-18 |
Family
ID=11417005
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
ZA200102221A ZA200102221B (en) | 1998-08-28 | 1999-08-27 | Use of polyester resins for the production of articles having good properties as barries to water vapour. |
Country Status (2)
Country | Link |
---|---|
IT (1) | IT1303548B1 (en) |
ZA (1) | ZA200102221B (en) |
-
1998
- 1998-08-28 IT IT98TO000729 patent/IT1303548B1/en active IP Right Grant
-
1999
- 1999-08-27 ZA ZA200102221A patent/ZA200102221B/en unknown
Also Published As
Publication number | Publication date |
---|---|
ITTO980729A1 (en) | 2000-02-28 |
IT1303548B1 (en) | 2000-11-14 |
ITTO980729A0 (en) | 1998-08-28 |
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