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WO2000063282A1 - Composition de resine pour films biodegradables utilises en agriculture et presentant une meilleure resistance aux intemperies - Google Patents

Composition de resine pour films biodegradables utilises en agriculture et presentant une meilleure resistance aux intemperies Download PDF

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Publication number
WO2000063282A1
WO2000063282A1 PCT/EP2000/003380 EP0003380W WO0063282A1 WO 2000063282 A1 WO2000063282 A1 WO 2000063282A1 EP 0003380 W EP0003380 W EP 0003380W WO 0063282 A1 WO0063282 A1 WO 0063282A1
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WO
WIPO (PCT)
Prior art keywords
weight
parts
aliphatic
film
bifunctional
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.)
Ceased
Application number
PCT/EP2000/003380
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English (en)
Inventor
Shoichi Satani
Akira Nishikata
Hirofumi Okuno
Hideaki Hashimoto
Nobuaki Wada
Shigeo Sano
Michael Voigt
Ralf Timmermann
Wolfgang Schulz-Schlitte
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
CI Kasei Co Ltd
Original Assignee
Bayer AG
CI Kasei Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG, CI Kasei Co Ltd filed Critical Bayer AG
Priority to IL14566600A priority Critical patent/IL145666A0/xx
Priority to KR1020017013140A priority patent/KR20020000800A/ko
Priority to EP00925213A priority patent/EP1173507A1/fr
Priority to AU44007/00A priority patent/AU4400700A/en
Publication of WO2000063282A1 publication Critical patent/WO2000063282A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • Resin composition for biodegradable agricultural films with enhanced weather- ability is provided
  • the present invention relates to a biodegradable resin composition and films and sheets made thereof with improved heat resistance and weather resistance when used as final products in outdoor applications while maintaining excellent biodegradability and compostability.
  • the products are used in the fields of agriculture, packaging and civil engineering such as a mulch film, polytunnel, greenhouse, masking film, riverbed sheet, stretch film for pallets, and silage film.
  • Biodegradable aliphatic polyester resins of the poly(hydroxyalkanoate) type such as poly(hydroxybutyrate) are known for a long time but have the drawback of poor flexibility and transparency (WO-A 9407940, WO-A 9923161). Also well known is polylactide with good transparency but poor flexibility (JP-A 07206773).
  • Aromatic- aliphatic copolyesters (WO-A 9615173, WO-A 9615174, WO-A 9615175, WO-
  • a 9615176 and aliphatic copolyester resins of the poly(alkylenedialkanoate) type also have the drawback of poor transparency.
  • Blends and compounds based on starch and polyester resins are well known in the art as biodegradable resins (WO-A 201743, WO-A 9631561) but have the drawback of poor transparency and poor resistance against water and changes of humidity.
  • Polyesteramides are also known (EP-A 641 817) as versatile materials appropriate for manufacturing flexible, transparent and water resistant films but are still poor in weatherability.
  • One of the methods for preventing weeds from budding without spraying any herbi- cides as well as saving the labor of manually removing the weeds is to cover the rice field with a mulch film.
  • biodegradable films based on starch-containing ma- terials with the drawback of missing water resistance a multi-sheet of paper also has been used. While the multi-sheet of paper also requires no withdrawal or disposal after use since it is biodegradable by leaving it alone after completing cultivation, thick layers have to be applied in order to maintain enough tear resistance even in wet conditions.
  • Another drawback of paper mulch is the poor flexibility which makes it hard to apply. No agricultural films simultaneously satisfying biodegradability, flexibility, tensile strength, extension and tear strength, transparency, cloud preventive property, durability, heat and water resistance have been reported yet.
  • the object of the present invention is to provide a composition for manufacturing films and sheets having adjustable biodegradability, satisfactory flexibility, tensile strength, extension and tear strength, transparency, cloud preven- tive property, durability, heat and water resistance by taking advantage of specified biodegradable resins and combinations thereof.
  • the present invention provides a biodegradable resin composition
  • a biodegradable resin composition comprising at least one stabilizing additive selected from the groups of antioxidants (a), of radical scavenging light stabilizers (b), UV and visible light absorbing compounds (c), and quenchers of photochemical excited states (d).
  • the biodegradable resin composition stabilized with at least one of the aforementioned stabilizing compounds provides a set of materials that can be easily processed to manifold mono- and multilayer film and sheet applications while providing a markable weatherability as well as an enhancement of durability in outdoor applications. For adopting the material to specific applications, e.g.
  • the biodegradable resin comprises at least one biodegradable polymer selected from the group consisting of aliphatic (co)polyesters, aromatic-aliphatic (co)polyesters, aliphatic polycarbonates, aromatic-aliphatic polycarbonates, aliphatic polyester-ure- thanes, partly aromatic polyester-urethanes, aliphatic polyesteramides, aliphatic-aromatic polyesteramides, polyetheresteramides, polysaccharide esters, polysaccharide ether esters such as cellulose or starch derivatives or copolymers and/or mixtures thereof.
  • the following polymers are preferably suitable:
  • A) aliphatic bifunctional alcohols preferably linear C2 to C ⁇ 0 -dialcohols, such as, for example, ethanediol, butanediol or hexanediol, particularly preferably butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably having 5 or 6 C atoms in the cycloaliphatic ring, such as, for example, cyclo- hexanedimethanol, and/or instead of some or all of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol or tetrahydro- furan or copolymers thereof having molecular weights of up to 8,000, pref- erably up to 4,000, and/or optionally small amounts of branched bifunctional alcohols, preferably C ⁇ -C ⁇ -alkyldiols, such as, for example, neopentylg
  • C) aliphatic bifunctional alcohols preferably linear C 2 to C j o-dialcohols, such as, for example, ethanediol, butanediol or hexanediol, particularly preferably bunaediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably with a C5 ⁇ or Cg-cycloaliphatic ring, such as, for example, cyclohexanedi- methanol, and/or, instead of some or all of the diols, monomeric or oligo- meric polyols based on ethylene glycol, propylene glycol or tetrahydrofuran or copolymers thereof having molecular weights of up to 4,000, preferably up to 1,000, and/or optionally small amounts of branched bifunctional alcohols, preferably C ⁇ -C ⁇ -alkyldiols, such as, for example, neopentylglycol, and
  • D) building blocks with acid and alcohol functional groups preferably having 2 to 12 C atoms, for example hydroxybutyric acid, hydroxyvaleric acid or lactic acid, or derivatives thereof, for example a-caprolactone or dilactide, or a mixture and/or a copolymer ofC and D, the aromatic acids making up a content of not more than 50 wt.%, based on all the acids,
  • tetramethylene diisocyanate hexamethylene diisocyanate or isophorone diisocyanate
  • optionally additionally with linear and/or branched and/or cycloaliphatic bifunctional alcohols and/or alcohols of higher functionality preferably C3-Ci2-alkyldi or -polyols, or 5 to 8 C atoms in the case of cycloaliphatic alcohols, e.g.
  • ethanediol hexanediol, butanediol or cyclohexanedimethanol, and/or optionally additionally with linear and/or branched and/or cycloaliphatic bifunctional amines and/or amino alcohols and/or amines and/or amino alcohols of higher functionality, having prefera- bly 2 to 12 C atoms in the alkyl chain, e.g. ethylenediamme or aminoethanol, and/or optionally further modified amines of alcohols, such as, for example, ethylenediaminoethanesulfonic acid, as the free acid or as a salt,
  • ester content C) and/or D) being at least 75 wt.%, based on the sum of C), D) and E).
  • aliphatic bifunctional alcohols preferably linear C2 to C 10 -dialcohols, such as, for example, ethanediol, butanediol or hexanediol, particularly preferably butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably having 5 to 8 C atoms in the cycloaliphatic ring, such as, for example, cyclohexanedimethanol, and or instead of some or all of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol or tetrahydro- furan or copolymers thereof having molecular weights of up to 4,000, preferably up to 1,000, and/or optionally small amounts of branched bifunctional alcohols, preferably with C 2 -Ci2-alkyldicarboxylic acids, such as, for example, neopentylglycol, and additionally optionally small amounts
  • aromatic acids making up a content of not more than 50 wt.%, based on all the acids
  • ester content F) and/or G) being at least 70 wt.%, based on the sum of F
  • aliphatic bifunctional alcohols preferably linear C 2 -C ⁇ o-dialcohols, such as, for example, ethanediol, butanediol or hexanediol, particularly preferably butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably having 5 to 8 C atoms, such as, for example, cyclohexanedimethanol, and/or, instead of some or all of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol or tetrahydrofuran or copolymers thereof having molecular weights of up to 10,000, preferably up to 8,000, particularly preferably up to 5,000, and/or optionally small amounts of branched bifunctional alcohols, preferably such as, for example, neo- pentylglycol, and additionally optionally small amounts of alcohols of higher functionality, preferably such as, for example, 1,
  • K building blocks with acid and alcohol functional groups, preferably having 2 to 12 C atoms in the carbon chain, for example hydroxybutyric acid, hydroxyvaleric acid or lactic acid, or derivatives thereof, for example a-cap- rolactone or dilactide,
  • the ester content I) and/or K) being at least 30 wt.%, based on the sum off), K), L) and M), and preferably the weight content of the ester structures is 30 to 70 wt.% and the content of the amide structures is 70 to 30 wt.%.
  • Preferred embodiments are aliphatic (co)polyesters, aromatic-aliphatic (co)poly- esters, polyetheresteramides and/or aliphatic polyesteramides with the aliphatic poly- esteramides being most preferable.
  • the polyesteramide resin to be used in the present invention has a mean molecular weight of 10,000 to 300,000, preferably 20,000 to 150,000.
  • the antioxidant (a) is at least one selected from the group of hindered phenol based compounds (al) and/or phosphite and or phosphonite ester based compounds (a2) and/or a sulfur containing synergists in antioxidation (a3).
  • the light stabilizer (b) is at least one selected from the hindered amine based light stabilizers, preferably a high molecular weight oligomer or polymer compound comprising at least two re- peating units.
  • the UV-absorber (c) is at least one selected from the group of benzophenones, benzotriazoles, benzylidene malonates, oxanilides, benzoaxazinones or triazines, preferred benzophenones, benzotriazoles.
  • the quencher (d) is selected from the metal organic compounds.
  • the invention relates to a resin composition wherein 0 - 1,0 preferred 0,1 to 0,8 parts by weight of c),
  • the above selection is not limited to compounds providing only one stabilizing mechanism but includes compounds comprising chemically different functional groups each acting as stabilizers but following different mechanisms. Combinations of different stabilizers being selected from only one of the groups (a) to (d) may be applied as well as combinations across those groups.
  • hindered phenol based compounds (al) to be used in the present invention are octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentadecyl-3- (3-t-butyl-5-methyl-4-hydroxyphenyl)propionate, triethyleneglycol-bis[3-(3-t-butyl- 5-methyl-4-hydroxyphenyl)propionate], l,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hy- droxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxy- phenyl)propionate], l,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)- benzene, N,N-hexam
  • Examples of the phosphite and or phosphonite ester based compounds (a2) to be used in the present invention are 2,2-methylenebis[(4,6-di-t-butylphenyl)octylphosphite, tris(2,4-di-t-butylphenyl)phosphite, 1 , 1 ,3-tris(2-methyl-4-ditridecylphosphite-5-t- butylphenyl)butane, dinonylphenyl pentaerythritol diphosphite, distearyl pentaery- thritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol di-phosphite, bis(2,6-di-t- butyl-4-methylphenyl) phosphite, pentaerythritol di-phosphite, diphenyl
  • Examples of the sulfur containing compounds (a3) are didodecyl 3,3'-thiodipropion- ate, di(tridecyl) 3,3'-thiodipropionate, and dioctadecyl 3,3'-thiodipropionate.
  • radical scavenging light stabilizer (b) to be used in the present invention are poly[(6-morpholino-s-triazine-2,4-diyl)[2,2,6,6-tetramethyl-4- piperidyl)imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]], the polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl-l,6-hexanediamine with mor- pholine-2,4,6-trichloro-l,3,5-triazine, poly ⁇ [6-(l,l,3,3-tetramethylbutyl)amino-l,3,5- triazin-2,4-diyl]-[(2,2,6,6-tetramethyl-piperidyl)imino]hexamethylene [(2,2,6,6- tetramethyl-piperidyl)imino]>, poly ⁇
  • UV-absorbers (c) examples of the UV-absorbers (c) being used in the present invention are 2-hydroxy-
  • An examples of a quencher (d) being used in the present invention is [2,2'-thio-bis(4- t-octylphenolato)]-n-butylamine nickel(II).
  • the anti-clouding agent (e) being used in the present invention is selected from the groups of partial esters of a polyfunctional alcohol or from the group of the conden- sation products of the polyfunctional alcohol with a higher fatty acid.
  • the cloud preventive agents include, for example, a sorbitane based surfactant such as sorbitan monostearate and sorbitan monopalmitate, a glycerine based surfactant such as glycerine monopalmitate and diglycerine monopalmitate, and a polyethylene glycol based surfactant such as polyethyleneglycol monostearate, polyethylene glycol monopalmitate and polyethylene glycol alkylphenyl ether, a trimethylol propane based surfactant and a pentaerythritol based surfactant, and an isomer or an alkylene oxide addition compound thereof.
  • Examples of the anti-fogging agent (f) being used in the present invention and pre- venting fog from generating in the vicinity of house cover films are fluorinated surfactants or silicone based surfactants.
  • the present invention provides a biodegradable film, preferred agricultural film in which at least one of the additives (a) to (f) are blended into a resin composition mainly composed of a biodegradable resin which is preferably an aliphatic polyester and/or copolyester and/or an aromatic-aliphatic copolyester and/or an aliphatic polyesteramide with the aliphatic polyesteramide being the most preferred one.
  • a biodegradable resin which is preferably an aliphatic polyester and/or copolyester and/or an aromatic-aliphatic copolyester and/or an aliphatic polyesteramide with the aliphatic polyesteramide being the most preferred one.
  • the biodegradable resin composition is prepared by blending relative to 100 parts by weight of the composition 0.03 to 1.2 parts by weight, preferably in the range of 0.05 to 1.0 parts by weight of an antioxidant (a), more preferably a hindered phenol based compound (al) and/or a phosphite and/or phosphonite ester (a2). It is not preferable that these ratios are smaller than the range described above, since heat stability tends to be decreased. It is also not preferable that the ratios are larger than the range described above, since appearance of the molded product is liable to be poor, or the product cost may be increased.
  • an antioxidant a
  • a a hindered phenol based compound
  • a2 phosphite and/or phosphonite ester
  • the biodegradable resin composition may also comprise a hindered amine based light stabilizer (b) in an amount of 0.03 to 1.0 parts by weight, preferably in the range of 0.05 to 0.8 parts by weight, relative to 100 parts by weight of the composition.
  • a hindered amine based light stabilizer b
  • the blending amounts of lower and higher than the ranges described above are not preferable, since weather resistance is decreased in the former case, and appearance of the product becomes poor or the production cost tend to increase in the latter case.
  • the biodegradable resin composition may also comprise an UV-absorber (c) preferably a benzophenone and or a benzotriazole in an amount of 0.01 to 1.0 parts by weight, preferably in the range of 0.05 to 0.5 parts by weight, relative to 100 parts by weight of the composition.
  • an UV-absorber preferably a benzophenone and or a benzotriazole in an amount of 0.01 to 1.0 parts by weight, preferably in the range of 0.05 to 0.5 parts by weight, relative to 100 parts by weight of the composition.
  • biodegradable polymer materials may be added to the formulation as described above in a range not inhibiting the effect of the present invention. It is also possible to add additives and reforming agents such as a sulfur based antioxidant (a3), a Ni based quencher (d), an anti-clouding agent (e), an anti-fogging agent (f), a plasticizer, filler, lubricant, reinforcing agent, inorganic heat insulator, antifungal agent, pigment and fluorescent substance in order to control forming ability and other properties of the film and sheet.
  • additives and reforming agents such as a sulfur based antioxidant (a3), a Ni based quencher (d), an anti-clouding agent (e), an anti-fogging agent (f), a plasticizer, filler, lubricant, reinforcing agent, inorganic heat insulator, antifungal agent, pigment and fluorescent substance in order to control forming ability and other properties of the film and sheet.
  • the thickness is usually in the range of 15 to 1000 ⁇ m, preferably in the range of 20 to 500 ⁇ m.
  • the preferred composition of the biodegradable resin comprises a blend of a biodegradable polyesteramide, preferably an aliphatic polyesteramide, and a biodegradable polyester, preferably an aliphatic polyester. It was found that the polyester present in these blends provided a diffusion barrier for water migrating into the polyesteramide phase. Thus photochemical initiation and photochemical formation of reactive species being responsible for chain scission reactions where water is actively involved in the reaction mechanism are markably retarded.
  • the preferred resin composition being used for transparent agricultural films and sheets comprises 60 to 95 parts by weight of the polyesteramide and 5 to 40 parts by weight of the aliphatic polyester.
  • the amount of the hindered amine based light stabilizer being added to this composition is in the range of 0.03 to 1.0 parts by weight, preferably in the range of 0.05 to 0.5 parts by weight.
  • the blending amount is smaller than the range described above, since weather resistance tends to decrease while, when the amount is larger, appearance of the molded product is compromised or the production cost may be increased.
  • biodegradable polymer materials may be added to the formulation as described above in a range not inhibiting the effect of the present invention. It is also possible to add additives and reforming agents such as antioxidants (a), an UV-absorber (c), a Ni based quencher (d), an anti-clouding agent (e), an anti-fogging agent (f), a plasti- cizer, filler, lubricant, reinforcing agent, inorganic heat insulator, antifungal agent, pigment and fluorescent substance in order to control forming ability and other properties of the film and sheet.
  • additives and reforming agents such as antioxidants (a), an UV-absorber (c), a Ni based quencher (d), an anti-clouding agent (e), an anti-fogging agent (f), a plasti- cizer, filler, lubricant, reinforcing agent, inorganic heat insulator, antifungal agent, pigment and fluorescent substance in order to control forming ability and other properties of the
  • the film thickness is in the range of 20 to 200 ⁇ m, preferably in the range of 40 to 150 ⁇ m.
  • a resin composition comprising 60 to 100 parts by weight, preferably 80 to 100 parts by weight of the polyesteramide resin and 0 to 40 parts by weight, preferably 0 to 20 parts by weight of the aliphatic polyester resin.
  • the ratio of the hindered phenol based antioxidant (al) and/or phosphite and/or phosphonite ester based antioxidant (a2) is in the range of 0.01 to 1.0 parts by weight, preferably in the range of 0.03 to 0.5 parts by weight, relative to 100 parts by weight of the resin composition.
  • An amount of larger than 0.01 parts by weight of an antioxidant improves durability. However, a larger amount than 1.0 parts by weight is not preferable since appearance of the molded product is compromised or the production cost may be increased.
  • Hindered amine based light stabilizers (b) are added into the composition for manufacturing agricultural multilayer films of the biodegradable resin, if necessary.
  • the ratio of the hindered amine based light stabilizer (b) is in the range of 0.01 to 1.0 parts by weight, preferably in the range of 0.05 to 0.5 parts by weight relative to 100 parts by weight of the resin composition.
  • examples of the inorganic fillers and/or colorants to be used in the multilayer films include hydrophobic inorganic fillers such as silica, talc, clay, calcium carbonate, magnesium carbonate, titanium oxide and alumina; and inorganic and organic color- lants such as carbon black. The latter one being used for non-transparent mulching films only.
  • hydrophobic inorganic fillers such as silica, talc, clay, calcium carbonate, magnesium carbonate, titanium oxide and alumina
  • inorganic and organic color- lants such as carbon black. The latter one being used for non-transparent mulching films only.
  • These additives are blended in a range of 0.5 to 50 parts by weight, preferably in the range of 1 to 40 parts by weight, relative to 100 parts by weight of the resin composition.
  • biodegradable polymer materials may be added to the formulation as described above in a range not inhibiting the effect of the present invention. It is also possible to add additives and reforming agents such as an UV-absorber (c), a Ni based quencher (d), an anti-clouding agent (e), an anti-fogging agent (f), a plasticizer, filler, lubricant, reinforcing agent, inorganic heat insulator, antifungal agent, pigment and fluorescent substance in order to control forming ability and other properties of the film and sheet.
  • additives and reforming agents such as an UV-absorber (c), a Ni based quencher (d), an anti-clouding agent (e), an anti-fogging agent (f), a plasticizer, filler, lubricant, reinforcing agent, inorganic heat insulator, antifungal agent, pigment and fluorescent substance in order to control forming ability and other properties of the film and sheet.
  • the film thickness is in the range of 15 to 100 ⁇ m, preferably in the range of 20 to
  • multilayer films comprising combinations of materials with each layer having its specific function are developed.
  • the number of layers in the biodegradable multilayer film according to the present invention is not especially limited.
  • the film is composed of at least two layers in the order of, for example, (A)/(B), (B)/(A)/(B), (B)/(A')/(A)/(B) or (B)/(A')/(A)/(A')/(B).
  • the layer (A) has characteristics such as transparency, flexibility and expansion, while the layer (B) contributes to improvement of water resistance. Therefore, it is preferable that both outer layers of the biodegradable multilayer film according to the present invention are composed of the layers (B), and the layers (A) and (A') consti- tute the intermediate layers, in order to render characteristics of the biodegradable multilayer film to be excellent in transparency, flexibility and water resistance.
  • the substrate layer (A) mainly composed of a polyesteramide resin, preferably an aliphatic polyester resin, is prepared by blending the polyesteramide resin in a range of 50 to 100% by weight, preferably in a range of 60 to 95% by weight, and a biodegradable polyester resin, preferably an aliphatic polyester resin, in a range of 0 to 50% by weight, preferably in a range of 5 to 45% by weight.
  • a blending amount of the polyesteramide resin of less than 50% by weight is not preferable since transparency, flexibility and extension tend to decrease.
  • the blending ratios of the aliphatic polyester resin in the surface layer (B) are in the range of 60 to 100% by weight, preferably in the range of 75 to 100% by weight, and that of the polyesteramide resin is in the range of 0 to 40% by weight, preferably in the range of 0 to 25% by weight, respectively. It is not preferable that the blending ratio of the aliphatic polyester resin is less than 60% by weight since water resistance is deteriorated.
  • the thickness of the layer (A) is 50 to 90%, preferably 60 to 85%, of the overall thickness of the film.
  • the thickness of the layer (A) is less than 50%, flexibility and transparency becomes poor while, when the thickness exceeds 90%, water resistance of the layer tends to be poor due to reduced thickness of the layer (B).
  • biodegradable polymer materials may be added to the formulation as described above in a range not inhibiting the effect of the present invention. It is also possible to add additives and reforming agents such as antioxidants (a), UV-stabilizers (b), UV-absorbers (c), a Ni based quencher (d), an anti-clouding agent (e), an anti-fog- ging agent (f), a plasticizer, filler, lubricant, reinforcing agent, inorganic heat insula- tor, antifungal agent, pigment and fluorescent substance in order to control forming ability and other properties of the film and sheet.
  • the thickness of the multilayer film, formed by using the compositions for respective layers according to the present invention is usually in the range of 20 to 2000 ⁇ m, preferably in the range of 40 to 500 ⁇ m.
  • the biodegradable multilayer agricultural films according to the present invention may be composed of at least three layers.
  • the layer construction may be such as (A)/(B)/(C), (A)/(C)/(B')/(C) and (A)/(B)/(B')/(B")/(C).
  • the layer (A) has characteristics such as water resistance and dust preventive property, while the layers (B), (B') and (B") contribute for improving transparency, duration of cloud preventive property, and flexibility.
  • the layer (C) serves for maintaining and duration of some cloud preventive agent. Accordingly, the completely biodegradable multilayer agricultural film according to the present invention is excellent in the characteristics such as transparency, flexibility and cloud preventive property.
  • the blending ratio of the polyester resin is in the range of 60 to 100% by weight, preferably in the range of 75 to 95% by weight, and the blending ration of a polyesteramide resin, preferably an aliphatic polyesteramide resin, is 0 to 40% by weight, preferably 5 to 25% by weight. It is not preferable that the blending ratio of the polyester resin is less than 60% by weight, since water resistance is decreased.
  • the blending ratio of the polyesteramide resin is in the range of 50 to 100% by weight, preferably in the range of 60 to 95% by weight, and the blending ratio of the polyester resin is in the range of 0 to 50% by weight, preferably in the range of 5 to 40% by weight.
  • a cloud preventive agent (e) is blended relative to 100 parts by weight of the resin composition. It is not preferable that the blending ratio of the polyesteramide resin is less than 50% by weight, since duration of cloud preventive property, transparency, flexibility and extension tend to be decreased.
  • the blending ratio of the polyester resin is in the range of 60 to 95% by weight, preferably in the range of 70 to 90% by weight, and the blending ratio of the polyesteramide resin, preferably an aliphatic polyesteramide resin, is in the range of 5 to 40% by weight, preferably in the range of 10 to 30% by weight according to the present invention.
  • the cloud preventive agent (e) is blended. It is not preferable that the blending ratio of the polyester resin is less than 60% by weight, since water resistance becomes poor.
  • At least 5% by weight of the sub-component resins are blended to the principal com- ponent resin in at least one of the layer (A) or layer (B). It is not preferable that the blending ratio is smaller than the ratio described above, since adhesive property becomes poor.
  • the thickness of the layer (B) is 45 to 90%, preferably 55 to 80%, of the overall thickness of the film.
  • the thickness of the layer (B) of less than 45% results in poor flexibility, transparency and duration of cloud preventive property. It is not preferable, on the other hand, that the thickness exceeds 90%, since water resistance of the biodegradable agricultural film tends to deteriorate because the thicknesses of the water resistant layers (A) and (C) are reduced.
  • the preferable cloud preventive agent (e) to be blended in the layers (B) and (C) of the biodegradable multilayer agricultural film according to the present invention is a partial ester of a polyfunctional alcohol or a condensation product of the polyfunctional alcohol with a higher fatty acid.
  • a so-called fog preventive property may be provided by adding an anti-fogging agent (f) such as fluorinated surfactants and silicone based surfactant for preventing fog generating in the vicinity of the inner face of the house cover.
  • an anti-fogging agent such as fluorinated surfactants and silicone based surfactant for preventing fog generating in the vicinity of the inner face of the house cover.
  • f anti-fogging agent
  • silicone based surfactant for preventing fog generating in the vicinity of the inner face of the house cover.
  • weatherabihty stabilizers such as a hindered phenol based compound (al) and/or phosphite and/or phosphonite ester based compound (a2) are blended in the range of 0.03 to 1.2 parts by weight, preferably in the range of 0.05 to 0.8 parts by weight, relative to 100 parts by weight of the resin components in each layer.
  • a hindered amine based light stabilizer (b) is blended in the range of 0.03 parts by weight, preferably in the range of 0.05 to 0.5 parts by weight, relative to 100 parts by weight of the resin components in each layer. It is not preferable that the amount of blending is smaller than the proportion described above since weather resistance is deteriorated while, when the proportion is larger, appearance of the molded products is compromised or the production cost is increased.
  • biodegradable polymer materials may be added to the formulation as described above in a range not inhibiting the effect of the present invention. It is also possible to add additives and reforming agents such as sulfur containing synergists in antioxi- dantion (a3), UV-absorbers (c), a Ni based quencher (d), a plasticizer, filler, lubricant, reinforcing agent, inorganic heat insulator, antifungal agent, pigment and fluorescent substance in order to control forming ability and other properties of the film and sheet.
  • additives and reforming agents such as sulfur containing synergists in antioxi- dantion (a3), UV-absorbers (c), a Ni based quencher (d), a plasticizer, filler, lubricant, reinforcing agent, inorganic heat insulator, antifungal agent, pigment and fluorescent substance in order to control forming ability and other properties of the film and sheet.
  • the thickness of the multilayer film, formed with the compositions in each layer according to the present invention is usually in the range of 20 to 200 ⁇ m, preferably in the range of 40 to 150 ⁇ m.
  • inorganic particles are blended to the biodegradable resin composition the biodegradability of the respective films and sheets can be controlled.
  • the inorganic particles to be used in the present invention preferably include those having hydrophobicity such as silica, talc, clay, calcium carbonate, calcium sulfate, magnesium carbonate, titanium oxide and alumina. Blending the hydrophobic inorganic particles allows permeation of water and hydrolysis of the resin at the initial stage of decomposition to be enhanced, thereby accelerating overall biodegradation reaction.
  • the particle size is not limited, a larger specific surface area is preferable for enhancing collapse effects.
  • the blending ratio is 2.5 to 50 parts by weight, preferably 3.5 to 40 parts by weight relative to 100 parts by weight of the resin composition.
  • the content of the inorganic par- tides is less than 2.5 parts by weight, degradability is not enhanced while, when the content is larger than 50 parts by weight, physical properties of the molded body, for example tensile strength, is decreased to compromise practical applicability.
  • the provided film and sheet, and a molded body comprising the film or sheet having biodegradability obtained as described above can be obtained by hot molding methods such as vacuum molding and compressed air molding, which can be used for manufacturing a blister processing body, and a food cup and tray.
  • the film or sheet can be also used for manufacturing a box-type package by ruling for bending the sheet.
  • the resin composition can be also used for a sheet or molded body laminated with a sheet of paper and other plastic films.
  • the thickness is usually in the range of 15 to 1000 ⁇ m, preferably in the range of20 to 500 ⁇ m.
  • the biodegradable multilayer films described above are used in rice fields.
  • Herbicides have been sprayed in rice cultivation for preventing weeds from budding. Since the herbicides may adversely affect human bodies and may be an important factor of environmental pollution, there are some rice fields where agricultural chemicals such as herbicides are not used at all. However, manually removing the weeds cost a person so much labor that weed removing methods that can save man's labor with no effects on human bodies have been desired.
  • the present invention further provides a method for planting young rice plants com- prising spreading the multi-film of the biodegradable resin for use in rice fields according to the present invention over a rice field, and planting the young rice plant by piercing the multi-film.
  • the resin composition for this application mainly composed of a polyesteramide comprises additives such as a hindered phenol based compound (al) and/or a phos- phite and/or phosphonite ester based compound (a2), and an inorganic filler and/or a colorant.
  • additives such as a hindered phenol based compound (al) and/or a phos- phite and/or phosphonite ester based compound (a2), and an inorganic filler and/or a colorant.
  • the hindered phenol based compound (al) and or phosphite and/or phosphonite ester based compound (a2) are blended in the range of 0.01 to 1.0 parts by weight, prefer- ably in the range of 0.03 to 0.5 parts by weight, relative to 100 parts by weight of the resin components.
  • the amount of blending is larger than 0.01 parts by weight, durability can be improved. However, when the amount is too large, appearance of the molded products is compromised or results in cost-up of the product.
  • a hindered amine based light stabilizer (b) may be blended to the multi-film of the biodegradable resin for use in rice fields, if necessary.
  • the amount of the hindered amine based light stabilizer (b) is in the range of 0.01 to 1.0 part by weight, preferably 0.03 to 0.5 parts by weight, relative to 100 parts by weight of the resin component.
  • Example of inorganic fillers and/or colorants to be used in the present invention include hydrophobic inorganic fillers such as silica, talc, clay, calcium carbonate, magnesium carbonate, titanium oxide and alumina, and inorganic and organic colorants such as carbon black.
  • the amount of these additives is in the range of 0.5 to 50 parts by weight, preferably in the range of 1 to 40 parts by weight, relative to 100 parts by weight of the resin component.
  • the thickness of the film in this mulching application is usually in the range of 15 to 100 ⁇ m, preferably in the range of 20 to 50 ⁇ m.
  • biodegradable resin comprising the biodegradable polymers and additives (a) to (f) described above may be mixed during the extrusion process, it is recom- mended to previously formulate each ingredient before forming pellets.
  • the methods for formulating the resin components and various additives are not especially limited, but any methods that have been used for preparing conventional plastic compositions, for example heat-melting and kneading using a kneading machine such as a kneader, Banbury mixer and roll, a mixing machine such as ribbon blender and Hen- shel mixer, and uniaxial or biaxial extruder, may be used.
  • the biodegradable films according to the present invention are manufactured, for example, by forming a film by a conventional extrusion-molding such as a T-die method or inflation method, followed by cooling with a cooling roll, water or air. Use of a calendar molding is also possible.
  • Co-extrusion method is preferably used in producing the biodegradable multilayer film according to the present invention.
  • the layers are melt-extruded with plural extruders corresponding to the lamination number to laminate the molten resin by a conventional method such as a T-die method or inflation method, followed by cooling with a cooling roller, water or air.
  • Biodegradable films and sheets are produced as described from the composition according to the present invention above, and are used for various applications.
  • the present invention is not limited in any sense by the examples as set forth hereinafter. Measurements and evaluations in the examples were carried out under the fol- lowing conditions.
  • Samples were placed in Sunshine W.O.H by attaching an aluminum plate on the back face of each sample, and the time lapse before the samples are broken by being degraded in the environment was measured.
  • Samples were placed in a weatherometer SUN-WOM (made by Suga Test Machine Co. or by Gas Test Equipment Co.) and the time required for exhibiting weather deterioration of the samples was measured: 0 : 300 hours or more than ⁇ : 150 hours or more and less than 300 hours x: less than 150 hours
  • Double-adhesive tapes are attached to the aluminum frame so as to be able to sandwich the test sample with a pair of the aluminum frames.
  • test sample sandwiched with the aluminum frame is subjected to a biodegradation test.
  • a sealable vessel with an appropriate size is prepared (with a depth of 5 cm or more).
  • a commercially available compost is moisturized before use. Water is added to the compost not to pool in the bottom of the vessel, but so that water slightly seeps out of the compost by holding it with the fingers, which prescribed the standard test condition.
  • Biodegradation tests are carried out in the compost.
  • the test sample is set at a depth about 3 cm deep from the surface of the prepared compost. 2. After setting the test sample, it is placed in a sealed oven heated at 58°C to start the biodegradation test.
  • the lid of the oven is open at least once a day during the biodegrada- tion test, if possible, for spraying water in order to maintain the initial moisture content in the compost.
  • the sample during biodegradation is occasionally taken out of the oven and, after washing with water and wiping the moisture on the surface of the sample, it is weighed to calculate the biodegradation rate from mass changes.
  • the days required for 80% or more of weight loss of the sample in the bio- degradation test is defined to be the days for biodegradation.
  • O 40 days or more and less than 60 days
  • ⁇ 60 days or more and less than 80 days x: 80 days or more
  • Haze values represented by % were measured with a haze meter (made by
  • the film was extended over a water bath warmed at a temperature of 40°C with a tilt angle of 30 degree at an ambient temperature of 5°C. Cloudiness of the film was measured 30 days after based on the following evaluation criterion: O: Water drops covered 20% or less of the total film area. ⁇ : Water drops covered 20% or more and less than 50% of the total film area, x: Water drops covered more than 50% of the total film area.
  • This test sample is dipped in water warmed at 70 °C and, after cooling to room temperature, the sample films are peeled off with each other.
  • ⁇ The films experience some resistance, but can be peeled off with difficulty.
  • x The films are not peeled off at all.
  • the tensile elasticity modulus was measured according to ASTM D-882 (in kg/mm 2 unit). 11) Wrinkles and slacks of the moist film
  • Wrinkles and slacks of the film extended over the agricultural house are observed when the inside surface of the film is moist.
  • ® No wrinkles and slacks
  • O Substantially no wrinkles and slacks
  • ⁇ A few wrinkles and slacks
  • x Marked wrinkles and slacks
  • the sample with a dimension of 25 cm in length and 5 cm in width is adhered on the back face of the lid, which is placed over a water bath warmed at 40°C for 24 hours so that the sample film comes downward of the lid. Then, the wet sample is wound around a glass tube with a diameter of 1 cm to leave the tube in an oven heated at 70°C for 24 hours. The sample taken out of the oven is further left in a constant temperature chamber at 23°C.
  • the sample wound around the galss tube is peeled off and its surface resistance is measured with a surface measurement apparatus (made by New TOYO Scientific Instrument Co., trade name HEIDON-14).
  • Pellets were produced by blending 0.2 parts by weight of a hindered phenol based compound (made by Asahi Electrochemical Co., trade name; AO-80) and 0.1 parts by weight of a phosphite ester based compound (made by Asahi Electrochemical Co., trade name; "2112") to 100 parts by wight of a polyesteramide resin (melting point: 137°C), prepared by polymerization of adipic acid, 1,4-butanediol and ⁇ -caprolactam, comprising 50% by weight of an aliphatic ester unit and 50% by weight of an ali- phatic amide unit.
  • a hindered phenol based compound made by Asahi Electrochemical Co., trade name; AO-80
  • a phosphite ester based compound made by Asahi Electrochemical Co., trade name; "2112"
  • a film with a thickness of 100 ⁇ m was formed from the pellets using a T-die type extruder equipped with a cylinder with a diameter of 30 mm. This film was evaluated as 120 hours under the weather resistance test conditions (a), and 100 hours under the weather resistance test conditions (b).
  • a film was prepared by the same method as used in Example 1.1, except that the hindered phenol based compound and phosphite ester based compound used in Example 1 were not blended.
  • Pellets were produced by blending 0.1 parts by weight of the hindered phenol basd compound (made by Asahi Electrochemical Co., trade name: AO-60), 0.1 parts by weight of the phosphite ester based compound (made by Asahi Electrochemical Co., trade name: "2112") and 0.3 parts by weight of the hindered amine based light stabilizer (made by Ciba Speciality Chemical Co., trade name: LS-944) to 100 parts by weight of the polyesteramide resin used in Example 1.1.
  • a film with a thickness of 100 ⁇ m was formed from the pellets using a T-die type extruder equipped with a cylinder with a diameter of 30 mm.
  • This film was evaluated as 250 hours under the weather resistance test conditions (a), and 180 hours under the weather resistance test conditions (b).
  • Pellets were produced by blending 0.1 parts by weight of the hindered phenol based compound (made by Asahi Electrochemical Co., trade name AO-80), 0.1 parts by weight of the phosphite ester based compound (made by Asahi Electrochemical Co., trade name: "2112"), 0.3 parts by weight of the hindered amine based light stabilizer
  • Example 1.1 A film with a thickness of 100 ⁇ m was formed from the pellets using a T- die type extruder equipped with a cylinder with a diameter of 30 mm.
  • a film was prepared by the same method as used in Example 1.3, except that only 0.2 parts by weight of the benzotriazole based UV absorbing agent (made by Kyodo Pharmacuticals Co., trade name: VS-550) used in Example 1.3 was blended.
  • This film was evaluated as 100 hours under the weather resistance test conditions (a), and 60 hours under the weather resistance test conditions (b).
  • a film with a thickness of 100 ⁇ m was prepared by the same method as used in Example 1.1, except that the polyesteramide resin (melting point: 116 °C), produced by polymerization of adipic acid, 1,4-butanediol and ⁇ -caprolactam, comprising 70% by weight of the aliphatic amide unit and 30% by weight of the aliphatic fatty acid unit was used.
  • the polyesteramide resin melting point: 116 °C
  • This film was evaluated as 130 hours under the weather resistance test conditions (a), and 100 hours under the weather resistance test conditions (b).
  • Pellets were produced by blending 0.1 parts by weight of the hindered phenol based compound (made by Asahi Electrochemical Co., trade name : AO-60), 0.1 parts by weight of the phosphite ester based compound (made by Asahi Electrochemical Co., trade name "2112") and 0.3 parts by weight of the hindered amine based light stabilizer (made by Ciba Speciality Chemical Co., trade name: LS-944) to 100 parts by weight of the polyesteramide resin (melting point: 172°C), produced by polymerization of adipic acid, 1 ,4-butanediol and hexamethylene diamine, comprising 80% by weight of the aliphatic ester unit and 20% by weight of the aliphatic amide unit.
  • a film with a thickness of 100 ⁇ m was prepared from the pellets using the T-die type extruder having a cylinder with a diameter of 30 mm.
  • This film was evaluated as 150 hours under the weather resistance test conditions (a), and 120 hours under the weather resistance test conditions (b).
  • a film was prepared by the same method as used in example 1.5, except that the hin- dered phenol based compound and phosphite ester based compound used in Example
  • This film was evaluated as 90 hours under the weather resistance test conditions (1), and 70 hours under the weather resistance test conditions (2).
  • Pellets were formed by blending 10 parts by weight of calcium carbonate (made by Maruo Calcium Co., trade name: Super SS, mean grain size: 2.2 ⁇ m) relative to 100 parts by weight of a polyesteramide resin (melting point: 137 °C), produced by polymerization of adipic acid, 1,4-butanediol and ⁇ -caprolactam, comprising 50% by weight of an aliphatic ester unit and 50% by weight of an aliphatic amide unit.
  • a film with a thickness of 30 ⁇ m was formed from the pellet using a T-die type extruder equipped with a cylinder with a diameter of 30 mm. The days required for biodegradation of this film were 35 days.
  • Example 2.3 A film was formed by the same method as used in Example 2.1, except that the amount of blending of calcium carbonate in Example 2.1 was changed to 40 parts by weight. The days required for biodegradation of this film were 25 days.
  • Example 2.3 A film was formed by the same method as used in Example 2.1, except that the amount of blending of calcium carbonate in Example 2.1 was changed to 40 parts by weight. The days required for biodegradation of this film were 25 days.
  • a film was formed by the same method as used in Example 2.1, except that the amount of blending of calcium carbonate in Example 2.1 was changed to 70 parts by weight.
  • the days required for biodegradation of this film were 20 days.
  • a film was formed by the same method as used in Example 2.2, except that 40 parts by weight of talc (made by Fuji Talc Co., mean grain size: 1.8 ⁇ m) was used in place of calcium carbonate used in Example 2.2.
  • the days required for biodegradation of this film were 27 days.
  • a film was formed by the same method as used in Example 2.1, except that calcium carbonate used in Example 2.1 was not blended at all.
  • the days required for biodegradation of this film were 45 days.
  • Pellets were formed by blending 40 parts by weight of calcium carbonate (made by Maruo Calcium Co., trade name: Super SS, mean grain size: 2.2 ⁇ m) relative to 100 parts by weight of a polyesteramide resin (melting point: 116°C), produced by polymerization of adipic acid, 1 ,4-butanediol and ⁇ -caprolactam, comprising 70% by weight of an aliphatic ester unit and 30% by weight of an aliphatic amide unit.
  • a film with a thickness of 30 ⁇ m was formed from the pellet using a T-die type extruder equipped with a cylinder with a diameter of 30 mm. The days required for biodegradation of this film were 30 days.
  • Example 2.6 Example 2.6
  • Pellets were formed by blending 40 parts by weight of calcium carbonate (made by Maruo Calcium Co., trade name: Super SS, mean grain size: 2.2 ⁇ m) relative to 100 parts by weight of a polyesteramide resin (melting point: 172°C), produced by polymerization of adipic acid, 1,4-butanediol and hexamethylene diamine, comprising 80% by weight of an aliphatic ester unit and 20% by weight of an aliphatic amide unit.
  • a film with a thickness of 30 ⁇ m was formed from the pellet using a T-die type extruder equipped with a cylinder with a diameter of 30 mm. The days required for biodegradation of this film were 33 days.
  • a film was formed by the same method as used in Example 2.1, except that calcium carbonate used in Example 2.6 was not blended at all. The days required for biodegradation of this film were 52 days.
  • This film was evaluated as follows: haze; 13%, cloud preventive property; O, tensile strength; 680 kg/cm 2 , extension; 500%, weather resistance; O, biodegradability; O
  • a biodegradable agricultural film was produced by the same method as in Example 3.1, except that the resin component comprises 95 parts by weight of the polyesteramide resin used in Example 3.1 and 5 parts by weight of an aliphatic polyester resin (made by Showa Polymer Industry Co., trade name Bionole 3001).
  • This film was evaluated as follows: haze; 15%, cloud preventive property; O, tensile strength; 710 kg/cm 2 , extension; 480%, weather resistance; O, biodegradability; O
  • a biodegradable agricultural film was produced by the same method as in Example 3.1, except that the resin component comprises 90 parts by weight of the polyesteramide resin used in Example 1 and 10 parts by weight of an aliphatic polyester resin (made by Showa Polymer Industry Co., trade name Bionole 3001).
  • This film was evaluated as follows: haze; 17%, cloud preventive property; O, tensile strength; 740 kg/cm 2 , extension; 450%, weather resistance; O, biodegradability; O
  • a commercially available agricultural soft polyvinyl chloride film with a thickness of 100 ⁇ (made by CI. Chemicals Co., trade name CI. agricultural polyvinyl chloride
  • a commercially available agricultural polyolefine film with a thickness of 100 ⁇ m (made by CI. Chemicals Co., trade name CI. agricultural polyvinyl chloride Sky Coat) was evaluated, obtaining the following results: haze; 15.5%, cloud preventive property; O, tensile strength; 224 kg/cm 2 , extension; 550%, weather resistance; O, biodegradability; x
  • a biodegradable agricultural film was produced by the same method as in Example 3.1, except that 100 parts by weight of the aliphatic polyester resin (made bay Showa
  • the film was evaluated as follows: haze; 68%, cloud preventive property; x, tensile strength; 610 kg/cm 2 , extension; 840%, weather resistance; O, biodegradability; O
  • a biodegradable agricultural film was produced by the same method as in Example 1, except that 100 parts by weight of a polyesteramide resin (melting point 116°C), produced by polymerization of adipic acid, 1 ,4-butanediol and ⁇ -caprolactam, comprising 70% by weight of an aliphatic amide unit and 30% by weight of an aliphatic polyester unit was used.
  • a polyesteramide resin melting point 116°C
  • the film was evaluated as: haze; 15%, cloud preventive property; O, tensile strength; 660 kg/cm 2 , extension; 520%, weather resistance; O, biodegradability; O Example 3.6
  • a biodegradable agricultural film was produced by the same method as in Example 3.1, except that 90 parts by weight of the polyesteramide resin (melting point 116°C) used in Example 3.5 and 10 parts by weight of the aliphatic polyester resin (made by
  • the film was evaluated as: haze; 19%, cloud preventive property; O, tensile strength; 710 kg/cm 2 , extension; 460%, weather resistance; O, biodegradability; O
  • a biodegradable agricultural film was produced by the same method as in Example 1, except that 100 parts by weight of a polyesteramide resin (melting point 172°C), produced by polymerization of adipic acid, 1,4-butanediol and hexamethylene dia- mine, comprising 80% by weight of an aliphatic ester unit and 20% by weight of an aliphatic amide unit was used.
  • a polyesteramide resin melting point 172°C
  • the film was evaluated as: haze; 19%, cloud preventive property; O, tensile strength;
  • Additives such as 0.1 parts by weight of the hindered phenol based antioxidant (made by Asahi Electrochemical Co., trade name AO-80), 0.1 parts by weight of the phosphite ester based compound (made by Asahi Electrochemical Co., trade name "2112"), 0.02 parts by weight of the hindered amine based light stabilizer (made by Ciba Speciality Chemicals Co., trade name LS-944), and 30 parts by weight of cal- cium carbonate (made by Maruo Calcium Co., mean grain size 2.2 ⁇ m) were blended into 100 parts by weight of the resin component composed of a polyesteramide resin (melting point 137°C), produced by polymerization of adipic acid, 1,4-butanediol and ⁇ -caprolactam, comprising 50% by weight of the aliphatic ester unit and 50% by weight of the aliphatic amide unit.
  • This multi-film was evaluated as: tensile strength; 310 kg/cm 2 , extension; 370%, perpendicular tear strength; 120 kg/cm , biodegradability; ®
  • An arvicultural multi-film of the biodegradable resin was produced by the same method as in Example 4.1, except that 3 parts by weight of carbon black was further added to the composition used in Example 4.1.
  • This multi-film was evaluated as: tensile strength; 320 kg/cm 2 , extension; 360%, perpendicular tear strength; 110 kg/cm 2 , biodegradability; ®
  • An arvicultural multi-film of the biodegradable resin was produced by the same method as in Example 4.1, except that the resin component comprising 95 parts by weight of the polyesteramide resin used in Example 4.1 and 5 parts by weight of an aliphatic polyester resin (made by Showa Polymer Industry Co., trade name Bionole 3001) was used.
  • This multi-film was evaluated as: tensile strength; 380 kg/cm 2 , extension; 330%, perpendicular tear strength; 130 kg/cm 2 , biodegradability; ® Example 4.4
  • Additives such as 0.1 parts by weight of the hindered phenol based antioxidant (made by Asahi Electrochemical Co., trade name AO-80), 0.1 parts by weight of the phos- phite ester based compound (made by Asahi Electrochemical Co., trade name AO-80), 0.1 parts by weight of the phos- phite ester based compound (made by Asahi Electrochemical Co., trade name
  • This multi-film was evaluated as: tensile strength; 320 kg/cm 2 , extension; 370%, perpendicular tear strength; 120 kg/cm 2 , biodegradability; ®
  • a commercially available black poly multi-film with a thickness of 100 ⁇ m was evaluated, obtaining the following results: tensile strength; 350 kg/cm 2 , extension; 410%, perpendicular tear strength; 160 kg/cm 2 , biodegradability; x
  • An arvicultural multi-film of the biodegradable resin was produced by the same method as in Example 4.1, except that a polyesteramide resin (melting point 116 °C), produced by polymerization of adipic acid, 1 ,4-butanediol and ⁇ -caprolactam, comprising 30% by weight of the aliphatic resin unit and 70% by weight of the aliphatic amide unit was used as the resin component.
  • a polyesteramide resin melting point 116 °C
  • This multi-film was evaluated as: tensile strength; 300 kg/cm 2 , extension; 390%, perpendicular tear strength; 130 kg/cm 2 , biodegradability; ® Example 4.6
  • An agricultural multi-film was produced by the same method as in Example 4.1, ex- cept that 90 parts by weight of the aliphatic polyesteramide resin (melting point
  • This multi-film was evaluated as: tensile strength; 380 kg/cm 2 , extension; 310%, perpendicular tear strength; 110 kg/cm 2 , biodegradability; ®
  • a hindered phe- nol based antioxidant made by Asahi Electrochemical Co., trade name AO-80
  • a phosphite ester based compound made by Asahi Electrochemical Co., trade name "2112”
  • a hindered amine based light stabilizer made by Ciba Speciality Chemical Co., trade name LS-944
  • a biodegradable multilayer film having a construction of (B)/(A)/(B) with a layer ratio of 10/80/10 and a thickness of 100 ⁇ m was formed using a three-layer inflation molding machine. This film was evaluated as: water resistance; ®, haze; 19%, flexibility; 41 kg/mm 2 , biodegradability; O
  • a resin component composed of 100 parts by weight of the polyesteramide resin, prepared by polymerization of adipic acid, 1 ,4-butane diol and ⁇ -caprolactam, comprising 50% of an aliphatic ester unit and 50% of an aliphatic amide umt was used as the layer (B), and a resin component composed of 80 parts by weight of the aliphatic polyester resin (made by Showa polymer Industry Co., trade name Bionole 3001) and 20 parts by weight of the polyesteramide resin was used as the layer (B).
  • a hindered phenol based antioxidant made by Asahi Electrochemical Co., trade name AO-80
  • a phosphite ester based compound 0.1 parts by weight of a phosphite ester based compound
  • a hindered amine based light stabilizer made by Ciba Speciality Chemical Co., trade name LS-944
  • This film was evaluated as: water resistance; O, haze; 21%, flexibility; 39 kg/mm 2 , biodegradability; ®
  • a resin component composed of 70 parts by weight of the polyesteramide resin, prepared by polymerization of adipic acid, 1,4-butane diol and ⁇ -caprolactam, comprising 30% of an aliphatic ester unit and 70% of an aliphatic amide unit was used as the layer (A), and a resin component composed of 100 parts by weight of the aliphatic polyester resin (made by Showa polymer Industry Co., trade name Bionole 3001) was used as the layer (B).
  • a hindered phenol based antioxidant made by Asahi Electrochemical Co., trade name AO-80
  • a phosphite ester based compound made by Asahi Electrochemical Co., trade name "2112”
  • a hindered amine based light stabilizer made by Ciba Speciality Chemical Co., trade name LS-944
  • 30 parts by weight of calcium carbonate made by Maruo Calcium Co., mean grain size: 2,2 ⁇ m
  • a biodegradable multilayer film having a layer construction of (B)/(A)/(B) with a layer ratio of 15/70/15 and a thickness of 100 ⁇ m was formed using a three-layer inflation molding machine.
  • This film was evaluated as: water resistance; ®, haze; 21%, flexibility; 46 kg/mm 2 , biodegradability; O
  • polyesteramide resin prepared by polymerization of adipic acid, 1,4-butanediol and ⁇ -caprolactam, comprising 50% of an aliphatic ester unit and 50% of an aliphatic amide unit, 0.1 parts by weight of the hindered phenol based antioxidant (made by Asahi Electrochemical Co., trade name AO-80), 0.1 parts by weight of a phosphite ester based compound (made by Asahi Electrochemical Co., trade name "2112”), and 0.2 pars by weight of the hindered amine based light stabilizer (made by Ciba Speciality Chemical Co., trade name LS-944) were blended. A single layer biodegradable film with a thickness of 100 ⁇ m was formed from this composition using a single layer inflation molding machine.
  • This film was evaluated as: water resistance; ⁇ , haze; 14%, flexibility; 36 kg/mm 2 , biodegradability; ® Comparative Example 5.2
  • This film was evaluated as: water resistance; ®, haze; 68%, flexibility; 800 kg/mm 2 , biodegradability; O, especially showing poor transparency and flexibility.
  • a resin component composed of 100 parts by weight of the aliphatic polyester resin made by Showa polymer Industry Co., trade name Bionole 3001 was used as the layer (B).
  • a hindered phenol based antioxidant made by Asahi Electrochemical Co., trade name AO-80
  • a phosphite ester based compound made by Asahi Electrochemical Co., trade name "2112”
  • a hindered amine based light stabilizer made by Ciba Speciality Chemical Co., trade name LS- 944
  • 30 parts by weight of calcium carbonate made by Maruo Calcium Co., mean grain size: 2,2 ⁇ m
  • a biodegradable multilayer film having a layer construction of (B)/(A)/(B) with a layer ratio of 15/70/15 and a thickness of 100 ⁇ m was formed using a three-layer inflation molding machine.
  • This film was evaluated as: water resistance; ®, haze; 24%, flexibility; 65 kg/mm 2 , biodegradability; O
  • a resin component composed of 100 parts by weight of an aliphatic polyester resin (made by Showa Polymer Industry Co., trade name Bionole 3001) was used as the layer (A); a resin component composed of 70 parts by weight of a polyesteramide rsin, prepared by polymerization of adipic acid, 1 ,4-bitanediol and ⁇ -caprolactam, comprising 50% of an aliphatic ester unit and 50% of an aliphatic amide umt, and 30 parts by weight of the aliphatic polyester resin described above was used as the layer (B); and a resin component composed of 80 parts by weight of the aliphatic polyester resin and 20 parts by weight of the polyesteramide resin was used as the layer (C).
  • a hindered phenol based anti-oxidant made by Asahi Electrochemical Co., trade name AO-80
  • a phosphite ester based compound made by Asahi Electrochemical Co., trade name "2112”
  • a hindered amine based light stabilizer made by Ciba Speciality Chemical Co., trade name LS-944
  • a cloud preventive agent comprising 1 part by weight of diglycerine distearate and 1 parts by weight of sorbitan monostearate, and a fog preventive agent comprising 0.1 parts by weight of a fluorinated surfactant (made by Daikin Industries Co., trade name DS-403) were blended to the layer (B); and a cloud preventive agent comprising 0.7 parts by weight of diglycerine distearate and 0.7 parts by weight of sorbitan monostearate, and a fog preventive agent comprising 0.1 parts by weight of a fluorinated surfactant (made by Daikin Industries Co., trade name DS-403) were blended to the layer (C).
  • a biodegradable multilayer agricultural film with a construction of (A)/(B)/(C), a layer ratio of 20/60/20 and a thickness of 100 ⁇ m was produced using a three-layer inflation molding machine.
  • a biodegradable multilayer agricultural film was produced by the same method as in
  • Example 6.1 except that the resin component in the layer (C) was replaced with 70 parts by weight of the aliphatic polyester resin and 30 parts by weight of the polyesteramide resin.
  • a resin component composed of 80 parts by weight of a polyesteramide resin, prepared by polymerization of adipic acid, 1,4-butanediol and ⁇ -caprolactam, comprising 30% of an aliphatic ester unit and 70% of an aliphatic amide unit, and 20 parts by weight of the aliphatic polyester resin described above was used as the layer (A);
  • the layer (C) a resin component composed of 70 parts by weight of the aliphatic polyester resin and 30 parts by weight of the polyesteramide resin was used as the layer (C).
  • a hindered phenol based anti-oxidant made by Asahi Electrochemical Co., trade name AO-80
  • a phosphite ester based compound made by Asahi Electrochemical Co., trade name AO-80
  • a cloud preventive agent comprising 1 part by weight of diglycerine distearate and 1 parts by weight of sorbitan monostearate, and a fog preventive agent comprising 0.1 parts by weight of a fluorinated surfactant (made by Daikin Industries Co., trade name DS-403) were blended to the layer (B); and a cloud preventive agent comprising 0.7 parts by weight of diglyceride stearate and 0.7 parts by weight of sorbitan monostearate, and a fog preventive agent comprising 0.1 parts by weight of a fluorinated surfactant (made by Daikin Industries Co., trade name DS- 403) were blended to the layer (C).
  • a biodegradable multilayer agricultural film with a construction of (A)/(B)/(C), a layer ratio of 15/70/15 and a thickness of 100 ⁇ m was produced using a three-layer inflation molding machine.
  • the layer (A) a resin component composed of 80 parts by weight of a polyesteramide resin, prepared by polymerization of adipic acid, 1 ,4-butanediol and hexamethylene diamine, comprising 80% of an aliphatic ester unit and 20% of an aliphatic amide unit, and 20 parts by weight of the aliphatic polyester resin described above was used as the layer (B); and a resin component composed of 70 parts by weight of the aliphatic polyester resin and 30 parts by weight of the polyesteramide resin was used as the layer (C).
  • a hindered phenol based anti-oxidant made by Asahi Electrochemical Co., trade name AO-80
  • a phosphite ester based compound made by Asahi Electrochemical Co., trade name AO-80
  • a cloud preventive agent comprising 1 part by weight of diglycerine distearate and 1 parts by weight of sorbitan monostearate, and a fog preventive agent comprising 0.1 parts by weight of a fluorinated surfactant (made by Daikin Industries Co., trade name DS-403) were blended to the layer (B); and a cloud preventive agent comprising 0.7 parts by weight of diglyceride stearate and 0.7 parts by weight of sorbitan monostearate, and a fog preventive agent comprising 0.1 parts by weight of a fluorinated surfactant (made by Daikin Industries Co., trade name DS-403) were blended to the layer (C).
  • a biodegradable multilayer agricultural film with a construction of (A)/(B)/(C), a layer ratio of 15/70/15 and a thickness of 100 ⁇ m was produced using a three-layer inflation molding machine.
  • a polyesteramide resin prepared by polymerization of adipic acid, 1,4-butanediol and ⁇ -caprolactam, comprising 50% of the aliphatic ester umt and 50% of the aliphatic amide unit, 0.1 parts by weight of a hindered phenol based anti-oxidant (made by Asahi Electrochemical Co., trade name AO-80), 0.1 parts by weight of a phosphite ester based compound (made by Asahi Electrochemi- cal Co., trade name "2112"), and 0.3 parts by weight of a hindered amine based light stabilizer (made by Ciba Speciality Chemical Co., trade name LS-944) were blended, as well as a cloud preventive agent comprising 1 part by weight of diglycerine distearate and 1 part by weight of sorbitan monostearate, and a fog preventive agent comprising 0.1 parts by weight of a fluorinated surfactant (made by Asahi Electrochemical
  • a biodegradable mono-layer agricultural film a thickness of 100 ⁇ m was produced using a mono-layer inflation molding machine. This film was evaluated as; haze: 14%, cloud preventive property: ®, water resistance: ⁇ , acceleration of weather resistance: O, heat resistant blocking property: ⁇
  • Additives such as 0.1 parts by weight of a hindered phenol based antioxidant (made by Asahi Electrochemical Co., trade name AO-80), 0.1 parts by weight of a phosphite ester based compound (made by Asahi Electrochemical Co., trade name "2112"), 0.2 parts by weight of a hindered amine based light stabilizer (made by Ciba Speciality Chemical Co., trade name LS-944), and 30 parts by weight of calcium carbonate (made by Maruo Calcium Co, mean grain size: 2.2 ⁇ m) as a filler were blended into 100 parts by weight of a resin component composed of a polyesteramide resin (melting point 137 °C), prepared by polymerization of adipic acid, 1,4-butane- diol and ⁇ -caprolactam, comprising 50% by weight of an aliphatic ester unit and 50% by weight of an aliphatic amide unit.
  • the multi-film was evaluated as; tensile strength (moist film): 250 kg/cm 2 , extension
  • a multi-film of a biodegradable resin for use in rice fields was produced by the same method as in Example 7.1, except that 3 parts by weight of carbon black was used in addition to the additive used in Example 7.1.
  • the multi-film was evaluated as; tensile strength (moist film): 260 kg/cm 2 , extension (moist film): 370%, flexibility (moist film): 19 kg/mm 2 , biodegradability ®
  • a multi-film of a biodegradable resin for use in rice fields was produced by the same method as in Example 7.1, except that the proportion of blending of the polyester amide resin and aliphatic polyester resin used in Example 7.1 were changed to 95 parts by weight and 5 parts by weight, respectively. It was possible to plant young rice plants into a rice field while covering the rice field with a multi-film of the biodegradable resin for use in rice fields by piercing the multi-film with a rice planting machine.
  • the multi-film was evaluated as; tensile strength (moist film): 330 kg/cm 2 , extension (moist film): 340%, flexibility (moist film): 22 kg/mm 2 , biodegradability ®.
  • Additives such as 0.1 parts by weight of a hindered phenol based antioxidant (made by Asahi Electrochemical Co., trade name AO-80), 0.1 parts by weight of a phosphite ester based compound (made by Asahi Electrochemical Co., trade name "2112"), 30 parts by weight of calcium carbonate (made by Maruo Calcium Co, mean grain size: 2.2 ⁇ m) as a filler, and 0.8 parts by weight of a green pigment
  • Example 7.1 A multi- film of a biodegradable resin for use in rice fields with a thickness of 30 ⁇ m was produced using an inflation molding machine.
  • the multi-film was evaluated as; tensile strength (moist film): 260 kg/cm 2 , extension
  • a commercially available black poly-multifilm with a thickness of 30 ⁇ m was evaluated as; tensile strength (moist film): 340 kg/cm 2 , extension (moist film): 400%, flexibility (moist film): 14 kg/mm 2 , biodegradability x
  • Additives such as 0.1 parts by weight of a hindered phenol based antioxidant (made by Asahi Electrochemical Co., trade name AO-80), 0.1 parts by weight of a phosphite ester based compound (made by Asahi Electrochemical Co., trade name "2112"), 0.2 parts by weight of a hindered amine based light stabilizer (made by Ciba Speciality Chemical Co., trade name LS-944), and 30 parts by weight of calcium carbonate (made by Maruo Calcium Co, mean grain size: 2.2 ⁇ m) as a filler were blended into 100 parts by weight of the aliphatic polyester resin (made by Showa
  • a multi-film of a biodegradable resin for use in rice fields with a thickness of 30 ⁇ m was produced using an inflation molding machine.
  • the film has so poor flexibility that it could not make close contact to the sur- face of the soil, causing such troubles as the film get rolled up by wind.
  • the multi-film was evaluated as; tensile strength (moist film): 590 kg/cm 2 , extension (moist film): 850%, flexibility (moist film): 76 kg/mm 2 , biodegradability O.
  • tensile strength (moist film): 590 kg/cm 2
  • extension (moist film): 850%
  • flexibility (moist film): 76 kg/mm 2
  • biodegradability O O.
  • a multi-film of a biodegradable resin for use in rice fields was produced by the same method as in Example 7.1, except that a polyesteramide resin (melting point: 116°C), prepared by polymerization of adipic acid, 1 ,4-butanediol and ⁇ -caprolactam, comprising 30% by weight of the aliphatic ester unit and 70% by weight of the aliphatic amide unit was used as the resin component.
  • a polyesteramide resin melting point: 116°C
  • the multi-film was evaluated as; tensile strength (moist film): 240 kg/cm 2 , extension (moist film): 400%, flexibility (moist film): 19 kg/mm 2 , biodegradability ®.
  • a multi-film of a biodegradable resin for use in rice fields was produced by the same method as in Example 7.1, except that 90 parts by weight of a polyesteramide resin (melting point: 172°C), prepared by polymerization of adipic acid, 1,4-butanediol and hexamethylene diamine, comprising 80% by weight of the aliphatic ester unit and 20%) by weight of the aliphatic amide unit, and 10 parts by weight of a aliphatic polyester resin (made by Showa Polymer Industry Co., trade name Bionole 3001) were used as the resin components.
  • a polyesteramide resin melting point: 172°C
  • the multi-film was evaluated as; tensile strength (moist film): 320 kg/cm 2 , extension

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur une composition de résine biodégradable, ainsi que sur des films et des feuilles comprenant cette composition et dont la résistance à la chaleur et aux intempéries a été améliorée lorsque ceux-ci sont utilisés comme produits finaux dans des applications extérieures tout en conservant une excellente biodégradabilité et une excellente aptitude au compostage. Ces produits tels que film d'humus, polytunnel, serre, film de masquage, feuille de lit fluvial, film étirable pour palettes et film d'ensilage sont utilisés dans les domaines de l'agriculture, de l'emballage et du génie civil.
PCT/EP2000/003380 1999-04-16 2000-04-14 Composition de resine pour films biodegradables utilises en agriculture et presentant une meilleure resistance aux intemperies Ceased WO2000063282A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
IL14566600A IL145666A0 (en) 1999-04-16 2000-04-14 Resin composition for biodegradable agricultural films with enhanced weatherability
KR1020017013140A KR20020000800A (ko) 1999-04-16 2000-04-14 내후성이 향상된 생분해성 농업용 필름을 위한 수지 조성물
EP00925213A EP1173507A1 (fr) 1999-04-16 2000-04-14 Composition de resine pour films biodegradables utilises en agriculture et presentant une meilleure resistance aux intemperies
AU44007/00A AU4400700A (en) 1999-04-16 2000-04-14 Resin composition for biodegradable agricultural films with enhanced weatherability

Applications Claiming Priority (14)

Application Number Priority Date Filing Date Title
JP11/108683 1999-04-16
JP11/108682 1999-04-16
JP11/108684 1999-04-16
JP10868399 1999-04-16
JP10868599 1999-04-16
JP10868499 1999-04-16
JP10868299 1999-04-16
JP11/108685 1999-04-16
JP11/110231 1999-04-19
JP11023299 1999-04-19
JP11/110230 1999-04-19
JP11023199 1999-04-19
JP11/110232 1999-04-19
JP11023099 1999-04-19

Publications (1)

Publication Number Publication Date
WO2000063282A1 true WO2000063282A1 (fr) 2000-10-26

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EP (1) EP1173507A1 (fr)
KR (1) KR20020000800A (fr)
AU (1) AU4400700A (fr)
IL (1) IL145666A0 (fr)
WO (1) WO2000063282A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001079334A1 (fr) * 2000-04-18 2001-10-25 Kureha Kagaku Kogyo K.K. Film de polyester-amide etire et procede de production de celui-ci
WO2003035820A1 (fr) * 2001-10-25 2003-05-01 Colgate-Palmolive Company Composition de savon transparente stabilisee
US7582690B2 (en) 2004-11-19 2009-09-01 Eastman Chemical Company Stabilized aliphatic polyester compositions
AT515545A4 (de) * 2014-06-05 2015-10-15 Coveris Flexibles Austria Gmbh Kunststofffolie
CN108264688A (zh) * 2018-03-02 2018-07-10 广州禾工材料科技有限公司 一种用于包装膜的防雾母粒及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040053010A (ko) * 2004-05-27 2004-06-23 이완채 슬러지 부상배출 초음파세척기
GB2635102A (en) * 2023-03-22 2025-05-07 Lambda Energy Ltd Wavelength downconverters

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US5216043A (en) * 1991-12-12 1993-06-01 Minnesota Mining And Manufacturing Company Degradable thermophastic compositions and blends with naturally biodegradable polymers
JPH06256481A (ja) * 1993-03-05 1994-09-13 Toyobo Co Ltd 生分解性農業用フィルム
WO1996021690A1 (fr) * 1995-01-13 1996-07-18 Basf Aktiengesellschaft Polymeres biodegradables, leur procede de fabrication et leur utilisation pour la fabrication de corps moules biodegradables
WO1996021691A1 (fr) * 1995-01-13 1996-07-18 Basf Aktiengesellschaft Polymeres biodegradables, leur procede de fabrication et leur utilisation pour la fabrication de corps moules biodegradables
US5644020A (en) * 1993-08-12 1997-07-01 Bayer Aktiengesellschaft Thermoplastically processible and biodegradable aliphatic polyesteramides
WO1999005207A1 (fr) * 1997-07-25 1999-02-04 Monsanto Company Compositions de pha et leur procede d'utilisation dans la production de films de pha
EP0937743A1 (fr) * 1998-02-20 1999-08-25 KABUSHIKI KAISHA KOBE SEIKO SHO also known as Kobe Steel Ltd. Stabilisateur amélioré pour la fabrication des polyesters biodégradables

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US5216043A (en) * 1991-12-12 1993-06-01 Minnesota Mining And Manufacturing Company Degradable thermophastic compositions and blends with naturally biodegradable polymers
JPH06256481A (ja) * 1993-03-05 1994-09-13 Toyobo Co Ltd 生分解性農業用フィルム
US5644020A (en) * 1993-08-12 1997-07-01 Bayer Aktiengesellschaft Thermoplastically processible and biodegradable aliphatic polyesteramides
WO1996021690A1 (fr) * 1995-01-13 1996-07-18 Basf Aktiengesellschaft Polymeres biodegradables, leur procede de fabrication et leur utilisation pour la fabrication de corps moules biodegradables
WO1996021691A1 (fr) * 1995-01-13 1996-07-18 Basf Aktiengesellschaft Polymeres biodegradables, leur procede de fabrication et leur utilisation pour la fabrication de corps moules biodegradables
WO1999005207A1 (fr) * 1997-07-25 1999-02-04 Monsanto Company Compositions de pha et leur procede d'utilisation dans la production de films de pha
EP0937743A1 (fr) * 1998-02-20 1999-08-25 KABUSHIKI KAISHA KOBE SEIKO SHO also known as Kobe Steel Ltd. Stabilisateur amélioré pour la fabrication des polyesters biodégradables

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DATABASE WPI Section Ch Week 199441, Derwent World Patents Index; Class A23, AN 1994-330141, XP002143312 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001079334A1 (fr) * 2000-04-18 2001-10-25 Kureha Kagaku Kogyo K.K. Film de polyester-amide etire et procede de production de celui-ci
WO2003035820A1 (fr) * 2001-10-25 2003-05-01 Colgate-Palmolive Company Composition de savon transparente stabilisee
US6696398B2 (en) 2001-10-25 2004-02-24 Colgate-Palmolive Company Stabilized composition comprising 2-(2-H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol
US7582690B2 (en) 2004-11-19 2009-09-01 Eastman Chemical Company Stabilized aliphatic polyester compositions
AT515545A4 (de) * 2014-06-05 2015-10-15 Coveris Flexibles Austria Gmbh Kunststofffolie
AT515545B1 (de) * 2014-06-05 2015-10-15 Coveris Flexibles Austria Gmbh Kunststofffolie
CN108264688A (zh) * 2018-03-02 2018-07-10 广州禾工材料科技有限公司 一种用于包装膜的防雾母粒及其制备方法
CN108264688B (zh) * 2018-03-02 2021-02-26 广州禾工材料科技有限公司 一种用于包装膜的防雾母粒及其制备方法

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EP1173507A1 (fr) 2002-01-23
KR20020000800A (ko) 2002-01-05
IL145666A0 (en) 2002-06-30

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