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WO2008026229A1 - Film polymère utilisable comme couverture en agriculture - Google Patents

Film polymère utilisable comme couverture en agriculture Download PDF

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Publication number
WO2008026229A1
WO2008026229A1 PCT/IT2006/000631 IT2006000631W WO2008026229A1 WO 2008026229 A1 WO2008026229 A1 WO 2008026229A1 IT 2006000631 W IT2006000631 W IT 2006000631W WO 2008026229 A1 WO2008026229 A1 WO 2008026229A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
thermoplastic polyurethane
weight
present
hindered amines
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/IT2006/000631
Other languages
English (en)
Inventor
Maurizio Zanon
Livio Stefani
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.)
PATI SpA
Original Assignee
PATI SpA
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 PATI SpA filed Critical PATI SpA
Priority to PCT/IT2006/000631 priority Critical patent/WO2008026229A1/fr
Publication of WO2008026229A1 publication Critical patent/WO2008026229A1/fr
Anticipated expiration legal-status Critical
Priority to SM200900019T priority patent/SMP200900019B/it
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00—Protection of plants
    • A01G13/30—Ground coverings
    • A01G13/32—Mats; Nets; Sheets or films
    • A01G13/33—Sheets or films
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14—Greenhouses
    • A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0853—Ethene vinyl acetate copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2310/00—Agricultural use or equipment
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor

Definitions

  • the present invention relates to a polymer film for use in agriculture as a cover for greenhouses and tunnels in accordance with the features set out in the preamble of the main claim.
  • polymer films as covers for agricultural greenhouses. These films have to meet numerous technical requirements both in terms of optical properties, in order to ensure maximum transparency to visible light and at the same time an effective barrier to far infrared radiation (greenhouse effect), and in terms of mechanical properties, such as, for example, tensile strength, yield point, impact strength and tear propagation strength.
  • optical properties in order to ensure maximum transparency to visible light and at the same time an effective barrier to far infrared radiation (greenhouse effect)
  • mechanical properties such as, for example, tensile strength, yield point, impact strength and tear propagation strength.
  • One of the more important technical characteristics sought in a polymer film for applications in the agricultural sector is that of resistance to the degradation caused by the action of sunlight and thermal oxidation. These latter damage the polymer chains over time, draining the film of both its mechanical characteristics and its optical characteristics.
  • a polymer film used as a cover for greenhouses has an average service life of a few dozen months (by way of reference, the example given by Appendix A of standard EN 13206:2001: a film of Class D in a climate zone with irradiation of from 100 to 130 kLy/year has a life of approximately 24 months), after which it becomes necessary to replace it because the film loses its inherent elasticity, becomes brittle and tends to become opaque.
  • the films used in this specific technical field are obtained from a polyolefin base formed, for example, from low density or linear low density polyethylene, commonly known by the acronyms LDPE and LLDPE, or also from ethylene-vinyl acetate or ethylene-butyl acrylate copolymers, commonly known by the respective acronyms EVA/C and EBA/C.
  • LDPE and LLDPE low density or linear low density polyethylene
  • EVA/C ethylene-vinyl acetate or ethylene-butyl acrylate copolymers
  • EVA/C ethylene-vinyl acetate or ethylene-butyl acrylate copolymers
  • UV absorbers Isuch as benzophenones, benzotriazoles, hydroxybenzophenones, benzoic acid esters, triazines, as well as some acrylates, salts and/or organometal complexes based on nickel or other metals, some oxamides and others still.
  • HALS hindered amine light stabiliser
  • UV-absorbing additives in percentages ranging from 2 to 4 times that of the UV absorber. They act by catalytically blocking the radicals which form owing to the effect of the absorption by the polymer chains of the energy provided by solar radiation, thus slowing down the rate of the photo-oxidation and depolymerisation reactions.
  • All types of HALS are potentially effective but, given their behaviour as Lewis bases, they suffer from interaction with acid substances which may block the functional groups thereof. In particular, in the case of films used as covers for greenhouses and tunnels, contact with numerous chemical products which are based on sulphur and halogens and which are normally used in agriculture may rapidly reduce their efficiency.
  • the object of the present invention is to provide a polymer film which is devised structurally and functionally to ⁇ maintain for a longer period the desired functional, mechanical and spectrophotometric characteristics by a greater resistance to the degradation caused by the action of solar radiation.
  • the film comprises a layer of polyolefin-based polymer material in which a light stabiliser based on hindered amines (HALS), and an effective amount of thermoplastic polyurethane, which is referred to hereinafter as TPU for the sake of brevity, are dispersed.
  • HALS hindered amines
  • TPU thermoplastic polyurethane
  • the film is normally of the single-layer type but may likewise be of the multi-layer type, which is coextruded or coupled, as long as the presence of a polyolefin material, of TPU and HALS, is provided for in at least one of the layers forming the film.
  • the polymer base which forms the film according to the invention is a polyolefin selected from those normally used in this type of application, such as, for example, a low density polyethylene (LDPE) or a linear low density polyethylene (LLDPE).
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • the film is formed from an ethylene-vinyl acetate copolymer (EVA/C) or from an ethylene-butyl acrylate copolymer (EBA/C).
  • EVA/C ethylene-vinyl acetate copolymer
  • EBA/C ethylene-butyl acrylate copolymer
  • a polymer mixture based on EVA/C or EBA/C with LDPE or LLDPE, in any proportion.
  • the polyolefin base is advantageously mixed with the normal additives used in the sector in order to confer the desired antioxidant, slip, antistatic and antidrip properties and the desired properties of selective photo-absorption in the visible light range and/or the ultraviolet range and/or the infrared range, etc., at the dosages suggested by the suppliers of the additives and at any rate known to the experts in the art.
  • the light stabiliser added to the polyolefin-based mixture comprises HALS, which are preferably oligomeric or polymeric and of the secondary and tertiary type and also methylated or at any rate modified and substituted, and is constituted in a preferred composition variant by those substances only.
  • HALS oligomeric or polymeric and of the secondary and tertiary type and also methylated or at any rate modified and substituted
  • the light stabiliser is constituted by methylated HALS or by sterically hindered aminoxyamines, also known as NOR-HALS, in order to make use of the lower basicity thereof.
  • an effective amount of TPU is also added to the basic polymer mixture.
  • the TPU may be either of the aromatic type or of the aliphatic type, with a polyester or polyether structure.
  • the use of aliphatic, polyester or polyether TPU is preferred because aromatic TPU may give rise, as a result of photo-oxidative reactions, to chromophore groups which tend to confer a brownish yellow colour on the film.
  • Films to which aromatic TPU, which is per se advantageously less expensive, is added, could also be used in particular applications where a possible colouring does not have negative effects.
  • TPUs having a polyester structure are generally less expensive, while TPUs based on polyether generally exhibit greater resistance to hydrolysis.
  • the TPU and the HALS are present in a ratio by weight of from 2:1 to 25: 1.
  • the TPU is added to the polymer mixture in such a manner as to attain a fraction by weight of from 5% to 30%, preferably from 7% to 15%, while, for their part, the HALS are added in such a manner as to attain a fraction by weight of from 0.2% to 2.5%, preferably from 0.8% to 1.6%, with respect to the film.
  • the polyolefin family and the TPUs have physico-chemical characteristics which are relatively diverse with respect to each other, so that, in liquid phase, the two compounds are poorly miscible in each other.
  • the TPU and the polyolefin base are selected in such a manner as to have comparable melting points, differing by less than 40 0 C, and similar apparent viscosities in the range of the speed gradients usual for extrusion processes. Examples
  • the criterion of reduction to 50% of the initial value for elongation at break in tensile stress tests according to EN ISO 527-1 and EN ISO 527-3 was used.
  • Specimen 1 did not reach the 750 hours of exposure, corresponding to the first sampling.
  • Specimen 2 test interrupted at 750 hours of exposure owing to the intense brownish yellow colour exhibited by the specimen.
  • Specimen 3 from 3,000 to 3,500 hours
  • Specimen 5 from 2,500 to 3,000 hours.
  • the films of type 4 were found to be sound even at the end of the third winter of use, but with residual mechanical characteristics which unexpectedly suggest that they might last at least another year, with an increase of from 30 to 50% in resistance to photodegradation with respect to the films of the conventional type used as controls.
  • the present invention therefore achieves the object proposed of providing a polymer film having greater resistance to polymer degradation caused by exposure to sunlight.
  • the invention offers numerous other advantages for use, including the fact that the polymer film so obtained has, compared with a conventional polyolefin-based film, improved characteristics of elasticity and tear resistance and greater IR efficiency (greenhouse effect), evaluated as absorption of radiation in the far infrared range, wavelengths of from 7,000 to 13,000 nm, in accordance with the standard EN 13206:2001.
  • the IR efficiency measured on specimens of type 5 film was 75%, against values higher than 85% for the type 4 film obtained in accordance with the present invention.

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

Abstract

L'invention concerne un film polymère utilisable comme couverture en agriculture, qui comprend au moins une couche d'un matériau polymérique à base de polyoléfine dans lequel un photostabilisant à base d'amines empêchées (HALS) et une quantité efficace de polyuréthane thermoplastique sont dispersés.
PCT/IT2006/000631 2006-08-29 2006-08-29 Film polymère utilisable comme couverture en agriculture Ceased WO2008026229A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/IT2006/000631 WO2008026229A1 (fr) 2006-08-29 2006-08-29 Film polymère utilisable comme couverture en agriculture
SM200900019T SMP200900019B (it) 2006-08-29 2009-03-26 Film polimerico per uso come copertura in agricoltura

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IT2006/000631 WO2008026229A1 (fr) 2006-08-29 2006-08-29 Film polymère utilisable comme couverture en agriculture

Publications (1)

Publication Number Publication Date
WO2008026229A1 true WO2008026229A1 (fr) 2008-03-06

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ID=37909690

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IT2006/000631 Ceased WO2008026229A1 (fr) 2006-08-29 2006-08-29 Film polymère utilisable comme couverture en agriculture

Country Status (2)

Country Link
SM (1) SMP200900019B (fr)
WO (1) WO2008026229A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2163571A1 (fr) * 2008-09-10 2010-03-17 Rohm and Haas Company Mélanges acryliques d'uréthane
CN108912468A (zh) * 2018-05-29 2018-11-30 厦门协四方工贸有限公司 一种抗老化气泡膜及其成型工艺
CN109721984A (zh) * 2017-10-31 2019-05-07 丹阳博亚新材料技术服务有限公司 一种隔热防雾大棚薄膜
EP3578036A1 (fr) 2018-06-06 2019-12-11 Thrace Nonwovens & Geosynthetics S.A. Développement d'un tissu de couverture végétale ignifuge pour serres
WO2022023782A1 (fr) * 2020-07-27 2022-02-03 Plastika Kritis S.A. Films pour structures agricoles
CN114347609A (zh) * 2022-01-10 2022-04-15 高碑店市立信神农科技发展有限责任公司 一种耐低温长寿棚膜
EP4538237A1 (fr) * 2023-10-13 2025-04-16 4Life Solutions ApS Désinfection solaire de l'eau

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57168928A (en) * 1981-04-10 1982-10-18 Toyo Soda Mfg Co Ltd Agricultural film
EP0612795A1 (fr) * 1993-02-24 1994-08-31 CONSTAB POLYMER-CHEMIE GmbH & Co. Compositions polymère stabilisées à la lumière
EP1184416A1 (fr) * 2000-08-29 2002-03-06 Ciba SC Holding AG Procédé pour réduire le dépôt de poussière sur des films de polyoléfine
JP2003000076A (ja) * 2001-06-20 2003-01-07 Mitsubishi Chem Mkv Co 農業用ポリオレフィン系樹脂フィルム
WO2005111142A1 (fr) * 2004-05-13 2005-11-24 Oleg Leonidovich Kulikov Materiau polymere thermoplastique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57168928A (en) * 1981-04-10 1982-10-18 Toyo Soda Mfg Co Ltd Agricultural film
EP0612795A1 (fr) * 1993-02-24 1994-08-31 CONSTAB POLYMER-CHEMIE GmbH & Co. Compositions polymère stabilisées à la lumière
EP1184416A1 (fr) * 2000-08-29 2002-03-06 Ciba SC Holding AG Procédé pour réduire le dépôt de poussière sur des films de polyoléfine
JP2003000076A (ja) * 2001-06-20 2003-01-07 Mitsubishi Chem Mkv Co 農業用ポリオレフィン系樹脂フィルム
WO2005111142A1 (fr) * 2004-05-13 2005-11-24 Oleg Leonidovich Kulikov Materiau polymere thermoplastique

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2163571A1 (fr) * 2008-09-10 2010-03-17 Rohm and Haas Company Mélanges acryliques d'uréthane
EP2163570A1 (fr) * 2008-09-10 2010-03-17 Rohm and Haas France SA Mélanges acryliques d'uréthane
US8455099B2 (en) 2008-09-10 2013-06-04 Rohm And Haas Company Urethane acrylic blends
AU2009212774B2 (en) * 2008-09-10 2014-11-13 Rohm And Haas Company Urethane acrylic blends
CN109721984A (zh) * 2017-10-31 2019-05-07 丹阳博亚新材料技术服务有限公司 一种隔热防雾大棚薄膜
CN108912468A (zh) * 2018-05-29 2018-11-30 厦门协四方工贸有限公司 一种抗老化气泡膜及其成型工艺
EP3578036A1 (fr) 2018-06-06 2019-12-11 Thrace Nonwovens & Geosynthetics S.A. Développement d'un tissu de couverture végétale ignifuge pour serres
GR20180100240A (el) * 2018-06-06 2020-02-13 Thrace Nonwovens & Geosynthetics Αβεε Μη Υφαντων Υφασματων Και Γεωσυνθετικων Προϊοντων Αναπτυξη ενος υφασματος που επιβραδυνει τη φλογα για θερμοκηπια
GR1009783B (el) * 2018-06-06 2020-07-07 Thrace Nonwovens & Geosynthetics Αβεε Μη Υφαντων Υφασματων Και Γεωσυνθετικων Προϊοντων Αναπτυξη ενος υφασματος που επιβραδυνει τη φλογα για θερμοκηπια
WO2022023782A1 (fr) * 2020-07-27 2022-02-03 Plastika Kritis S.A. Films pour structures agricoles
CN114347609A (zh) * 2022-01-10 2022-04-15 高碑店市立信神农科技发展有限责任公司 一种耐低温长寿棚膜
EP4538237A1 (fr) * 2023-10-13 2025-04-16 4Life Solutions ApS Désinfection solaire de l'eau
WO2025078287A1 (fr) * 2023-10-13 2025-04-17 4Life Solutions Aps Désinfection solaire d'eau

Also Published As

Publication number Publication date
SMP200900019B (it) 2010-01-19
SMAP200900019A (it) 2009-05-11

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