WO2024256443A1 - Mélange de stabilisants uv et de stabilisants lumière à amine encombrée pour obtenir une excellente stabilité thermique et uv à long terme - Google Patents

Mélange de stabilisants uv et de stabilisants lumière à amine encombrée pour obtenir une excellente stabilité thermique et uv à long terme Download PDF

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WO2024256443A1
WO2024256443A1 PCT/EP2024/066186 EP2024066186W WO2024256443A1 WO 2024256443 A1 WO2024256443 A1 WO 2024256443A1 EP 2024066186 W EP2024066186 W EP 2024066186W WO 2024256443 A1 WO2024256443 A1 WO 2024256443A1
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alkyl
group
independently selected
alkoxy
unsubstituted phenyl
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Inventor
Minna Kaarina AARNIO-WINTERHOF
Francis Reny COSTA
Dietrich Gloger
Jeroen Oderkerk
Jessica HESSELGREN
Yuliia ROMANENKO
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Borealis GmbH
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Borealis GmbH
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    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/804—Materials of encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/85—Protective back sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/12—Photovoltaic modules

Definitions

  • the present invention relates to a photovoltaic module having a protective back layer element that comprises a polypropylene composition comprising a certain combination of hindered amine light stabilizers and UV stabilizers, as well as to the use of the certain blend of hindered amine light stabilizers and UV stabilizers for maintaining elongation at break after UV or oven treatment.
  • the mechanical properties of polymeric articles have particular requirements.
  • the polymeric material must, for example, withstand UV light that can be severe in some geographical regions.
  • the temperature can vary within wide range. Therefore, long-term thermal stability, especially at high temperatures, is also often required.
  • polypropylenes used as external elements in photovoltaic modules in particular in bifacial photovoltaic modules, it is important to combine good UV and thermal stability with excellent optical properties to ensure that the polypropylene external elements do not reduce the amount of light arriving at the photovoltaic elements of the photovoltaic module.
  • the present invention is based on the finding that a combination of certain polymeric hindered amine light stabilizers, certain triazine -based UV stabilizers and certain further UV stabilizers combine to give excellent UV protection for polypropylenes, making polypropylene compositions comprising such a combination of additives an excellent choice for use as an external layer of a photovoltaic module.
  • the present invention is directed to a photovoltaic (PV) module, comprising, in the given order, a protective front layer element (1), a front encapsulation layer element (2), a photovoltaic element (3), a rear encapsulation layer element (4) and a protective back layer element (5), wherein the protective back layer element (5) comprises a polypropylene composition (PC) that comprises: a) 90.00 to 99.90 wt.-%, relative to the total weight of the polypropylene composition (PC), of a polypropylene or mixture of polypropylenes (PP); and b) 0.10 to 4.00 wt.-%, relative to the total weight of the polypropylene composition (PC), of a blend (B) of UV stabilizers and hindered amine light stabilizers, said blend (B) comprising, more preferably consisting of: i) one or more polymeric hindered amine light stabilizers (HAUS) having a structure according to formula (I)
  • PC polypropylene
  • R A is selected from the group consisting of hydrogen and Ci to Cw alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to Cw alkyl and unsubstituted phenyl;
  • R B is selected from the group consisting of Ci to Cw alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to C10 alkyl and unsubstituted phenyl, wherein R c is selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy;
  • a 1 and B 1 are each independently selected from the group consisting of direct single bond, Ci to Ce alkylene, and phenylene;
  • a 2 and B 2 are each independently selected from the group consisting of direct single bond, wherein each of R A1 , R A2 and R A3 are each independently selected from the group consisting of hydrogen and Ci to Cw alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to Cw alkyl and unsubstituted phenyl, and R B1 is selected from the group consisting of Ci to Cw alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to Cw alkyl and unsubstituted phenyl, and , wherein R D is selected from the group consisting of hydrogen,
  • UV1 triazine-based UV stabilizers having a structure according to formula (II) wherein R 1 represents from 0 to 4 substitutions, each independently selected from the group consisting of hydroxy, Ci to Cw alkyl, Ci to C12 alkoxy, unsubstituted phenyl, and phenyl substituted by one or more groups independently selected from the group consisting of hydroxy, Ci to C10 alkyl and Ci to C 12 alkoxy, and
  • R 2 and R 3 each independently represent from 0 to 5 substitutions, each independently selected from the group consisting of hydroxy, Ci to C10 alkyl, Ci to C12 alkoxy, unsubstituted phenyl, and phenyl substituted by one or more groups independently selected from the group consisting of hydroxy, Ci to C10 alkyl and Ci to C12 alkoxy; and iii) one or more further UV stabilizers (UV2) having a structure according to formula (III) wherein X is selected from the group consisting of O and direct single bond; R’ represents from 0 to 5 substitutions, each independently selected from the group consisting of hydroxy, Ci to C10 alkyl, Ci to C12 alkoxy, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to C10 alkyl and Ci to C12 alkoxy; and R’ ’ is selected from the group consisting of Ci to C20 alkyl, unsubstituted phenyl and
  • the present invention is directed to a polypropylene composition (PC) that comprises: a) 90.00 to 99.90 wt.-%, relative to the total weight of the polypropylene composition (PC), of a polypropylene or mixture of polypropylenes (PP); and b) 0.10 to 4.00 wt.-%, relative to the total weight of the polypropylene composition (PC), of a blend (B) of UV stabilizers and hindered amine light stabilizers, said blend (B) comprising, more preferably consisting of: i) one or more polymeric hindered amine light stabilizers (HALS) having a structure according to formula (I) wherein m is an integer in the range from 2 to 8 and n is an integer in the range from 2 to 10, each R is independently selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy;
  • PC polypropylene composition
  • PC polypropylene composition
  • PP polypropylene or mixture of polypropylene
  • R A is selected from the group consisting of hydrogen and Ci to Cio alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to Cio alkyl and unsubstituted phenyl;
  • R B is selected from the group consisting of Ci to Cio alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to Cio alkyl and unsubstituted phenyl, wherein R c is selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy;
  • a 1 and B 1 are each independently selected from the group consisting of direct single bond, Ci to Ce alkylene, and phenylene;
  • a 2 and B 2 are each independently selected from the group consisting of direct single bond, wherein each of R A1 , R A2 and R A3 are each independently selected from the group consisting of hydrogen and Ci to Cio alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to Cio alkyl and unsubstituted phenyl, and R B1 is selected from the group consisting of Ci to Cio alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to Cio alkyl and unsubstituted phenyl, and , wherein R D is selected from the group consisting of hydrogen,
  • UV1 triazine-based UV stabilizers having a structure according to formula (II) wherein R 1 represents from 0 to 4 substitutions, each independently selected from the group consisting of hydroxy, Ci to Cw alkyl, Ci to C12 alkoxy, unsubstituted phenyl, and phenyl substituted by one or more groups independently selected from the group consisting of hydroxy, Ci to C10 alkyl and Ci to C 12 alkoxy, and
  • R 2 and R 3 each independently represent from 0 to 5 substitutions, each independently selected from the group consisting of hydroxy, Ci to C10 alkyl, Ci to C12 alkoxy, unsubstituted phenyl, and phenyl substituted by one or more groups independently selected from the group consisting of hydroxy, Ci to C10 alkyl and Ci to C12 alkoxy; and iii) one or more further UV stabilizers (UV2) having a structure according to formula (III) wherein X is selected from the group consisting of O and direct single bond; R’ represents from 0 to 5 substitutions, each independently selected from the group consisting of hydroxy, Ci to C10 alkyl, Ci to C12 alkoxy, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to C10 alkyl and Ci to C12 alkoxy; and R’ ’ is selected from the group consisting of Ci to C20 alkyl, unsubstituted phenyl and
  • the present invention is directed to a use of a blend (B) of UV stabilizers and hindered amine light stabilizers for maintaining elongation at break, determined according to ISO 527-3 on monolayer fdm specimens having a thickness of 400 pm, of a polypropylene composition comprising said blend (B) after UV aging for 3000 h as described in the determination methods, wherein the blend (B) comprises, more preferably consists of: i) one or more polymeric hindered amine light stabilizers (HALS) having a structure according to formula wherein m is an integer in the range from 2 to 8 and n is an integer in the range from 2 to 10, each R is independently selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy;
  • HALS polymeric hindered amine light stabilizers
  • R A is selected from the group consisting of hydrogen and Ci to C alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to Cw alkyl and unsubstituted phenyl;
  • R B is selected from the group consisting of Ci to Cw alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to C alkyl and unsubstituted phenyl, wherein R c is selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy;
  • a 1 and B 1 are each independently selected from the group consisting of direct single bond, Ci to Ce alkylene, and phenylene;
  • a 2 and B 2 are each independently selected from the group consisting of direct single bond, wherein each of R A1 , R A2 and R A3 are each independently selected from the group consisting of hydrogen and Ci to C alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to Cw alkyl and unsubstituted phenyl, and R B1 is selected from the group consisting of Ci to C alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to Cw alkyl and unsubstituted phenyl, wherein R D is selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy, wherein if A 1 and A 2 are both direct single bond then A 1 and A 2 together form a single bond linking the nitrogen atom to the 6-membered ring, and wherein if B 1 and B 2 are both direct single bond then B 1 and B 2 together form
  • R’ represents from 0 to 5 substitutions, each independently selected from the group consisting of hydroxy, Ci to Cio alkyl, Ci to C12 alkoxy, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to Cio alkyl and Ci to C12 alkoxy; and
  • R’ ’ is selected from the group consisting of Ci to C20 alkyl, unsubstituted phenyl and phenyl with from 1 to 5 substitutions, each of which are independently selected from the group consisting of hydroxy, Ci to Cio alkyl being optionally substituted by acrylate substitution, Ci to C12 alkoxy being optionally substituted by acrylate substitution, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to Cw alkyl being optionally substituted by acrylate substitution and Ci to C12 alkoxy being optionally substituted by acrylate substitution, wherein the structure according to formula (III) contains a phenol moiety, wherein either at least one instance of R’ is hydroxy or R’ ’ is phenyl substituted by at least a hydroxy, wherein maintaining the elongation at break is achieved when the value of the elongation at break after UV aging for 3000 h as described in the determination methods is at least 40% of the value
  • the present invention is directed to a use of a blend (B) of UV stabilizers and hindered amine light stabilizers for maintaining elongation at break, determined according to ISO 527-3 on monolayer film specimens having a thickness of 400 pm, of a polypropylene composition comprising said blend (B) after oven aging at 120 °C for 2000 h, wherein the blend (B) comprises, more preferably consists of: i) one or more polymeric hindered amine light stabilizers (HALS) having a structure according to formula wherein m is an integer in the range from 2 to 8 and n is an integer in the range from 2 to 10, each R is independently selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy; R A is selected from the group consisting of hydrogen and Ci to Cw alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to C alkyl and unsubstituted phen
  • R B is selected from the group consisting of Ci to Cw alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to Cw alkyl and unsubstituted phenyl, wherein R c is selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy;
  • a 1 and B 1 are each independently selected from the group consisting of direct single bond, Ci to Ce alkylene, and phenylene;
  • a 2 and B 2 are each independently selected from the group consisting of direct single bond, wherein each of R A1 , R A2 and R A3 are each independently selected from the group consisting of hydrogen and Ci to Cw alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to Cw alkyl and unsubstituted phenyl, and R B1 is selected from the group consisting of Ci to Cw alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to C10 alkyl and unsubstituted phenyl, wherein R D is selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy, wherein if A 1 and A 2 are both direct single bond then A 1 and A 2 together form a single bond linking the nitrogen atom to the 6-membered ring, and wherein if B 1 and B 2 are both direct single bond then B 1 and B 2 together
  • R’ represents from 0 to 5 substitutions, each independently selected from the group consisting of hydroxy, Ci to Cw alkyl, Ci to C12 alkoxy, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to C10 alkyl and Ci to C12 alkoxy; and
  • R’ ’ is selected from the group consisting of Ci to C20 alkyl, unsubstituted phenyl and phenyl with from 1 to 5 substitutions, each of which are independently selected from the group consisting of hydroxy, Ci to Cw alkyl being optionally substituted by acrylate substitution, Ci to C12 alkoxy being optionally substituted by acrylate substitution, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to Cw alkyl being optionally substituted by acrylate substitution and Ci to C12 alkoxy being optionally substituted by acrylate substitution, wherein the structure according to formula (III) contains a phenol moiety, wherein either at least one instance of R’ is hydroxy or R’ ’ is phenyl substituted by at least a hydroxy, wherein maintaining the elongation at break is achieved when the value of the elongation at break after oven aging at 120 °C for 2000 h is at least 50% of the value determined before
  • a propylene homopolymer is a polymer that essentially consists of propylene monomer units. Due to impurities especially during commercial polymerization processes, a propylene homopolymer can comprise up to 0.1 mol% comonomer units, preferably up to 0.05 mol% comonomer units and most preferably up to 0.01 mol% comonomer units.
  • a propylene copolymer is a copolymer of propylene monomer units and comonomer units, preferably selected from ethylene and C4-C8 alpha-olefins.
  • a propylene random copolymer is a propylene copolymer wherein the comonomer units are randomly distributed along the polymer chain, whilst a propylene block copolymer comprises blocks of propylene monomer units and blocks of comonomer units.
  • Propylene random copolymers can comprise comonomer units from one or more comonomers different in their amounts of carbon atoms.
  • Heterophasic propylene copolymers typically comprise: a) a crystalline propylene homopolymer or copolymer matrix (M); and b) an elastomeric rubber, preferably a propylene -ethylene copolymer (E).
  • said crystalline matrix phase is a random copolymer of propylene and at least one alpha-olefin comonomer.
  • a plastomer is a polymer that combines the qualities of elastomers and plastics, such as rubber-like properties with the processing abilities of plastic.
  • An ethylene-based plastomer is a plastomer with a molar majority of ethylene monomer units.
  • a bifacial photovoltaic module is a photovoltaic module that produces solar power from the front and the rear side of the solar cells of the photovoltaic element.
  • PV Photovoltaic
  • the present invention is directed to a photovoltaic (PV) module, comprising, in the given order, a protective front layer element (1), a front encapsulation layer element (2), a photovoltaic element (3), a rear encapsulation layer element (4) and a protective back layer element (5).
  • the protective back layer element (5) comprises, more preferably consists of, the polypropylene composition (PC) as defined below.
  • the “photovoltaic element” means that the element has photovoltaic activity.
  • the photovoltaic element can be e.g. an element of photovoltaic cell(s), which has a well-known meaning in the art.
  • Silicon based material e.g. crystalline silicon
  • Crystalline silicon material can vary with respect to crystallinity and crystal size, as well known to a skilled person.
  • the photovoltaic element can be a substrate layer on one surface of which a further layer or deposit with photovoltaic activity is subjected, for example a glass layer, wherein on one side thereof an ink material with photovoltaic activity is printed, or a substrate layer on one side thereof a material with photovoltaic activity is deposited.
  • a substrate layer on one side thereof a material with photovoltaic activity is deposited.
  • photovoltaic elements e.g. an ink with photovoltaic activity is printed on one side of a substrate, which is typically a glass substrate.
  • the photovoltaic element is most preferably an element of photovoltaic cell(s).
  • Photovoltaic cell(s) means herein a layer element(s) of photovoltaic cells, as explained above, together with connectors.
  • the materials of the above elements other than the protective back layer element (5) are well known in the prior art and can be chosen by a skilled person depending on the desired PV module.
  • the front and rear encapsulation layers (2 and 4) may be selected from any known encapsulation layers known in the art. Suitable materials for encapsulation layers include ethylene vinyl acetate (EVA) and silane-functionalized polyethylenes, such as those disclosed in WO 2017/076629 Al.
  • EVA ethylene vinyl acetate
  • silane-functionalized polyethylenes such as those disclosed in WO 2017/076629 Al.
  • the photovoltaic (PV) module of the present invention is a bifacial photovoltaic module, meaning that light may enter from either the front side or the rear (back) side.
  • the protective back layer element (5) has a total luminous transmittance, determined according to ASTM DI 003- 13, in the range from 70 to 100%, more preferably in the range from 75 to 100%, most preferably in the range from 78 to 100%.
  • the protective front layer element (1) and the protective back layer element (5) may be rigid or flexible.
  • the protective front layer element (1) and the protective back layer element (5) are flexible.
  • the protective back layer element is preferably a fdm having a thickness in the range from 100 to 1000 pm, more preferably in the range from 200 to 800 pm, most preferably in the range from 300 to 600 pm.
  • the fdm may be either a monolayer fdm or a multilayer fdm. If the fdm is a multilayer fdm, then it is preferred that each layer contains the blend (B) of UV stabilisers, although only one layer is required to comprise the polypropylene composition (PC).
  • PC polypropylene composition
  • the fdm is a multilayer fdm, it is also preferred that the fdm is a three-layered fdm, having, in the given order, an adhesive layer, a core layer and a skin layer, wherein at least the core layer, more preferably each of the core layer and the skin layer, comprises the polypropylene composition (PC).
  • PC polypropylene composition
  • each of the adhesive layer, the core layer and the skin layer contains the blend (B) of UV stabilisers.
  • the back layer element Due to the presence of the blend (B) of UV stabilizers and hindered amine light stabilizers in the polypropylene composition (PC) of the protective back layer element, the back layer element has exceptionally good UV protection. This may be evaluated by comparing the elongation at break before and after aging treatments, such as UV aging and thermal (i.e. oven) aging.
  • the protective back layer element (5) has an elongation at break, determined according to ISO 527-3, after UV aging for 3000 h as described in the determination methods is at least 40%, more preferably at least 50%, most preferably at least 70% of the elongation at break, determined according to ISO 527-3, before the UV aging.
  • the protective back layer element (5) has an elongation at break, determined according to ISO 527-3, after oven aging at 120 °C for 2000 h is at least 50%, more preferably at least 65%, most preferably at least 80% of the elongation at break, determined according to ISO 527-3, before the oven aging.
  • the protective back layer element (5) has an elongation at break, determined according to ISO 527-3, in the range from 300 to 1000%, more preferably in the range from 400 to 900%, most preferably in the range from 500 to 800%.
  • PC Polypropylene composition
  • the protective back layer element (5) of the photovoltaic (PV) module comprises a polypropylene composition (PC).
  • the polypropylene composition (PC) is disclosed independently of the other photovoltaic module components.
  • the polypropylene composition (PC) of the first and second aspects comprises: a) 90.00 to 99.90 wt.-%, relative to the total weight of the polypropylene composition (PC), of a polypropylene or mixture of polypropylenes (PP); and b) 0.10 to 4.00 wt.-%, relative to the total weight of the polypropylene composition (PC), of a blend (B) of UV stabilizers and hindered amine light stabilizers.
  • the polypropylene composition (PC) of the first and second aspects comprises: a) 95.00 to 99.70 wt.-%, relative to the total weight of the polypropylene composition (PC), of a polypropylene or mixture of polypropylenes (PP); and b) 0.30 to 3.00 wt.-%, relative to the total weight of the polypropylene composition (PC), of a blend (B) of UV stabilizers and hindered amine light stabilizers.
  • the polypropylene composition (PC) of the first and second aspects comprises: a) 97.00 to 99.50 wt.-%, relative to the total weight of the polypropylene composition (PC), of a polypropylene or mixture of polypropylenes (PP); and b) 0.50 to 2.00 wt.-%, relative to the total weight of the polypropylene composition (PC), of a blend (B) of UV stabilizers and hindered amine light stabilizers.
  • the remaining amount of the polypropylene composition (PC) that is not the polypropylene or mixture of polypropylenes (PP), or the blend (B) is made up of one or more further additives (A) other than hindered amine light stabilizers and UV stabilizers.
  • the polypropylene composition (PC) of the first and second aspects consists of: a) 90.00 to 99.90 wt.-%, relative to the total weight of the polypropylene composition (PC), of a polypropylene or mixture of polypropylenes (PP); b) 0.10 to 4.00 wt.-%, relative to the total weight of the polypropylene composition (PC), of a blend (B) of UV stabilizers and hindered amine light stabilizers; and c) 0.00 to 6.00 wt.-%, relative to the total weight of the polypropylene composition (PC), of one or more further additives (A) other than hindered amine light stabilizers and UV stabilizers.
  • PC polypropylene composition
  • the polypropylene composition (PC) of the first and second aspects consists of: a) 95.00 to 99.70 wt.-%, relative to the total weight of the polypropylene composition (PC), of a polypropylene or mixture of polypropylenes (PP); b) 0.30 to 3.00 wt.-%, relative to the total weight of the polypropylene composition (PC), of a blend (B) of UV stabilizers and hindered amine light stabilizers; and c) 0.00 to 4.00 wt.-%, relative to the total weight of the polypropylene composition (PC), of one or more further additives (A) other than hindered amine light stabilizers and UV stabilizers.
  • PC polypropylene composition
  • the polypropylene composition (PC) of the first and second aspects consists of: a) 97.00 to 99.50 wt.-%, relative to the total weight of the polypropylene composition (PC), of a polypropylene or mixture of polypropylenes (PP); b) 0.50 to 2.00 wt.-%, relative to the total weight of the polypropylene composition (PC), of a blend (B) of UV stabilizers and hindered amine light stabilizers; and c) 0.00 to 2.00 wt.-%, relative to the total weight of the polypropylene composition (PC), of one or more further additives (A) other than hindered amine light stabilizers and UV stabilizers.
  • PC polypropylene composition
  • the polypropylene composition (PC) of the first and second aspects is free from benzotriazole -based UV stabilizers.
  • PC polypropylene composition
  • PP polypropylene or mixture of polypropylenes
  • this component may be any polypropylene or mixture of polypropylenes.
  • Suitable polypropylenes for use in back layer elements of photovoltaic (PV) modules are well known in the art.
  • the polypropylene or mixture of polypropylenes is a heterophasic propylene -ethylene copolymer (HECO), comprising: a) a crystalline matrix (M) being a propylene homopolymer; and b) an amorphous propylene -ethylene elastomer (E) that is dispersed in said crystalline matrix (M).
  • HECO heterophasic propylene -ethylene copolymer
  • the crystalline matrix (M) has a melt flow rate (MFR2), determined according to ISO 1133 at 230 °C and 2.16 kg, in the range from 0.5 to 15.0 g/10 min, more preferably in the range from 1.0 to 10.0 g/10 min, most preferably in the range from 1.5 to 5.0 g/10 min.
  • MFR2 melt flow rate
  • the polypropylene or mixture of polypropylenes PP
  • MFR2 melt flow rate
  • the polypropylene or mixture of polypropylenes (PP), more preferably the heterophasic propylene-ethylene copolymer (HECO), has a xylene cold soluble (XCS) content, determined according to ISO 16152, in the range from 2.0 to 30.0 wt.-%, more preferably in the range from 5.0 to 25.0 wt.-%, most preferably in the range from 10.0 to 20.0 wt.-%.
  • XCS xylene cold soluble
  • the xylene cold soluble content of the polypropylene or mixture of polypropylenes (PP), more preferably of the heterophasic propylene-ethylene copolymer (HECO), has an ethylene content (C2(XCS)), determined by FT-IR spectroscopy, calibrated using quantitative 13 C-NMR spectroscopy, in the range from 20.0 to 60.0 wt.-%, more preferably in the range from 25.0 to 50.0 wt.-%, most preferably in the range from 30.0 to 45.0 wt.-%.
  • the polypropylene or mixture of polypropylenes (PP), more preferably the heterophasic propylene-ethylene copolymer (HECO), has a melting temperature (Tm), determined by differential scanning calorimetry (DSC), in the range from 155 to 171 °C, more preferably in the range from 160 to 170 °C, most preferably in the range from 165 to 169 °C.
  • Tm melting temperature
  • the polypropylene or mixture of polypropylenes (PP), more preferably the heterophasic propylene-ethylene copolymer (HECO), has an ethylene content (C2(total)), determined by FT-IR spectroscopy, calibrated using quantitative 13 C-NMR spectroscopy, in the range from 0.5 to 20.0 wt.-%, more preferably in the range from 1.0 to 10.0 wt.-%, most preferably in the range from 2.0 to 6.0 wt.-%.
  • the polypropylene or mixture of polypropylenes (PP), more preferably the heterophasic propylene-ethylene copolymer (HECO), has a Vicat softening temperature, determined according to ASTM D 1525 method A, in the range from 125 to 170 °C, more preferably in the range from 135 to 165 °C, most preferably in the range from 145 to 160 °C.
  • the polypropylene or mixture of polypropylenes (PP), more preferably the heterophasic propylene-ethylene copolymer (HECO), has a flexural modulus, determined according to ISO 178 using 80x 10x4 mm 3 test bars injection-moulded in line with ISO 19069-2, in the range from 1000 to 2500 MPa, more preferably in the range from 1100 to 2000 MPa, most preferably in the range from 1200 to 1600 MPa.
  • the polypropylene or mixture of polypropylenes (PP), more preferably the heterophasic propylene-ethylene copolymer (HECO), has a Charpy Notched Impact Strength (NIS), determined according to ISO 178 using 80x 10x4 mm 3 test bars injection-moulded in line with ISO 19069-2, in the range from 20 to 100 kJ/m 2 , more preferably in the range from 30 to 80 kJ/m 2 , most preferably in the range from 40 to 60 kJ/m 2 .
  • NIS Charpy Notched Impact Strength
  • One of the essential components of the polypropylene composition is the blend (B) of UV stabilizers and hindered amine light stabilizers.
  • the blend (B) comprises, more preferably consists of, one or more polymeric hindered amine light stabilizers (HALS), one or more triazine -based UV stabilizers (UV1), and one or more further UV stabilizers (UV2).
  • HALS polymeric hindered amine light stabilizers
  • UV1 triazine -based UV stabilizers
  • UV2 further UV stabilizers
  • the blend (B) may further comprise further hindered amine light stabilizers other than the one or more polymeric hindered amine light stabilizers (HALS) and UV stabilizers other than the one or more triazine -based UV stabilizers (UV1) and one or more further UV stabilizers (UV2).
  • HALS polymeric hindered amine light stabilizers
  • UV1 triazine -based UV stabilizers
  • UV2 further UV stabilizers
  • the blend (B) consists of: i) an amount in the range from 20 to 80 wt.-%, more preferably in the range from 25 to 75 wt.-%, most preferably in the range from 30 to 70 wt.-%, relative to the total weight of the blend (B), of the one or more polymeric hindered amine light stabilizers (HALS); ii) an amount in the range from 10 to 40 wt.-%, more preferably in the range from 13 to 35 wt.-%, most preferably in the range from 15 to 30 wt.-%, relative to the total weight of the blend (B), of the one or more triazine-based UV stabilizers (UV1); iii) an amount in the range from 10 to 40 wt.-%, more preferably in the range from 13 to 35 wt.-%, most preferably in the range from 15 to 30 wt.-%, relative to the total weight of the blend (B), of the one or more further UV stabilize
  • the blend (B) consists of: i) an amount in the range from 20 to 80 wt.-%, relative to the total weight of the blend (B), of the one or more polymeric hindered amine light stabilizers (HALS); ii) an amount in the range from 10 to 40 wt.-%, relative to the total weight of the blend (B), of the one or more triazine-based UV stabilizers (UV1); iii) an amount in the range from 10 to 40 wt.-%, relative to the total weight of the blend (B), of the one or more further UV stabilizers (UV2); and iv) optionally an amount in the range from 0 to 50 wt.-%, relative to the total weight of the blend (B), of further hindered amine light stabilizers other than the one or more polymeric hindered amine light stabilizers (HALS) and UV stabilizers other than the one or more triazine-based UV stabilizers (UV1) and one or more
  • the blend (B) consists of: i) an amount in the range from 25 to 75 wt.-%, relative to the total weight of the blend (B), of the one or more polymeric hindered amine light stabilizers (HAUS); ii) an amount in the range from 13 to 35 wt.-%, relative to the total weight of the blend (B), of the one or more triazine-based UV stabilizers (UV1); iii) an amount in the range from 13 to 35 wt.-%, relative to the total weight of the blend (B), of the one or more further UV stabilizers (UV2); and iv) optionally an amount in the range from 0 to 40 wt.-%, relative to the total weight of the blend (B), of further hindered amine light stabilizers other than the one or more polymeric hindered amine light stabilizers (HAUS) and UV stabilizers other than the one or more triazine-based UV stabilizers (UV1) and one or
  • the blend (B) consists of: i) an amount in the range from 30 to 70 wt.-%, relative to the total weight of the blend (B), of the one or more polymeric hindered amine light stabilizers (HAUS); ii) an amount in the range from 15 to 30 wt.-%, relative to the total weight of the blend (B), of the one or more triazine-based UV stabilizers (UV1); iii) an amount in the range from 15 to 30 wt.-%, relative to the total weight of the blend (B), of the one or more further UV stabilizers (UV2); and iv) optionally an amount in the range from 0 to 35 wt.-%, relative to the total weight of the blend (B), of further hindered amine light stabilizers other than the one or more polymeric hindered amine light stabilizers (HAUS) and UV stabilizers other than the one or more triazine-based UV stabilizers (UV1) and one
  • the blend (B) is free from benzotriazole-based UV stabilizers.
  • the individual components of the blend (B) of UV stabilizers and hindered amine light stabilizers will now be described in more detail.
  • HALS polymeric hindered amine light stabilizers
  • One of the essential components of the blend (B) of UV stabilizers and hindered amine light stabilizers is one or more polymeric hindered amine light stabilizers (HALS).
  • HALS polymeric hindered amine light stabilizers
  • the one or more polymeric hindered amine light stabilizers have a structure according to formula (I) m is an integer in the range from 2 to 8, more preferably in the range from 4 to 8, yet more preferably in the range from 4 to 6, most preferably is 6. n is an integer in the range from 2 to 10.
  • Each R is independently selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy, more preferably from the group consisting of hydrogen and Ci to C4 alkyl, yet more preferably from the group consisting of hydrogen, methyl, ethyl, n-propyl and n- butyl, even more preferably from the group consisting of hydrogen and methyl, most preferably R is hydrogen.
  • R A is selected from the group consisting of hydrogen and Ci to Cw alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to Cw alkyl and unsubstituted phenyl, more preferably R A is selected from the group consisting of hydrogen and Ci to Cs alkyl, yet more preferably from the group consisting of hydrogen and C2 to Ce alkyl, even more preferably from the group selected from C3 to Ce alkyl, most preferably R A is n-butyl.
  • R B is selected from the group consisting of Ci to Cw alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to Cw alkyl and unsubstituted phenyl, wherein R c is selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy, more preferably wherein R B is selected from the group consisting wherein R c is selected from the group consisting of hydrogen, and Ci to Ce alkyl, yet more preferably R B is selected from the group selected from the group consisting wherein R c is selected from the group consisting of H and Me, most preferably
  • a 1 and B 1 are each independently selected from the group consisting of direct single bond, Ci to Ce alkylene, and phenylene.
  • a 2 and B 2 are each independently selected from the group consisting of direct single bond, wherein each of R A1 , R A2 and R A3 are each independently selected from the group consisting of hydrogen and Ci to Cio alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to Cio alkyl and unsubstituted phenyl, and R B1 is selected from the group consisting of Ci to Cio alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from
  • Ci Ci to Cio alkyl and unsubstituted phenyl, wherein R D is selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy.
  • a 1 and B 1 are each independently selected from the group consisting of Ci to Ce alkylene
  • a 2 and B 2 are each independently selected from the group consisting wherein each of R A1 , R A2 and R A3 are each independently selected from the group consisting of hydrogen and Ci to Cio alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to Cio alkyl and unsubstituted phenyl
  • R B1 is selected from the group consisting of Ci to C 10 alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to Cio alkyl and unsubstituted phenyl
  • R D is selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy.
  • a 1 and B 1 are each independently selected from the group consisting of C2 to Ce alkylene
  • a 2 and B 2 are each independently selected from the group consisting wherein each of R
  • R A3 are each independently selected from the group consisting of Ci to Cw alkyl, and R B1 is , wherein R D is selected from the group consisting of hydrogen and Ci to Ce alkyl.
  • a 1 and B 1 are each independently selected from the group consisting of C3 to C5 alkylene, and A 2 and B 2 are each independently selected from the group consisting wherein each of R A1 , R A2 and
  • R A3 are each independently selected from the group consisting of C2 to Ce alkyl, and R B1 is In one particular embodiment, A 1 and B 1 are both n-butylene (i.e. linear C4 alkylene), whilst In all of the above embodiments having the following substructure , the NR A2 group is bonded to the 6-membered ring, whilst the NR A3 group is bonded to A 1 or B 1 .
  • a 1 , B 1 , A 2 and B 2 are each direct single bond, meaning that A 1 and A 2 together form a single bond linking the nitrogen atom to the 6- membered ring and that B 1 and B 2 together form a single bond linking the nitrogen atom to the 6-membered ring.
  • the one or more polymeric hindered amine light stabilizers has a structure according to formula (la) m is an integer in the range from 2 to 8, more preferably in the range from 4 to 8, yet more preferably in the range from 4 to 6, most preferably is 6. n is an integer in the range from 2 to 10.
  • R A is selected from the group consisting of hydrogen and Ci to Cw alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to Cw alkyl and unsubstituted phenyl, more preferably R A is selected from the group consisting of hydrogen and Ci to Cs alkyl, yet more preferably from the group consisting of hydrogen and C2 to Ce alkyl, even more preferably from the group selected from C3 to Ce alkyl, most preferably R A is n-butyl.
  • R B is selected from the group consisting of Ci to Cio alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to Cw alkyl and unsubstituted phenyl, wherein R c is selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy, more preferably wherein R B is selected from the group consisting wherein R c is selected from the group consisting of hydrogen, and Ci to Ce alkyl, yet more preferably R 1 is selected from the group selected from the group consisting wherein R c is selected from the group consisting of H and Me, most preferably It is particularly preferred that the one or more polymeric hindered amine light stabilizers (HALS) are selected from the group consisting of
  • the one or more polymeric hindered amine light stabilizers are selected from the group consisting of thereof.
  • the one or more polymeric hindered amine light stabilizer(s) is a single polymeric hinder amine light stabilizer (HALS) being
  • UV1 One or more triazine-based UV stabilizers (UV1)
  • UV1 Another essential component of the blend (B) of UV stabilizers and hindered amine light stabilizers is one or more triazine-based UV stabilizers (UV1) having a structure according to formula (II)
  • R 1 represents from 0 to 4 substitutions, each independently selected from the group consisting of hydroxy, Ci to Cw alkyl, Ci to C12 alkoxy, unsubstituted phenyl, and phenyl substituted by one or more groups independently selected from the group consisting of hydroxy, Ci to C10 alkyl and Ci to C12 alkoxy, more preferably R 1 represents from 0 to 2 substitutions, each independently selected from the group consisting of hydroxy, Ci to C10 alkyl, and C3 to C12 alkoxy, yet more preferably R 1 represents no substitution or a single substitution selected from hydroxy and C3 to C12 alkoxy, most preferably R1 is a single substitution located para to the triazine ring, being selected from C to C alkoxy.
  • R 2 and R 3 each independently represent from 0 to 5 substitutions, each independently selected from the group consisting of hydroxy, Ci to C alkyl, Ci to C12 alkoxy, unsubstituted phenyl, and phenyl substituted by one or more groups independently selected from the group consisting of hydroxy, Ci to Cw alkyl and Ci to C12 alkoxy, more preferably each independently represent from 0 to 2 substitutions, each independently selected from the group consisting of Ci to Cw alkyl, unsubstituted phenyl, and phenyl substituted by one or more groups independently selected from the group consisting of Ci to Cw alkyl.
  • R 2 and R 3 are the same.
  • R 2 and R 3 both represent no substitution.
  • R 2 and R 3 both represent 2,4-dimethyl substitution.
  • R 2 and R 3 both represent 4-phenyl substitution.
  • UV 1 is selected from the group consisting of One or more further UV stabilizers (UV2)
  • UV stabilizers Another essential component of the blend (B) of UV stabilizers and hindered amine light stabilizers is one or more further UV stabilizers (UV2) having a structure according to formula (III)
  • X is selected from the group consisting of O and direct single bond.
  • R’ represents from 0 to 5 substitutions, each independently selected from the group consisting of hydroxy, Ci to Cw alkyl, Ci to C12 alkoxy, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to Cw alkyl and Ci to C12 alkoxy.
  • R’ ’ is selected from the group consisting of Ci to C20 alkyl, unsubstituted phenyl and phenyl with from 1 to 5 substitutions, each of which are independently selected from the group consisting of hydroxy, Ci to Cw alkyl being optionally substituted by acrylate substitution, Ci to C12 alkoxy being optionally substituted by acrylate substitution, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to Cw alkyl being optionally substituted by acrylate substitution and Ci to C12 alkoxy being optionally substituted by acrylate substitution.
  • the structure according to formula (III) contains a phenol moiety, wherein either at least one instance of R’ is hydroxy or R” is phenyl substituted by at least a hydroxy.
  • X is O
  • R’ represents form 1 to 5 substitutions, each of which are independently selected from the group consisting of hydroxy, Ci to Cw alkyl, Ci to C12 alkoxy, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to Cw alkyl and Ci to C12 alkoxy, wherein at least one instance of R’ is hydroxy
  • R” is selected from the group consisting of Ci to C20 alkyl, unsubstituted phenyl and phenyl with from 1 to 5 substitutions, each of which are independently selected from the group consisting of hydroxy, Ci to Cw alkyl, Ci to C12 alkoxy, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to Cw alkyl and Ci to C12 alkoxy.
  • R’ represents 3, 5 -ditert-butyl, 4-hydroxy- substitution, wherein R” is preferably selected from Ce to C20 alkyl, unsubstituted phenyl and phenyl with from 1 to 5 substitutions, each of which are independently selected from Ci to C10 alkyl.
  • R’ represents from 0 to 5 substitutions, each independently selected from the group consisting of hydroxy, Ci to Cw alkyl, Ci to C12 alkoxy, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to Cw alkyl and Ci to C12 alkoxy, and R” is a phenyl substituted by one or more groups independently selected from hydroxy, Ci to Cw alkyl being optionally substituted by acrylate substitution and Ci to C12 alkoxy being optionally substituted by acrylate substitution, wherein at least one substitution is hydroxy, preferably 2-hydroxy substitution.
  • R’ represents no substitution, whilst R” represents 2- hydroxy and 4-Ci-Cw alkoxy being optionally substituted by acrylate substitution.
  • UV stabilizers are selected from the group consisting of mixtures thereof.
  • UV stabilizers are selected from the group consisting mixtures thereof.
  • One or more further additives (A)
  • the polypropylene composition (PC) may contain one or more further additives (A) other than hindered amine light stabilizers and UV stabilizers.
  • the one or more further additives (A) are selected from the group consisting of antioxidants, nucleating agents, pigments, fdlers, clarifiers, brighteners, acid scavengers, slip agents, processing aids, release agents and mixtures thereof.
  • the content of additives includes any carrier polymers used to introduce the additives to the polypropylene composition (PC), i.e. masterbatch carrier polymers.
  • PC polypropylene composition
  • An example of such a carrier polymer would be a polypropylene homopolymer in the form of powder.
  • the present invention is directed to a use of a blend (B) of UV stabilizers and hindered amine light stabilizers for maintaining elongation at break, determined according to ISO 527-3 on monolayer fdm specimens having a thickness of 400 pm, of a polypropylene composition comprising said blend (B) after UV aging for 3000 h as described in the determination methods, wherein the blend (B) comprises, more preferably consists of: i) one or more polymeric hindered amine light stabilizers (HALS) having a structure according to formula wherein m is an integer in the range from 2 to 8 and n is an integer in the range from 2 to 10, each R is independently selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy;
  • HALS polymeric hindered amine light stabilizers
  • R A is selected from the group consisting of hydrogen and Ci to C10 alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to C10 alkyl and unsubstituted phenyl;
  • R B is selected from the group consisting of Ci to C10 alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to C10 alkyl and unsubstituted phenyl, wherein R c is selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy;
  • a 1 and B 1 are each independently selected from the group consisting of direct single bond, Ci to Ce alkylene, and phenylene;
  • a 2 and B 2 are each independently selected from the group consisting of direct single bond, wherein each of R A1 , R A2 and R A3 are each independently selected from the group consisting of hydrogen and Ci to C10 alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to C alkyl and unsubstituted phenyl, and R B1 is selected from the group consisting of Ci to Cw alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to C10 alkyl and unsubstituted phenyl, wherein R D is selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy, wherein if A 1 and A 2 are both direct single bond then A 1 and A 2 together form a single bond linking the nitrogen atom to the 6-membered ring, and wherein if B 1 and B 2 are both direct single bond then B 1 and B 2 together form
  • R’ represents from 0 to 5 substitutions, each independently selected from the group consisting of hydroxy, Ci to Cw alkyl, Ci to C12 alkoxy, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to C10 alkyl and Ci to C12 alkoxy; and
  • R’ ’ is selected from the group consisting of Ci to C20 alkyl, unsubstituted phenyl and phenyl with from 1 to 5 substitutions, each of which are independently selected from the group consisting of hydroxy, Ci to Cw alkyl being optionally substituted by acrylate substitution, Ci to C12 alkoxy being optionally substituted by acrylate substitution, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to Cw alkyl being optionally substituted by acrylate substitution and Ci to C12 alkoxy being optionally substituted by acrylate substitution, wherein the structure according to formula (III) contains a phenol moiety, wherein either at least one instance of R’ is hydroxy or R’ ’ is phenyl substituted by at least a hydroxy, wherein maintaining the elongation at break is achieved when the value of the elongation at break after UV aging for 3000 h as described in the determination methods is at least 40% of the value
  • the present invention is directed to a use of a blend (B) of UV stabilizers and hindered amine light stabilizers for maintaining elongation at break, determined according to ISO 527-3 on monolayer film specimens having a thickness of 400 pm, of a polypropylene composition comprising said blend (B) after oven aging at 120 °C for 2000 h, wherein the blend (B) comprises, more preferably consists of: i) one or more polymeric hindered amine light stabilizers (HALS) having a structure according to formula wherein m is an integer in the range from 2 to 8 and n is an integer in the range from 2 to 10, each R is independently selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy;
  • HALS polymeric hindered amine light stabilizers
  • R A is selected from the group consisting of hydrogen and Ci to C10 alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to C10 alkyl and unsubstituted phenyl;
  • R B is selected from the group consisting of Ci to C10 alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to C10 alkyl and unsubstituted phenyl, wherein R c is selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy;
  • a 1 and B 1 are each independently selected from the group consisting of direct single bond, Ci to Ce alkylene, and phenylene;
  • a 2 and B 2 are each independently selected from the group consisting of direct single bond, wherein each of R A1 , R A2 and R A3 are each independently selected from the group consisting of hydrogen and Ci to C10 alkyl, unsubstituted phenyl and phenyl substituted by one or more groups independently selected from Ci to C alkyl and unsubstituted phenyl, and R B1 is selected from the group consisting of Ci to Cw alkyl, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from Ci to C10 alkyl and unsubstituted phenyl, wherein R D is selected from the group consisting of hydrogen, Ci to Ce alkyl and Ci to C5 alkoxy, wherein if A 1 and A 2 are both direct single bond then A 1 and A 2 together form a single bond linking the nitrogen atom to the 6-membered ring, and wherein if B 1 and B 2 are both direct single bond then B 1 and B 2 together form
  • R’ represents from 0 to 5 substitutions, each independently selected from the group consisting of hydroxy, Ci to Cw alkyl, Ci to C12 alkoxy, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to C10 alkyl and Ci to C12 alkoxy; and
  • R’ ’ is selected from the group consisting of Ci to C20 alkyl, unsubstituted phenyl and phenyl with from 1 to 5 substitutions, each of which are independently selected from the group consisting of hydroxy, Ci to Cw alkyl being optionally substituted by acrylate substitution, Ci to C12 alkoxy being optionally substituted by acrylate substitution, unsubstituted phenyl, phenyl substituted by one or more groups independently selected from hydroxy, Ci to Cw alkyl being optionally substituted by acrylate substitution and Ci to C12 alkoxy being optionally substituted by acrylate substitution, wherein the structure according to formula (III) contains a phenol moiety, wherein either at least one instance of R’ is hydroxy or R’ ’ is phenyl substituted by at least a hydroxy, wherein maintaining the elongation at break is achieved when the value of the elongation at break after oven aging at 120 °C for 2000 h is at least 50% of the value determined before
  • the comonomer content was determined by quantitative Fourier transform infrared spectroscopy (FTIR) after basic assignment calibrated via quantitative 13 C nuclear magnetic resonance (NMR) spectroscopy in a manner well known in the art. Thin films are pressed to a thickness of between 100-500 micrometer and spectra recorded in transmission mode. Specifically, the ethylene content of a polypropylene-co-ethylene copolymer is determined using the baseline corrected peak area of the quantitative bands found at 720-722 and 730-733 cm 1 . Specifically, the butene or hexene content of a polypropylene copolymer is determined using the baseline corrected peak area of the quantitative bands found at 1377-1379 cm 1 . Quantitative results are obtained based upon reference to the film thickness.
  • FTIR quantitative Fourier transform infrared spectroscopy
  • NMR nuclear magnetic resonance
  • C is the content of comonomer in weight-%
  • w is the weight fraction of the component in the mixture
  • subscripts b, 1 and 2 refer to the overall mixture, component 1 and component 2, respectively.
  • the comonomer content in weight basis in a binary copolymer can be converted to the comonomer content in mole basis by using the following equation where c m is the mole fraction of comonomer units in the copolymer, c w is the weight fraction of comonomer units in the copolymer, MW C is the molecular weight of the comonomer (such as ethylene) and MW m is the molecular weight of the main monomer (i.e., propylene).
  • the crystalline and amorphous fractions are separated through temperature cycles of dissolution at 160 °C, crystallization at 40 °C and re-dissolution in 1 ,2,4-trichlorobenzene at 160 °C.
  • Quantification of SF and CF and determination of ethylene content (C2) are achieved by means of an integrated infrared detector (IR4) and for the determination of the intrinsic viscosity (IV) an online 2-capillary viscometer is used.
  • the IR4 detector is a multiple wavelength detector measuring IR absorbance at two different bands (CPF stretching vibration (centred at app. 2960 cm 1 ) and the CH stretching vibration (2700-3000 cm 1 ) that are serving for the determination of the concentration and the Ethylene content in Ethylene-Propylene copolymers.
  • the IR4 detector is calibrated with series of 8 EP copolymers with known Ethylene content in the range of 2 wt.-% to 69 wt.-% (determined by 13 C-NMR) and each at various concentrations, in the range of 2 and 13mg/ml. To encounter for both features, concentration and ethylene content at the same time for various polymer concentrations expected during Crystex analyses the following calibration equations were applied:
  • the CH3/IOOOC is converted to the ethylene content in wt.-% using following relationship:
  • Amounts of Soluble Fraction (SF) and Crystalline Fraction (CF) are correlated through the XS calibration to the “Xylene Cold Soluble” (XCS) quantity and respectively Xylene Cold Insoluble (XCI) fractions, determined according to standard gravimetric method as per ISO16152.
  • XCS Xylene Cold Soluble
  • XCI Xylene Cold Insoluble
  • the samples to be analyzed are weighed out in concentrations of lOmg/ml to 20mg/ml.
  • the sample is dissolved at 160 °C until complete dissolution is achieved, usually for 60 min, with constant stirring of 400rpm. To avoid sample degradation, the polymer solution is blanketed with the N2 atmosphere during dissolution.
  • BHT 2,6-tert-butyl-4- methylphenol
  • a defined volume of the sample solution is injected into the column filled with inert support where the crystallization of the sample and separation of the soluble fraction from the crystalline part is taking place. This process is repeated two times. During the first injection the whole sample is measured at high temperature, determining the IV[dl/g] and the C2[wt.%] of the PP composition. During the second injection the soluble fraction (at low temperature) and the crystalline fraction (at high temperature) with the crystallization cycle are measured (wt.-% SF, wt.-% C2, IV).
  • the intrinsic viscosity (iV) is measured according to DIN ISO 1628/1, October 1999, in Decalin at 135 °C.
  • the melt flow rate is determined according to ISO 1133 and is indicated in g/10 min.
  • the MFR is an indication of the flowability, and hence the processability, of the polymer.
  • the MFR2 of polypropylene is determined at a temperature of 230 °C and a load of 2.16 kg.
  • the density is measured according to ISO 1183-187. Sample preparation is done by compression moulding in accordance with ISO 1872-2:2007.
  • the xylene soluble fraction at room temperature (XCS, wt.-%): The amount of the polymer soluble in xylene is determined at 25 °C according to ISO 16152; 5 th edition; 2005- 07-01.
  • the Vicat softerin temperature was measured according to ASTM D 1525 method A (50°C/h, 10N).
  • Flexural Modulus is determined according to ISO 178 method A (3-point bending test) on 80 mm x 10 mm x 4 mm specimens. Following the standard, a test speed of 2 mm/min and a span length of 16 times the thickness was used. The testing temperature was 23 ⁇ 2 ° C. Injection moulding was carried out according to ISO 19069-2 using a melt temperature of 230 °C for all materials irrespective of material melt flow rate.
  • the Charpy notched impact strength is measured according to ISO 179 leA at +23 °C or -20 °C, using injection moulded bar test specimens of 80x 10x4 mm 3 prepared in accordance with ISO 19069-2 using a melt temperature of 230 °C for all materials irrespective of material melt flow rate.
  • Tensile properties i.e. Elongation at Break
  • ISO 527-3 Tensile properties in machine and transverse direction were determined according to ISO 527-3 at 23 °C on the monolayer films produced in the experimental section. Testing was performed at a cross-head speed of 1 mm/min.
  • Total luminous transmittance was determined according to ASTM D1003-13 directly on the monolayer films produced in the experimental section.
  • the monolayer films produced in the experimental section were heated at 120°C for the specified amount of time. No protective atmosphere was employed, the samples simply being exposed to the air present in the oven during the test.
  • UV aging was carried out according to IEC 62788-2-2, conditions A5. Specimens are mounted in aluminium frames such that the surface faces a xenon arc and are rotated around the irradiation source. The rotation and the air-flow is put such that the defined reference black standard (defined black surface without enhanced heat dissipation) or black panel (defined black surface with enhanced heat dissipation by metal back surface) is at a defined temperature.
  • defined reference black standard defined black surface without enhanced heat dissipation
  • black panel defined black surface with enhanced heat dissipation by metal back surface
  • the irradiation of the xenon arc is filtered by a suprax filter as to accurately reflect spectral power distribution of sunlight especially in the ultraviolet region of radiation.
  • the humidity of the environment is defined. Conditioning is performed for a defined time interval without any testing.
  • inventive, comparative, and reference compositions were prepared in a co-rotating twin- screw extruder (Coperion ZSK 57 for RE1 to RE3 and Coperion ZSK 18 for all other examples) at 220 °C according to the recipes in Table 1.
  • PP Ziegler-Natta catalysed heterophasic propylene copolymer composition with a propylene homopolymer matrix phase having a MFR2 of 2.5 g/10 min and an ethylene-propylene elastomeric phase in an amount of 14 wt.-% (measured as XCS content), and an ethylene content in the elastomeric phase of 37 wt.-%.
  • the heterophasic propylene copolymer composition has a MFR2 of 3.6 g/10 min, a total ethylene content of 4.2 wt.-%, a melting temperature of 168 °C, a Vicat A softening temperature of 153°C, a flexural modulus of 1400 MPa and a Charpy notched impact strength at 23 °C of 45 kJ/m 2 and has been produced using the process as described for the heterophasic propylene copolymer Inv. 2 in the example section of WO 2015/173175. Contains 0.60 wt.-% of an additive blend, commercially available from BASF AG (Germany) under the trade name Irganox CB OP 124.
  • HALS1 Hindered amine light stabilizer (CAS No. 65446-77-0, commercially available from BASF AG (Germany) under the trade name Tinuvin 622) having a structure:
  • HALS2 Hindered amine light stabilizer (CAS No. 71878-19-8, commercially available from BASF AG (Germany) under the trade name Chimassorb 944) having a structure: HALS3 Hindered amine light stabilizer (CAS No. 192268-64-7, commercially available from BASF AG (Germany) under the trade name Chimassorb 2020) having a structure:
  • HALS4 Hindered amine light stabilizer (CAS No. 52829-07-9, commercially available from BASF AG (Germany) under the trade name Tinuvin 770) having a structure:
  • UV1 Triazine-based UV stabilizer (CAS No. 204583-39-1, commercially available from BASF AG (Germany) under the trade name Tinuvin 1600) having a structure: UV2a UV stabilizer (CAS No. 1843-05-6, commercially available from
  • UV2b UV stabilizer (CAS No. 4221-80-1, commercially available from
  • UV3 Benzotriazole-based UV stabilizer (CAS No. 70321-86-7, commercially available from BASF AG (Germany) under the trade name Tinuvin 234) having a structure:
  • Monolayer fdms having a thickness of 400 pm were produced on a Collin line (single screw) with calendaring on both sides, chill roll temperature 25 °C.
  • the total luminous transmittance was in the range from 85 to 91% for each of the films.
  • A4 samples were cut from the resulting films, for use in the UV and oven aging experiments. 2.2 Evaluation of HALS additive
  • the performance of the HALS additives were evaluated by comparing the elongation at break in the machine direction before UV aging and after 1000 or 2000 hours of UV aging as described in the determination methods section.
  • HALS3 Although HALS2 also results in reasonable UV protection.
  • RE4 and RE5 which have higher amounts of HALS3 are less effective than RE3, thus it can be seen that a simple correlation between amount of HALS and UV protection cannot be assumed.
  • a comparative fdm containing only the base PP was completely degraded after 1000 hours of UV aging, thus no tensile properties could be measured.
  • inventive and comparative examples were subjected to UV aging and to oven aging as described in the determination methods section, with the elongation at break in the machine direction again measured at to determine the UV and thermal stability of the polypropylene compositions.
  • Table 3 UV aging behavior of inventive and comparative examples n.m. - not measured, n/a - not applicable (due to sample decomposition)
  • IE1 and IE2 have an improved balance of protection from UV and oven aging (see Table 5 for the average values, reflecting the improved balance), with IE1 having superior long term (i.e. 2000 h) oven aging and IE2 having superior long term (i.e. 2000 h) UV aging relative to CE1 to CE3, with CE4 being worse.
  • Similar tests on fdms prepared from compositions without UV1 and UV2 i.e. only containing various hindered amine light stabilizers) showed that these fdms completely degraded after 2000 h of UV aging and the % retention after 2000 h of oven aging was less than 5%.

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  • Polymers & Plastics (AREA)
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Abstract

La présente invention se rapporte à un module photovoltaïque ayant un élément de couche arrière de protection qui comprend une composition de polypropylène comprenant une certaine combinaison de stabilisants lumière à amine encombrée et de stabilisants UV, et à l'utilisation de ladite combinaison de stabilisants lumière à amine encombrée et de stabilisants UV pour maintenir l'allongement à la rupture après un traitement aux UV ou au four.
PCT/EP2024/066186 2023-06-13 2024-06-12 Mélange de stabilisants uv et de stabilisants lumière à amine encombrée pour obtenir une excellente stabilité thermique et uv à long terme Pending WO2024256443A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8431235B2 (en) * 2008-11-06 2013-04-30 Dow Global Technologies Llc Co-extruded, multilayered polyolefin-based backsheet for electronic device modules
WO2015173175A1 (fr) 2014-05-12 2015-11-19 Borealis Ag Composition de polypropylène servant à produire une couche d'un module photovoltaïque
CN105176071A (zh) * 2015-08-14 2015-12-23 明冠新材料股份有限公司 一种无氟两层共挤光伏背板及其制备方法
WO2017076629A1 (fr) 2015-11-04 2017-05-11 Borealis Ag Module photovoltaïque
EP3161059B1 (fr) * 2014-06-24 2019-07-24 Dow Global Technologies LLC Feuille arrière photovoltaïque de polyolefine comprenant une couche de polypropylène stabilise
US20220169829A1 (en) * 2020-11-27 2022-06-02 Cytec Industries Inc. Compositions and methods for protecting organic polymeric materials from the deleterious effects of exposure to uv-c light

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8431235B2 (en) * 2008-11-06 2013-04-30 Dow Global Technologies Llc Co-extruded, multilayered polyolefin-based backsheet for electronic device modules
WO2015173175A1 (fr) 2014-05-12 2015-11-19 Borealis Ag Composition de polypropylène servant à produire une couche d'un module photovoltaïque
EP3161059B1 (fr) * 2014-06-24 2019-07-24 Dow Global Technologies LLC Feuille arrière photovoltaïque de polyolefine comprenant une couche de polypropylène stabilise
CN105176071A (zh) * 2015-08-14 2015-12-23 明冠新材料股份有限公司 一种无氟两层共挤光伏背板及其制备方法
WO2017076629A1 (fr) 2015-11-04 2017-05-11 Borealis Ag Module photovoltaïque
US20220169829A1 (en) * 2020-11-27 2022-06-02 Cytec Industries Inc. Compositions and methods for protecting organic polymeric materials from the deleterious effects of exposure to uv-c light

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LJILJANA JEREMICANDREAS ALBRECHTMARTINA SANDHOLZERMARKUS GAHLEITNER: "Rapid characterization of high-impact ethylene-propylene copolymer composition by crystallization extraction separation: comparability to standard separation methods", INTERNATIONAL JOURNAL OF POLYMER ANALYSIS AND CHARACTERIZATION, vol. 25, no. 8, 2020, pages 581 - 596

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