EP3083780A1 - Uninflammable pvdf film that is resistant to tearing at low temperatures - Google Patents
Uninflammable pvdf film that is resistant to tearing at low temperaturesInfo
- Publication number
- EP3083780A1 EP3083780A1 EP14830819.0A EP14830819A EP3083780A1 EP 3083780 A1 EP3083780 A1 EP 3083780A1 EP 14830819 A EP14830819 A EP 14830819A EP 3083780 A1 EP3083780 A1 EP 3083780A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- film
- vinyl
- alkyl
- film according
- core
- 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.)
- Withdrawn
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- 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
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- 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
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- 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
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
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- 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
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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- 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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/582—Tearability
- B32B2307/5825—Tear resistant
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- 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
- B32B2419/00—Buildings or parts thereof
- B32B2419/06—Roofs, roof membranes
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- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- 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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/08—Homopolymers or copolymers of acrylic acid esters
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- 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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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- 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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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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
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
Definitions
- the present invention relates to a fluorinated film having properties making it suitable for use outdoors, particularly in the field of breeding as cover films houses or shelters for livestock.
- the film according to the invention comprises a polyvinylidene fluoride matrix, at least one impact modifier and a flame retardant.
- Agricultural greenhouses are used to shelter livestock, protecting them from climatic elements.
- the cover of these greenhouses is translucent and generally made of glass, but also of plastic (for example: polyethylene film, semi-rigid PVC sheets) rigid or flexible, generally treated to withstand ultraviolet light. This film can be armed to increase its resistance to rips.
- the films used for the roofs of livestock buildings must have multiple properties:
- WO 2011/121228 discloses multilayer fluorinated films comprising at least 3 layers, including a layer A in a first copolymer of vinylidene fluoride having a crystallization temperature TcA, and a layer B in a second copolymer of vinylidene fluoride having a crystallization temperature TcB, TcA being greater than TcB, layers A and B being alternate, layer A being placed on the outside and layer B between two layers A.
- TcA being greater than TcB
- layers A and B being alternate, layer A being placed on the outside and layer B between two layers A.
- the tear resistance of these films has been significantly improved, compared to known fluorinated films, however it remains insufficient at low temperature.
- fluorinated films for application as a roof and / or facade of livestock buildings which, in addition to the general characteristics described above, have good tear resistance properties in a temperature range from - 20 ° C to + 60 ° C and leave partially light, contributing to the welfare of animals by a harmonious distribution of natural light, while having a good fire resistance.
- One of the objects of the present invention consists of a PVDF monolayer film modified by addition of at least one heart-bar shock modifier ("coreshell”) and also containing a flame-retardant agent.
- coreshell heart-bar shock modifier
- PVDF layer a multilayer film comprising at least one modified PVDF layer as described above, and at least one layer of unmodified PVDF, that is to say a PVDF which contains neither a modified shock nor a flame retardant (hereinafter referred to as "PVDF layer").
- PVDF layer a PVDF which contains neither a modified shock nor a flame retardant
- this PVDF layer is located outside the multilayer film.
- Another subject of the invention relates to the use of the films according to the invention as roofing materials for agricultural buildings, in particular as roofs and / or facades for greenhouses for animals.
- the invention relates to a monolayer polymer film comprising a polyvinylidene fluoride (PVDF) matrix, at least one impact modifier and a flame retardant, in which the impact modifier mass ratio varies between 2.5% and less. 40%.
- PVDF polyvinylidene fluoride
- the object of the invention therefore relates to the addition of a second flame retardant additive, which makes it possible to restore the fire resistance of the product while maintaining an improved tear resistance by the presence of impact modifiers.
- a second flame retardant additive which makes it possible to restore the fire resistance of the product while maintaining an improved tear resistance by the presence of impact modifiers.
- phosphorus flame retardants for example metal or organometallic salts of phosphonate,
- the ratio of the total amount of flame retardant to that of impact modifier is between 1/30 and 1/1, preferably between 1/15 and 1/7.
- the thickness of the film according to the invention is between 30 and 200 microns, preferably between 80 and 150 microns (inclusive).
- the impact modifying rate is greater than 5% and less than or equal to 30% of the total weight of the film.
- the level of impact modifier is greater than or equal to 10% and less than or equal to 30%.
- the monolayer film according to the invention consists of a PVDF matrix, at least one core-shell shock modifier and a flame retardant agent.
- VDF vinylidene fluoride
- VF3 trifluoroethylene
- CTFE chloro
- said matrix is made of PVDF homopolymer.
- said matrix consists of a VDF copolymer.
- the fluorinated comonomer is chosen from chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoroethylene (VF3) and tetrafluoroethylene (TFE), and mixtures thereof.
- the comonomer is advantageously the HFP.
- the copolymer comprises only VDF and HFP.
- the fluorinated copolymers are copolymers of VDF such as VDF-HFP containing at least 50% by weight of VDF, advantageously at least 75% by weight of VDF and preferably at least 80% by weight of VDF.
- VDF-HFP a copolymer of VDF containing more than 75% of VDF and HFP supplement marketed by Arkema under the name Kynar Flex ®.
- the core-shell shock modifier is, in one embodiment, in the form of fine particles having an elastomeric core (having a glass transition temperature of less than 25 ° C, preferably less than 0 ° C, more preferably less than -5 ° C, even more preferably less than -25 ° C), and at least one thermoplastic bark (comprising at least one polymer having a glass transition temperature greater than 25 ° C).
- the size of the particles is generally less than one micron and advantageously between 50 and 300 nm.
- homopolymers of isoprene or butadiene may be mentioned, copolymers of isoprene with at most 30 mol% of a vinyl monomer and copolymers of butadiene with at most 30 mol% of a vinyl monomer.
- the vinyl monomer may be styrene, alkylstyrene, acrylonitrile or alkyl (meth) acrylate.
- Another family of cores consists of the homopolymers of an alkyl (meth) acrylate and the copolymers of an alkyl (meth) acrylate with at most 30 mol% of a monomer chosen from another (meth) ) alkyl acrylate and a vinyl monomer.
- the alkyl (meth) acrylate is advantageously butyl acrylate.
- the core of the impact modifier consists of 2-ethyl-exyl acrylate, which gives a gain in tear-resistance properties equivalent to the product based on butyl-acrylate.
- the core of the core shell copolymer may be crosslinked in whole or in part. It suffices to add at least difunctional monomers during the preparation of the core, these monomers may be chosen from poly (meth) acrylic esters of polyols such as butylene di (meth) acrylate and trimethylolpropane trimethacrylate. Other difunctional monomers are, for example, divinylbenzene, trivinylbenzene, vinyl acrylate and vinyl methacrylate.
- the core may also be cross-linked by grafting or as a comonomer during the polymerization, unsaturated functional monomers such as unsaturated carboxylic acid anhydrides, unsaturated carboxylic acids and unsaturated epoxides. Mention may be made, for example, of maleic anhydride, (meth) acrylic acid and glycidyl methacrylate.
- the bark or barks are homopolymers of styrene, alkylstyrene or methyl methacrylate or copolymers comprising at least 70 mol% of one of these monomers and at least one comonomer selected from the other monomers above another alkyl (meth) acrylate, vinyl acetate and acrylonitrile.
- the bark may be functionalized by introducing, by grafting or as comonomer during the polymerization, unsaturated functional monomers such as unsaturated carboxylic acid anhydrides, unsaturated carboxylic acids and unsaturated epoxides. Mention may be made, for example, of maleic anhydride, (meth) acrylic acid and glycidyl methacrylate.
- the bark may be partially reticulated.
- the bark polymer is made of polystyrene or PMMA.
- core-bark polymers with two barks, one made of polystyrene and the other outside PMMA.
- the core represents, by weight, 70 to 98% of the core-shell polymer and the bark at 2%.
- All of these heart-shell shock modifiers are sometimes called soft / hard because of the elastomeric core.
- bark-like shock modifiers such as hard / soft / hard, that is to say they have in this order a hard heart, soft bark and hard bark.
- the hard parts may consist of the above soft / hard bark polymers and the soft part may consist of the above soft / hard core polymers. For example, those made in this order:
- a bark copolymer of methyl methacrylate and ethyl acrylate is a bark copolymer of methyl methacrylate and ethyl acrylate.
- heart-bar shock modifiers such as hard (heart) / soft / hard.
- the intermediate bark is a copolymer of methyl methacrylate, styrene and at least one monomer selected from alkyl acrylates, butadiene and isoprene.
- the outer bark is a PMMA homopolymer or copolymer. For example, those made in this order:
- the impact modifier contains a core consisting of butylene acrylate or butylene-co-butadiene acrylate or else 2-ethyl-exyl acrylate.
- the bark is formed of poly (methyl methacrylate) or copolymer of methyl methacrylate and another acrylic monomer. These include products from the DURASTRENGTH ® range from ARKEMA.
- acrylic impact modifiers can be used such as the Paraloid TM EXL range from Dow or the range of KANE ACE® on Kaneka.me KANE ACE ® acrylic based Kaneka.
- the impact modifier contains an acrylate-polysiloxane copolymer core and a hard resin bark.
- the heart is a flexible rubber-like material prepared by polymerizing one or more vinyl monomers in the presence of a rubber-like polymer obtained from monomers such as alkyl acrylates or alkyl methacrylates, wherein the alkyl group contains 2 to 10 carbon atoms.
- Polyfunctional monomers such as divinylbenzene, ethylene dimethacrylate, triallyl cyanurate, or triallyl isocyanurate may be added during the polymerization as crosslinking agents.
- the rubber-like polymer thus obtained is combined with a rubber containing polysiloxane.
- the elastomers thus prepared contain at least 20% by weight of rubber-like polymer, preferably at least 40% by weight.
- this type of impact modifier are rubber-based graft copolymers prepared by graft copolymerization of a composite rubber with at least one vinyl monomer, wherein the composite rubber comprises from 5 to 95% by weight of a rubber based on polysiloxane and 5 to 95% by weight of a polyacryl (meth) acrylate rubber.
- the particle size of these impact modifiers varies between 0.01 and 1 micron.
- this type of impact modifier consists of a copolymer core of polysiloxane and butyl acrylate surrounded by a bark of poly (methyl methacrylate). Products of this type are marketed by Mitsubishi Rayon under the reference Metablen ® S-2001.
- the impact modifier is composed of a poly (organosiloxane) core and a thermoplastic resin bark.
- the organic groups of the poly (organosiloxane) cores are preferably alkyl or vinyl radicals containing between 1 and 18 carbons, advantageously between 1 and 6 carbons, or substituted aryl radicals or hydracarbones.
- the poly (organosiloxane) contains one or more of these groups.
- the siloxanes have a variable degree of functionahsation which defines the degree of crosslinking of the poly (organosiloxane).
- the average degree of functionahsation is between 2 and 3 thus forming a partially crosslinked core.
- the bark is formed of polymers or copolymers derived from monomers such as acrylates or alkyl methacrylate, acrylonitrile, styrene, vinylstyrene, vinylpropionate maleimide, vinyl chloride, ethylene, butadiene, isoprene and chloroprene.
- the bark is composed of styrene or acrylate or alkyl methacrylate, the alkyl having between 1 and 4 carbons.
- the fraction of the core represents between 0.05 and 90% by weight of the particles, preferably between 60 and 80% by weight.
- the particle size is between 10 and 400 nm.
- This shock modifier can also be in the form of a heart surrounded by 2 successive barks.
- the description of the core and the outer bark remains identical to that of the silicone shock modifiers with a single bark previously presented.
- the intermediate bark consists of a poly (organosiloxane) different from that of the heart but chosen from the same family of composition.
- this type of impact modifier consists of a polydimethyl siloxane core and a poly (methyl methacrylate) bark.
- Genioperl® range of Silicone Waker can be cited as an example.
- the monolayer film according to the invention comprises an additive reflecting infrared radiation.
- This additive may be a titanium oxide or a mixed compound such as a mother-of-pearl constituted in its center of mica and covered with a layer of titanium oxide.
- Metal alloys can also be used as infrared reflectors. They contain two or more of the following: iron, chromium, cobalt, aluminum, manganese, antimony, zinc, titanium, magnesium.
- this alloy consists of two elements: cobalt and aluminum, or it is a ternary alloy of cobalt, chromium and aluminum.
- the monolayer film according to the invention further comprises at least one additive chosen from:
- plasticizers chosen preferably from dibutyl sebacate, dioctyl phthalate, N-n-butylsulfonamide and polymeric polyesters such as those derived from the combination of adipic, azelaic or sebacic acid and diols. Combinations of these compounds may also be used.
- the films according to the invention have the particularity of combining a high resistance to cold tear with a fire resistance equivalent to that of PVDF.
- the film according to the invention comprises a VDF / HFP copolymer matrix (the compound Al in the examples), an impact modifier having a poly (methyl methacrylate) bark (30%) containing cores of polydimethylsiloxane (70%), and 2% by weight of calcium tungstate as flame retardant.
- the film according to the invention comprises a PVDF homopolymer matrix, an impact modifier having a poly (methacrylate) bark. methyl) (30%) contain polydimethyl-siloxane cores (70%), and 2% by weight calcium tungstate as flame retardant.
- the film according to the invention comprises a VDF / HFP copolymer matrix (the compound Al in the examples), an impact modifier containing a partially crosslinked butyl polyacrylate core (90% by weight) and a bark consists of a copolymer of methyl methacrylate and ethyl acrylate (10%), and 3% of calcium tungstate as flame retardant.
- the film according to the invention comprises a VDF / HFP copolymer matrix (the compound Al in the examples), an impact modifier containing a partially crosslinked butyl polyacrylate core (90% by weight) and a bark is composed of a copolymer of methyl methacrylate and ethyl acrylate (10%), and 2% by weight of benzyl penta-brominated polyacrylate as flame retardant.
- the invention relates to a multilayer film comprising at least one layer of the described monolayer film and at least one other layer of PVDF.
- the overall thickness is between 30 and 200 microns.
- the multilayer film consists of a central layer of PVDF modified with a core - shell shock modifier and containing a flame retardant, and two outer layers of PVDF. These may have the same structure, or they may have different structures.
- modified PVDF layer 20%> - 95%>
- unmodified PVDF layer 5% - 80%
- modified PVDF layer 21 microns
- unmodified PVDF layer 9 microns.
- the invention relates to the methods of preparing films described above.
- PVDF / impact modifier / flame retardant mixtures are obtained by melt compounding techniques known to those skilled in the art, such as BUSS or twin screw.
- the films are then obtained by jacket blowing or by the technique of cast film, these techniques advantageously making it possible to obtain films of large widths.
- the films can be extruded at a temperature between 200 and 280 ° C.
- the inflation rate should be between 1.2 and 4, preferably between 1.5 and 3.
- the stretching ratio should be between 2 and 15, preferably between 5 and 10.
- the invention relates to the use of the monolayer film or multilayer film comprising at least one layer of said monolayer film, as material for the manufacture of films for roofs and / or facades of buildings, particularly agricultural buildings such as livestock buildings.
- These films then have the advantage of having improved durability combined with good resistance to deformation and fire.
- the compounds are produced according to the rules of the art in a twin-screw corotative extruder.
- the films are then made by flat extrusion at 220 ° C. using a flat die with a gap of 1 mm, and stretched by a calendrette to adjust the thickness of the product to the desired target (100 ⁇ ).
- VDF / HFP copolymer having a melt flow rate (MFR) of 7 g / 10min (5kg, 230 ° C), a melting temperature (Tf) of 142 ° C and a Young's modulus of 650 MPa at 23 ° C., measured according to ISO 178.
- MFR melt flow rate
- Tf melting temperature
- Young's modulus 650 MPa at 23 ° C.
- A2 PVDF homopolymer of melt index of 0.14 g / 10 min (5 kg, 230 ° C.) and melting point 168 ° C.
- Shock modifier :
- Bl Durastrength ® D380 acrylic impact modifier from Arkema, in the form of core-shell particles 250 nm in diameter. 90% of partially cross-linked butyl polyacrylate forms the core of the particles.
- the bark (10%>) consists of a copolymer of methyl methacrylate and ethyl acrylate.
- Characterization of the fire resistance the film is placed on a vertical support and is ignited by a flame calibrated according to the UL94 standard. The flame is placed 10 mm below the bottom end of the film and is maintained for 5s. The flame persistence time, the area burned and the presence of inflamed drop are noted. 5 test pieces are analyzed for each sample. Characterization of the resistance to cold tearing: a film of thickness 100 ⁇ is supported by a frame so as to stretch it by applying a tension of IN. A conical 980 g striker is released from a height of 230 mm and pierces the sample. Depending on the rupture profile of the film (long crack propagated in the film or localized stretching), the fragile or ductile nature of the deformation can be estimated. This test is performed at different temperatures to estimate the ductile / brittle transition temperature of the products.
- the most influencing parameter on puncture resistance of the films is in the shock modifier incorporated in the formulation. Its mass fraction and its nature directly impact the ductile or fragile nature of the deformation after cold impact.
- plasticizer in the mixture allows a slight improvement of the ductile behavior of the film at low temperature but its effect is limited as shown by the lack of property noted between Examples 10 and 11 and 12 and 13.
- the change in nature of the Shock modifier in these last 2 examples also causes a significant evolution of the ductile-brittle transition.
- the intrinsic fire resistance of the films is degraded by the presence of the impact modifying particles which are dispersed in the sample, as illustrated in Examples 1 to 5.
- the addition of specific flame retardants in the film formulation makes it possible to simultaneously achieve high fire resistance of the film and a low temperature brittle ductile transition temperature as shown in Examples 14-17.
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1362876A FR3014878B1 (en) | 2013-12-18 | 2013-12-18 | LOW TEMPERATURE AND NON-FLAMMABLE RESISTANT PVDF FILM |
PCT/FR2014/053399 WO2015092282A1 (en) | 2013-12-18 | 2014-12-17 | Uninflammable pvdf film that is resistant to tearing at low temperatures |
Publications (1)
Publication Number | Publication Date |
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EP3083780A1 true EP3083780A1 (en) | 2016-10-26 |
Family
ID=50289962
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP14830819.0A Withdrawn EP3083780A1 (en) | 2013-12-18 | 2014-12-17 | Uninflammable pvdf film that is resistant to tearing at low temperatures |
Country Status (11)
Country | Link |
---|---|
US (1) | US20180163041A1 (en) |
EP (1) | EP3083780A1 (en) |
JP (1) | JP2017502136A (en) |
KR (1) | KR20160101995A (en) |
CN (1) | CN105814122A (en) |
AU (1) | AU2014369588B2 (en) |
CA (1) | CA2933636A1 (en) |
FR (1) | FR3014878B1 (en) |
IL (1) | IL246198A0 (en) |
MX (1) | MX2016007847A (en) |
WO (1) | WO2015092282A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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EP3268429B1 (en) * | 2015-03-11 | 2021-07-21 | Arkema, Inc. | High impact blends of vinylidene fluoride-containing polymers |
JP6712445B2 (en) * | 2015-05-27 | 2020-06-24 | 株式会社バルカー | Thermoplastic fluororesin composition and method for producing crosslinked body |
FR3070042B1 (en) | 2017-08-09 | 2020-08-21 | Arkema France | ORGANIC FIELD-EFFECT TRANSISTOR CONTAINING A DIELECTRIC LAYER WITH HIGH DIELECTRIC PERMITTIVITY AND TEMPERATURE STABLE |
FR3070041B1 (en) * | 2017-08-09 | 2019-08-30 | Arkema France | FORMULATIONS BASED ON ELECTROACTIVE FLUOROPOLYMERS AND THEIR APPLICATIONS |
US11952471B2 (en) * | 2019-09-20 | 2024-04-09 | Korea Advanced Institute Of Science And Technology | Ultrathin and stretchable polymer dielectric and its formation method |
CN116948238B (en) * | 2023-07-20 | 2024-01-30 | 嘉兴高正新材料科技股份有限公司 | Ultra-low temperature-resistant ultraviolet-resistant transparent polyvinylidene fluoride film and preparation method thereof |
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US20070185270A1 (en) * | 2004-05-14 | 2007-08-09 | Roehm Gmbh | Polymer mixture consisting of an impact-resistance modified poly (meth) acrylate and a fluoropolymer |
US20070225430A1 (en) * | 2004-05-17 | 2007-09-27 | Daikin Industries Ltd. | Thermoplastic Polymer Composition |
Family Cites Families (8)
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JP2995790B2 (en) * | 1990-03-19 | 1999-12-27 | ジェイエスアール株式会社 | Thermoplastic resin composition |
DE69816529D1 (en) * | 1997-06-12 | 2003-08-28 | Atofina | Soft and impact resistant polyvinylidene fluoride compositions and process for their manufacture |
KR100638434B1 (en) * | 2004-10-25 | 2006-10-24 | 주식회사 엘지화학 | Silicone-Acrylic Impact Modifier Having Improved Colorability And Thermoplastic Resin Composition Comprising The Same |
KR100838451B1 (en) * | 2005-12-30 | 2008-06-16 | 제일모직주식회사 | Flame retardant polycarbonate resin composition having good impact, high heat resistance |
DE102007007336A1 (en) * | 2007-02-14 | 2008-08-21 | Wacker Chemie Ag | Redispersible core-shell polymers and a process for their preparation |
FR2935706A1 (en) * | 2008-09-08 | 2010-03-12 | Arkema France | Fluorinated polymer composition, used e.g. in pipe for conveying fluid pressure, comprises optionally plasticizer with fluoropolymer, shock modifying particles of core-shell type, and homopolymer or copolymer of vinylidene fluoride |
JP2011195721A (en) * | 2010-03-19 | 2011-10-06 | Fuji Xerox Co Ltd | Modifier, resin composition and resin molded product |
FR2958206A1 (en) | 2010-03-30 | 2011-10-07 | Arkema France | MULTILAYER FLUORINATED FILMS |
-
2013
- 2013-12-18 FR FR1362876A patent/FR3014878B1/en not_active Expired - Fee Related
-
2014
- 2014-12-17 EP EP14830819.0A patent/EP3083780A1/en not_active Withdrawn
- 2014-12-17 CA CA2933636A patent/CA2933636A1/en not_active Abandoned
- 2014-12-17 KR KR1020167019501A patent/KR20160101995A/en not_active Application Discontinuation
- 2014-12-17 CN CN201480069322.XA patent/CN105814122A/en active Pending
- 2014-12-17 AU AU2014369588A patent/AU2014369588B2/en not_active Ceased
- 2014-12-17 WO PCT/FR2014/053399 patent/WO2015092282A1/en active Application Filing
- 2014-12-17 MX MX2016007847A patent/MX2016007847A/en unknown
- 2014-12-17 JP JP2016541047A patent/JP2017502136A/en active Pending
- 2014-12-17 US US15/103,044 patent/US20180163041A1/en not_active Abandoned
-
2016
- 2016-06-14 IL IL246198A patent/IL246198A0/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US20070185270A1 (en) * | 2004-05-14 | 2007-08-09 | Roehm Gmbh | Polymer mixture consisting of an impact-resistance modified poly (meth) acrylate and a fluoropolymer |
US20070225430A1 (en) * | 2004-05-17 | 2007-09-27 | Daikin Industries Ltd. | Thermoplastic Polymer Composition |
Non-Patent Citations (1)
Title |
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See also references of WO2015092282A1 * |
Also Published As
Publication number | Publication date |
---|---|
IL246198A0 (en) | 2016-07-31 |
FR3014878A1 (en) | 2015-06-19 |
CN105814122A (en) | 2016-07-27 |
WO2015092282A1 (en) | 2015-06-25 |
AU2014369588A1 (en) | 2016-06-30 |
MX2016007847A (en) | 2017-02-13 |
KR20160101995A (en) | 2016-08-26 |
US20180163041A1 (en) | 2018-06-14 |
FR3014878B1 (en) | 2015-12-18 |
JP2017502136A (en) | 2017-01-19 |
AU2014369588B2 (en) | 2018-01-04 |
CA2933636A1 (en) | 2015-06-25 |
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