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    • 专利摘要:
    The present invention relates to a waterproofing membrane composition containing polyvinyl chloride (PVC), at least a core-shell impact modifier; at least one polymeric processing aid, characterized in that it further comprises at least one thermoplastic elastomer containing PVC and polyacrylates, and at least one polar copolymer containing at least ethylene vinyl acetate or ethylene N-butyl acrylate, and a polar group selected from the group which consists of hydroxyl, alkoxy, carbonyl, carboxylic acid, carboxylic anhydride, ether, ester, carboxylic esters, epoxy, sulfonyl, nitrile, amide, silane and mixtures thereof.
    公开号:BE1024673B1
    申请号:E2017/5143
    申请日:2017-03-08
    公开日:2018-05-22
    发明作者:Hans Aerts
    申请人:S.A. Imperbel N.V.；
    IPC主号:
    专利说明:

    Holder:
    S.A. IMPERBEL N.V. 1651, LOT Belgium
    Inventor:
    AERTS Hans 1731 ZELLIK Belgium
    Waterproof membrane composition
    The present invention relates to a waterproofing membrane composition containing polyvinyl chloride (PVC), at least one core shell impact modifier; at least one polymeric processing aid, characterized in that it further contains at least a PVC and polyacrylates-containing thermoplastic elastomer, and at least one polar copolymer containing at least ethylene vinyl acetate or ethylene-N-butyl acrylate, and a polar group selected from the group consisting of from hydroxyl, alkoxy, carbonyl, carboxylic acid, carboxylic anhydride, ether, ester, carboxylic acid esters, epoxy, sulfonyl, nitrile, amide, silane and mixtures thereof.
    BELGIAN INVENTION PATENT
    FPS Economy, K.M.O., Self-employed & Energy
    Intellectual Property Office
    Publication number: 1024673 Filing number: BE2017 / 5143
    International classification: C08L 27/06 Date of issue: 22/05/2018
    The Minister of Economy,
    Having regard to the Paris Convention of 20 March 1883 for the Protection of Industrial Property;
    Having regard to the Law of March 28, 1984 on inventive patents, Article 22, for patent applications filed before September 22, 2014;
    Having regard to Title 1 Invention Patents of Book XI of the Economic Law Code, Article XI.24, for patent applications filed from September 22, 2014;
    Having regard to the Royal Decree of 2 December 1986 on the filing, granting and maintenance of inventive patents, Article 28;
    Having regard to the application for an invention patent received by the Intellectual Property Office on 08/03/2017.
    Whereas for patent applications that fall within the scope of Title 1, Book XI, of the Code of Economic Law (hereinafter WER), in accordance with Article XI.19, § 4, second paragraph, of the WER, the granted patent will be limited. to the patent claims for which the novelty search report was prepared, when the patent application is the subject of a novelty search report indicating a lack of unity of invention as referred to in paragraph 1, and when the applicant does not limit his filing and does not file a divisional application in accordance with the search report.
    Decision:
    Article 1
    S.A. IMPERBEL N.V., Bergensesteenweg 32, 1651 LOT Belgium;
    represented by
    GEVERS PATENTS, Holidaystraat 5, 1831, DIEGEM;
    a Belgian invention patent with a term of 20 years, subject to payment of the annual fees as referred to in Article XI.48, § 1 of the Code of Economic Law, for: Waterproof membrane composition.
    INVENTOR (S):
    AERTS Hans, Henri Rosseelslaan 5, 1731, ZELLIK;
    PRIORITY:
    08/03/2016 EP 16159206.8;
    BREAKDOWN:
    Split from basic application: Filing date of the basic application:
    Article 2. - This patent is granted without prior investigation into the patentability of the invention, without warranty of the Merit of the invention, nor of the accuracy of its description and at the risk of the applicant (s).
    Brussels, 22/05/2018,
    With special authorization:
    BE2017 / 5143
    Waterproof membrane composite
    The present invention relates to a waterproofing membrane composition which allows to provide a synthetic waterproofing membrane suitable for covering a roof of a building.
    In general, known waterproofing membranes contain a reinforcing layer with bitumen on at least one side,
    Bitumen contains olls and is obtained ult crude olle,
    When known waterproofing membranes are applied to a building roof, the ollen contained in the bitumen can migrate to the top of waterproofing membranes. Dir oil migration phenomenon is called exudation. This is a known drawback of bitumen-based membranes since the olls can come into contact with rainwater and cause pollution.
    Current trends In waterproofing products for roof20 covering, more attention is being paid to eco-solutions.
    Thanks to the use of synthetic membranes, there are economic solutions on the market, especially for new buildings. Clean synthetic membranes yield cost savings compared to bitumen based membranes. In particular, the production of synthetic membranes requires less material than bitumen-based waterproofing membranes, resulting in a reduced thickness of the final product,
    Synthetic membranes can be fire-resistant, have a good aesthetic appearance, and can be flexible and piodic, so that they can be applied to all deck metrics. In addition, they must be durable and exhibit appropriate physical properties. Physical properties mainly include tensile strength, elongation, hardness and cold brittleness.
    In addition, synthetic membranes, in order to be able to lay them on the roofs of buildings, must have suitable waterproofing
    BE2017 / 5143 properties, These waterproofing properties must be guaranteed over time
    Typically, a synthetic membrane 5 made of PVC contains a reinforcing layer of, for example, polyester and another layer of a PVC-based composition. The PVC is generally modified with a number of plasticizers, coupled with other additives such as pigment, flame retardant, biocide, lubricants, UV stabilizers, etc.,
    The presence of the plasticizers makes it possible to give the PVC in the membrane the desired filiality. In this way, the PVC is protected by the presence of the plasticizers in the mix. PVC is thereby sufficiently embedded in the body of the waterproofing membrane, which is protected from the external environment when mounted on a roof.
    PVC can be used to provide a waterproofing membrane that will remain effective over time provided that the membrane is not adversely affected by its external environment. That is to say that the PVC must remain flexible due to the presence of plasticizers.
    However, it has been established in northern months in northern climates that cold weather conditions can adversely affect the synthetic membrane, thereby significantly shortening the life of the membrane.
    More specifically, synthetic membranes are especially vulnerable when they become brittle over time, leading to PVC embrittlement over their lifetime. This phenomenon is mainly probismatic in international circumstances.
    As described above, PVC membranes owe their fidelity to the additive of plasticizers. However, it has been found that these plasticizers, both in warm and cold directions, end the membrane
    3S can migrate causing it to drown and shrink.
    BE2017 / 5143
    The sudden and catastrophic splintering of a PVC roof membrane is known in the art.
    The lifespan of smooth synthetic waterproofing
    S membranes cannot therefore be guaranteed in the long term.
    In addition to this publication, it has also been observed that known waterproofing membranes with PVC and EVA-CO, plasticizer requirement, allow to avoid the migration of the plasticizer from the body of the membrane.
    However, this type of membrane breaks at a low temperature, especially at -35 ° C, due to the felt that the PVC is not sufficiently flexible. Moreover, the problem of splintering also arises with this type of synthetic membrane.
    Document WO 2015 160 579 A1 relates to the use of core schii impact modifiers with PVC formulations to reduce PVC brittleness and improve impact resistance. This document also describes the possibility of using at least one technical cover fabric in the PVC formings.
    Clean PVC formings do not have a long life since, used in an elndprodoct such as eon waterproofing membrane for roofing, they cannot withstand low temperature, especially around 35 ° C.
    To provide instead of an improved PVC molding, the document describes EP i 152 033 Al eon protective hood coat with climatic properties, which are applied over PVC products.
    The document EP 0 342 283 A1 provides light-scattering polymer compositions and / or polymer compositions with a reduced flange finish than a matte surface.
    There is also a need to provide a water35 sealing membrane composition that allows to provide a synthetic waterproofing membrane with a longer service life than the known synthetic membranes, and for which the splintering4
    BE2017 / 5143 can be reduced, especially at low temperatures (approx. 35 C-.
    It is an object of the present invention to provide a waterproofing membrane composition which makes it possible to provide a synthetic waterproofing membrane with a longer life than the known synthetic membrane, and which can remain efficient for a longer period of time, especially in a cold surroundings,
    For this purpose, the present invention presupposes In a PVC-containing waterproofing membrane composition, at least one pore copolymer, at least one core impact modifier, at least one polymer technical shell material, characterized in that it further contains at least one PVC and polyacrylates thermoplastic egg polymer and at least one polar copolymer containing at least ethylene vinyl acetate (EVA) or at least ethylene N-butyl acrylate (ESA), and a polar group selected from the group consisting of hydroxyl, alkoxy, carbonyl, carboxylic acid, carboxylic anhydride, ether, ester, carboxylic acid esters, epoxy, sulfonyl, nltrlsl, amide, siian, and mixture thereof.
    It has been found that the combination between the at least one polar copolymer containing at least ethylene vinyl acetate (EVA) or ethylene N-butyl acrylate (EBA) and a polar group and the at least one thermoplastic egg-steamer containing PVC and polyacrylates in the presence of PVC to provide In a composition with a longer service life than known waterproofing membrane compositions.
    More specifically, the flexibility of PVC is guaranteed for a longer period of time, thanks to the specific combination as described above. In this way, the fragmentation phenomenon and the cold embrittlement can be greatly reduced. In particular, it has been determined that the composition of this invention can remain stable in cold weather (-35 ° C).
    In practice, according to the present invention, the composition can therefore be applied ορ a reinforcing layer to see In a synthetic membrane for roofing. This example of end use remains stable over time, even in cold weather (-35 ®C). Moreover, the fragmentation phenomenon
    BE2017 / 5143 as described above can be greatly reduced. This offers the possibility of longer retaining the physical properties of the waterproofing membrane when it is mounted on a roof.
    More specifically, the at least one polar copolymer containing at least ethylene vinyl acetate (EVA) or ethylene n-butyl acrylate (EBA) and a polar group exhibits a suitable chemical affinity with PVC in terms of poiarity. This affinity is enhanced due to the presence of the at least one PVC and polyacrylates-containing thermoplastic egg elastomer. This. is extremely cheerful.
    The most important physical properties of a synthetic membrane include elongation, tensile strength, splintering behavior and cold brittleness.
    In the context of the present invention, terms such as containing, containing, comprising, characterized by, having, having, or having any synonym or variation thereof, refer to a non-exclusive presence. For example, a composition, process, use, or product, described as containing a specific list of elements, is not necessarily limited to these specifically listed elements, but may also contain other elements, not specifically listed or inherent in such composition, process, use, or product. ,
    The classical phrase consists of any element, step or ingredient that is not specified in the claim and excludes the conclusion for the inclusion of materials other than the avoidance, please for normas! impurities associated with it,
    When an invention or a part thereof is described with open terms such as containing, it is to be understood that, unless otherwise stated, the invention also includes a description of the invention using the terms existing as previously described.
    In other words, for example, the expression containing can be replaced by the expression consisting of.
    BE2017 / 5143
    Conveniently, the at least one core shell impact modifier has a rubber content of at least 90 weight percent.
    In a specific embodiment, the at least one core shell impact modifier is selected from the group consisting of methacrylate-butadiene-styrene copolymers (MBS), acrylonitrile-butadiene-styrene copolymers (ASS), acrylic core / schi-polymers (AIM), and a combination thereof.
    Preferably, the at least one polymeric engineering fabric is an acrylic polymer.
    In a specific preferred embodiment of this invention, the acrylic polymer is an acrylic polymer with a Tg less than SO ° C, preferably less than 80 ° C, more preferably less than 70 ° C, even more preferably Sager than 60 ° C.
    In addition, In a specific embodiment, said acrylic polymer copolymer contains methyl methacrylate units and at least one other acr / Smonomer.
    In particular, said acrylic polymer copolymer contains from 50 to 79 weight percent of methylimethacrylate units and at least one other acrylic monomer in an amount of from 20 to 50 weight percent.
    Conveniently, the acrylic polymer is an acrylic polymer with a reductive weight of 50,000 to 10,000,000 g / moi.
    Even more finely, the acrylic polymer is an acrylic terpolymer containing methyl methacrylate monomer units, butyl acrylate monomer units and styrene monomer units.
    In particular, said acrylic polymer copolymer contains from 50 to% by weight of methyl methacrylate units and at least one other acrylic monomer in an amount of from 20 to 50% by weight.
    BE2017 / 5143
    According to a preferred embodiment of this invention, the composition contains from 5 to 50 weight percent, preferably from 10 to 40 weight percent, more preferably from 15 to 37 weight percent PVC.
    The present invention preferably contains from 0 to weight percent stabilizer in the liquid state, in particular 3a-Zen stabilizer, whey weight percentage is defined relative to the total weight vsr; the composition,
    In addition, in a specific embodiment, the composition of this invention includes from 5 to 40 weight percent, preferably from 5 to 30 weight percent, more preferably from 8 to 25 weight percent, even more preferably from 9 to 20 weight percent, advantageously less than 20 weight percent , of the at least one polar copolymer containing (EVA15 CO) or (EBA-CO), defined relative to the aggregate weight.
    The hit EVA or EBA in the resp. polar copolymer may in general be between 20 and 50% by weight, and the cage monoxide 20 in the polar copolymer may in general be between 5 and 40% by weight
    More preferably, EVA-CO in accordance with this invention
    28.5 weight percent vinyl acetate units and 9 weight percent cage monoxide25 units, and has a melt flow index of 35 g / 10 min.
    Conveniently, the EBA-CO of the present invention contains 29 weight percent butyl acrylate units and 10 weight percent carbon monoxide units, with a melt index of 12 g / min.
    In a preferred embodiment of this invention, the ethylene / vinyl acetate / cage monoxide copolymer (EVA-CO) is the handcrafted product Eivaioy® 741 or 742 from Dupont,
    According to a preferred embodiment of this invention, the at least one polar copolymer is made of EVA, in this convenient
    BE2017 / 5143 embodiment, the EVA may be the product Afceva® 2820 A from Ceianese.
    More preferably, the polar copolymer may be the product S AMPLIFY ™ TY 1052 H from Dow. In the context of the present invention, the term poial copolymer is to be understood to mean a copolymer made of EVA or EBA containing a polar group selected from the group consisting of hydroxyi, alkoxy, carbonyl, carboxylic acid, carboxylic anhydride, ether, ester, carboxylic acid esters, epoxy, suifonyi, oitriel, srrslde, siiaan and mongels thereof.
    The term "polar group" is to be understood as any group having a bonded dipole moment at an otherwise substantially nopoial olefin moiecuie,
    The polar group can be introduced into the copolymer by grafting or copolymerization.
    According to a specific preferred embodiment of the composition of this invention, the at least one core sehii impact modifier is present in an amount of from 2 to 2S weight percent, more preferably from 4 to 20 weight percent, even more preferably from 5 to 15 weight percent, defined relative to the total weight of the ssmonstelllog.
    Preferably, the at least one bulk is present in an amount of from 2 to 25 weight percent, more preferably from 4 to 20 weight percent, even more preferably from 5 to IS weight percent, relative to the total weight of the composition.
    More preferably, the composition of this invention further contains from 0 to 20 weight percent of a plasticizer defined relative to the weight of the composition.
    Even more preferably, the composition of this invention contains from 0 to 20 weight percent, preferably from 0.1 to 25 weight percent9
    BE2017 / 5143 percent, of a thermoplastic elastomer containing PVC and polyacrylates, defined relative to the total weight of the composition
    In a preferred embodiment, it is thermoplastic
    S elastomer is a copolymer made of PVC grafted with polyacrylates, more preferably PVC grafted with poly (butyl) acrylate. In a preferred embodiment, the thermoplastic PVC is grafted with polyacrylates, more preferably PVC grafted with poly (butyi) acrylate in a 50/50 ratio,
    Other embodiments of the composition according to this invention are described in the appended claims.
    The present invention also relates to a synthetic membrane for roofing, said synthetic membrane containing at least one reinforcing layer as well as at least one layer made from the composition of any of the preceding claims.
    Other embodiments of the synthetic membrane according to this invention are set out in the appended claims.
    so
    Other features and advantages of the invention become more apparent after the following description of a specific non-limiting embodiment of the invention.
    The composition of this invention includes PVC, EVA - CO or
    EBA-CÖ, PVC grafted with poly (butyi) acrylate, at least one core impact modifier and at least one polymeric technical shell material.
    The at least one core impact modifier can be in the form of a particulate requirement with an inner elastomer core (rubber core and at least one outer thermoplastic shell located on the inner elastomer core.
    Preferably, the particle size of a core disc impact modifier is generally less than 1 µm, conveniently between about 59 to about 1099 nm, or between about 50 to about 500 nm f, or between about 80 rsm and approx. 709 nrrs, rnsest preferably between approx. 90 orn and approx.
    BE2017 / 5143
    350 µm, For example, the particle size can be measured with a NIComp® Model 380 ZLS.
    The core scion polymer particulate requirement typically exhibits a steric shape. However, they can take any suitable form.
    In a preferred embodiment, the core-shell polymer particles in the waterproofing membrane composition according to the present invention may exhibit equivalent or substantially equivalent average particle diameter diameters (that is, the waterproofing membrane composition contains no more than one population of core-shell modifier particles with variables).
    More particularly, the core of the at least one core-shell modifier used in the composition of the present invention may be made of isoprene homopolymers or butadiene homopolymer, isoprene-butadiene copolymer, isoprene copolymer with up to 98 weight percent of a vinyl monomer and copolymers of butadiene with up to 98% by weight of a vinyl monomer. The vinyl monomer can be styrene, an akyystyrene, acrylic ion, an alkyl (meth) acrylate, butadiene or isoprene. The core of the core scopolymer can be wholly or partially cross-linked. At least bifunctional monomers can be added during the core calculation. These monomers can be selected from the group consisting of poly (meth) acrylic esters of polyyienes, such as butylene di (meth) acrylate and trimethylolpropane trimethacrylate. Other bifunctional monomers are, for example, divinyl benzene, trivinybenzene, vinyl crystalline, vinyl methacrylate and triali cyanurate. The core can also be cross-linked by introduites, by anting or sis a comonomer during polymerization, of unsaturated functional monomers such as anhydrides of unsaturated carboxylic acids, unsaturated carboxylic acids, and unsaturated epoxides. For example, maleic anhydride, (meth) acrylic acid and glycidyl methacrylate can be avoided. Cross-linking can also be carried out using the intrinsic reactivity of the monomers, for example the diene monomers.
    BE2017 / 5143
    Conveniently, the core-schi impact modifier may be made from styrene homopolymer, alkyl styrene homopolymer or methyl methacrylate bomopolymer, or copolymer with at least 70% by weight of one of said monomers and at least one comonomer selected from the group consisting of the others said monomers, another alkyl (meth) acrylate, vinyl acetate and acrylonitrile. The core can be functionalized by introduces, by grafting or as a comonomer during the polymerization, of unsaturated functional monomers such as anhydrides of unsaturated carboxylic acids, unsaturated carboxylic acids and unsaturated epoxides. For example, maleic anhydride, (meth) acrylic acid glycidyl methacrylate, hydroxyethyl methacrylate and alkyl (meth) acrylamides can be mentioned. As an example, core schiopo polymers with a polystyrene sci and core schiopo polymers with a PMMA shell can be avoided. The sch11 may also contain imide functional groups, by copolymerization with a maleimide or by chemical modification of the PMMA by a primary amine. There are also two-core nuclear plastic copolymers, one made of polystyrene and the other, outer, made of PMMA.
    Non-limiting examples of the types of core-shell impact modifiers that can be used In accordance with the present invention are methacrylate-butadiene-styrene copolymers (MBS), which typically have a core containing a copolymer of butadiene and styrene and a schll containing poly ( methyl methacrylate) (PMMA); acrylonitrile butadiene-styrene copolymers (A3S); or acrylic impact modifiers (AIM), which typically have an acrylic core (e.g., butyl acrylate or 2-ethylhexiacryate) and a PMMA shell.
    The core-shell impact modifier used in the waterproofing membrane of this invention can be defined in accordance with the features disclosed in patent application WO 20X5 / 160579.
    The PVC of this invention preferably has a K value In the range of 40 K to 100 K or a weighted average moiecuiasr weight In the range of 25000 Da to 200000 Da,
    BE2017 / 5143
    The PVC can be finely defined in accordance with the properties stated in patent application WO 2015/160579.
    According to another embodiment of the present invention, the waterproofing membrane composition contains at least one polymeric engineering aid, for example, at least one linear, non-core / polymer polymeric engineering fabric.
    It is known in the art that different types of technical fabrics have an influence on thermoplastic resin-based compositions in various ways, in particular PVC compositions. For example, some polymer technical engineering materials contribute to the fusion of a thermoplastic composition (e.g. a PVC composition),
    IS while others add melt strength or provide lubrication. Polymeric engineering fabrics typically do not alter the mechanical properties of a PVC composition, but they can increase shear efficiency and improve PVC fusion. The incorporation of a polymeric processing aid often improves the impact performance of a thermoplastic composition.
    The polymeric engineering fabric used in the cis composition of this invention is preferably an acrylic copolymer. As an acrylic copolymer, as used herein, is also meant copolymers, terpolymers, and other polymers containing two or more different alkyl methacrylate and / or alkyl diacryl monomer units and mixtures thereof. The polymer architecture of the Copolymers can be random, block, kegei, comb, rigid or otherwise. The alkyl methacrylate monomer units are preferably methyl methacrylate (MMA), which can occupy from 50 to 79 weight percent, more preferably from 50 to 75 weight percent, even more preferably from SO to 70 weight percent of the monomer mixture. The remaining weight percent of the polymer is comprised of at least one other alkyl acrylate and / or alkyl methacrylate type monomer units, and may also contain other ethylenically unsaturated monomers. Other (non-acrylic) monomers Note The copolymer composition includes, but is not limited to, styrene, aphamethyistyrene, acrylic ion, and crossiinkers may also be present in the monomer mixture.
    BE2017 / 5143
    The Tg of the acrylic copolymer is preferably less than 90 ° C, preferably less than 80 ° C, more preferably less than 70 ° C, even more preferably less than 65 ° C, even more preferably less than 60 ° C C.
    In addition to the methyl methacrylate monomer units, examples of aromeric methacrylate and aerylate monomers are useful. and ethyl / imethacrylate, stearyl acrylate and stearyl methacrylate, isobornyl acrylate and methacrylate, methoxyethyl acrylate and methacrylate, 2-ethoxyethyl acrylate and methacrylate methyl acrylate-methyl acrylate and methyl acrylate can be useful for the monomer mixture,
    A preferred acrylic copolymer is one formed of methyl methacrylate (MMA) and butyl acrylate (BA) monomer units, 1 M with MMA / BA copolymer, the level of MMA is 79 weight percent or less, preferably 75 weight percent or less, even more preferably 70 weight 20 percent or less, and the level of BA monomer units is 21 weight percent or more, preferably tes! at least 25 weight percent or more, even more preferably 30 weight percent or more.
    The acrylic copolymer can be formed into powder or granulate.
    The powder can be formed by any means such as spray drying, drum drying, freeze drying, vacuum drying or coagulation with physical or chemical agents. The acrylic copolymer can be supplied before use In productif In a user-friendly form such as, but not limited to, a powder, granulate or pellets,
    The at least one polymeric processing aid used in the composition of this invention can be defined in accordance with the properties stated in patent application WO 2011 G41 195.
    J
    In a preferred embodiment of this invention, the polymeric processing aid is an acrylic copolymer bet two or more
    BE2017 / 5143 may have different monomer units, including terpolymers and polymers with three or more different monomers. The copolymer architecture can be random, block, gradient, or other. The copolymer can be lneslr, branched or cross-linked, the copolymer can be one or more
    S contain multiple functional groups or may be non-functionalized. In this particular embodiment, acrylic copolymer as used herein refers to copolymers with 60% or more acrylic and / or methacrylic monomer units. (Methyl acrylate “is used in this text as containing both acrylate and methacrylate as a mixture of both acrylate and methacrylate.
    Useful acrylic monomers include, but are not limited to, methyl (meth) acrylate, ethyl {meth) acrylate, n-propyl (meth) acrylate, lsopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate . sec-butyl (meth) aerylate, tert-butyl (meth) acrylic, amyl-methacrylate, isoamyl (methacrylate, rshexyl (meth) acrylate, cyciohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, pentadecyl (meth) acrylate, dodecyl) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (mefch) acrylate, 2-hydroxyethyl (meth) acrylate and 2-methoxyethyl (meth) acrylate. Preferred acrylic monomers include methyl acrylate, butyl acrylate, but 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate.
    The polymeric engineering fabric used in the composition of this invention can be defined in accordance with the properties disclosed in patent application WO 2010099160.
    In a specific preferred embodiment of the composition according to this invention, the polymeric technical shell is an acrylic polymer technical shell which is a terpolymer polymerized from a monomer mixture of 41 to 44 weight percent methyl methacrylate (MMA), 22 to
    24% by weight of butyl acrylate (BA) and 33 to 36% by weight of styrene.
    The terpolymer can be made by any conventional polymerization technique such as, but not limited to, bulk, solution, suspension, emulsion, and Inverse emulsion polymerization.
    BE2017 / 5143
    Also, the acrylic polymeric technical fabric can be defined in accordance with the properties described in patent application US 7572862 B2.
    Non-limiting examples include polymer polymer technical trimmings such as Plastistrength® 530, 550, 551, 552, 557, 559, 576, 770 and
    L1000.
    In addition, a specific embodiment of this invention may be the Stabilizer and Ca / Zn Stabilizer, preferably Solid State,
    However, any known stabilizer can be used in the composition of this invention.
    The Ba / zn stabilizer In the liquid state is particularly preferred since it provides the ability to obtain a suitable dispersion of all compounds according to this invention.
    In a specific preferred embodiment, the thermoplastic elastomer containing PVC and polyacrylates is a PVC grafted with polybutyl acrylate.
    Conveniently, the composition of this invention may contain filler, pigment, flame retardant, biocide, lubricant, and a UV stabilizer such as TiO 2 .
    The production of a synthetic membrane with the composition of this invention comprises the following steps:
    the production of a synthetic layer containing the composition of the present invention;
    providing At least one reinforcing layer having a first side and a second side;
    applying the synthetic layer to the first side of the at least one reinforcing layer.
    Such membranes can then be fixedly mounted on a roof by means of known techniques.
    BE2017 / 5143
    The synthetic membrane can be produced by an extrusion process known in the art.
    In a preferred embodiment, a first and a second synthetic layer are obtained with the composition of this invention. The first layer can be fixedly applied to a first side of a reinforcing layer and the second layer can be fixedly applied to the second side of a reinforcing layer.
    A t
    It is also possible to form a waterproofing composition based on a multi-layered structure and preferably with different reinforcing layers,
    The reinforcing layer can be made from a material selected from the group consisting of woven or non-woven polyester, glass and fiber gias.
    The most important physical properties of a synthetic waterproofing membrane can be judged by the parameters elongation at break, tensile strength, cold fracture, fragmentation and surface damage.
    The elongation and tensile strength of a synthetic waterproofing membrane obtained with the composition of this invention can be determined by the standard method of EN-3-3-2.
    The cold bending temperature, according to the cold rupture test, of a synthetic waterproofing membrane obtained with the composition of this invention can be gascuffed using the standard method of EN-495-5.
    The spalling fragmentation test consists of placing a mass of 0.5 kg at a height of 1 m above the synthetic membrane placed in an environment with a temperature of -30 ° C and then determining whether the synthetic membrane breaks completely (-) , completely resists (+), or partially resists (*).
    BE2017 / 5143
    The surface sagging is proportional to the presence of defects that may occur on the surface and / or in the body of the waterproofing membrane immediately after its production,
    When waterproofing membranes show such defects, on or on the inside, It is necessary to remove these products and not put them on the market,
    An additional advantage of the composition of the present invention is related to the fact that it renders reliable and reproducible production of a range of synthetic waterproofing membranes by reducing the presence of defects in the grain product,
    Therefore, at the end of the process of producing a synthetic membrane obtained according to this invention, different cameras are placed in the production line to identify whether the defects are redo (±), problematic (-) or acceptable (+} on top of). the membrane or sift the membrane randomly.
    Vgprbeeld.l läfeeLl
    Connect Weight percent PVC K60 (53160) 30/7 Ca / Zn stabilizer 3.1 Epoxy bars 1..93 Organic phosphite 0.2 Wes Kranker 9/1 PVC grafted with polybutyric crystalline 21.5 EVA-CO copolymer 13.74 Nuclear schii impact modifier 7.5 Polymer technical shell fabric 2.86 Additives (biocides / kiei) 5.37 UV steblllsstor 4
    BE2017 / 5143
    A mix is obtained by mixing the compounds mentioned in Table 1 of Example 1,
    In this example the PVC with a 50 K-value 1rs can be available under the brand name Vinnolit® S3160.
    The Ca / Zn stabilizer may be available as the product Stabiol cz 32.97 / 1.
    The epoxy resin can be the commercial product Beckopox®.
    The organic phosphite may be available as the product Stabiol
    P2Ö29.
    The plasticizer is diisononyl phthalate (DIMP).
    PVC grafted with polybutyiacryphate (thermoplastic eiastomer) is available as the product ®Vinnolit VK 701.
    The EVA-CO copolymer can be the commercial product Elvaioy®
    741.
    The core schii impact modifier can be the product Durastrength® 25 D380 and the polymer technical shell fabric the product Piasbstrength® P SSI.
    The biocides may be available through the product Interside ™,
    The UV stabilizer can contain titanium dioxide and carbon dioxide.
    The plasticizer can be replaced with a diisode cyanate (DÎDP), or by the commercially available product Edenof® 888R, Edenoi® D81 or Edenof® S8R,
    The PVC grafted with polybutyl acrylate can be replaced by the hand-sold product ®Vinnolit VK 7Q7e.
    BE2017 / 5143
    The composition of Example 1 was processed to obtain a synthetic layer applied to a first side of the reinforcing layer of polyester,
    As described above, the reinforcing layer can be made of a different material.
    The results of the various tests performed are shown in Table 2 of Example 1,
    Sn tabe 2, the results show that the membrane exhibits an elongation to break of 286%, a tensile strength of 13.1 N / mm 2 , a cold fracture below -35 ° C, a positive fragmentation test and a surface with reasonable defects.
    Tsbel2
    fest Results Rack 286% Tensile strength 13.1 N / rom 2 Cold fracture 35 * C Splintering test - »· Surface
    Example 2
    Connections Weight percent PVC KSÖ 30 Ba / Zn stsblilsator 2.86 Epoxy resin 1.82 Organic phosphlet 0.18 Plasticizer 7.73 PVC grafted with polybutyl sheet 20.71 EVA-CO copolymer 13.21
    BE2017 / 5143
    Kem-schii impact modiffcator 7.5 Polymer technical shell fabric 2.86 Additives (hiocid / keel) 3.47 UV stabilizer 3.65
    In this specific example, the compounds of the composition are listed in Table 3. Identical to that of Example 1, except that the stabilizer is a Ba / Zn stabilizer.
    As in Example 1, the UV stabilizer may contain titanium dioxide and carbon back.
    The plasticizer can be replaced by a diisode cyanate (DIDP), or by the commercially available product Edenol® 888R, Edenol® D81 or Edenol® 88R.
    The PVC grafted with polybutyric crystalline can be replaced by the commercially available product Virsnollt® VK 707e.
    The composition of Example 2 was processed to obtain a synthetic layer applied to a first side of a polyester reinforcing layer.
    The results of the different tests performed are shown in Table 4 of Example 2.
    In Table 4, the results show that the membrane exhibits an elongation at break of 293%, a tensile strength of 13.6 N / mm 2 , a cold fracture below -40 ° C, a positive fragmentation test and an acceptable surface.
    Tehe: 4
    Test Results Rsk 293%
    BE2017 / 5143
    Tensile strength 13.§ N / mm * Cold braisk <40 ° C Splintering test 7 upperviak · Ί ·
    ïàbëis
    Connections Weight percent PVC KS4 2S, 48 Ca / Zn stabilizer 3.04 Epoxy resin 0 Organic phosphite 0 Plasticizer 13 PVC inoculated with poiybutylacryiaaï 20.07 EVÄ-CO copolymer 13 Nuclear Flash MAC Modifier 7.7 Polymeric technical buttocks 3.07 Additives (biocides / kiei) 0.6 UV stabilizer 4.04
    According to this specific example, the compounds of the composition mentioned in Table 5 are identical to those of Example 1, except that the PVC has a 64 K value (available as the commercially available product Soivin RC26PC) and the epoxy resin and the organic phosphite are not present in the composition,
    IS As in Example 1, the UV stabilizer may contain titanium dioxide and carbon fiber. The plasticizer can be replaced with a diisode cyanate (DIOR), or with the hand-made product Edenoi® 888R, Edenoi® D81 or EdenoF 88R. The PVC grafted with polybutyric cryphate can be replaced by the commercially available product Vinnoiit® VK
    707e.
    BE2017 / 5143
    The composition of Example S was processed to obtain a synthetic layer applied to a first side of a polyester reinforcing layer,
    S
    The results of the different tests carried out are shown in table 5 of example 3, in table 6 the results show that the merobrasn shows an elongation at break of 267%, a tensile strength of 13 N / mm 2 , a cold fracture below 40 ° C, a positive dispersion probe and a surface with reasonable defects.
    IsbeLS
    Test Results Rack 267% Tensile strength 13 N / mm 2 Cold fracture -40 ° C Splinter test + Surface -t
    ÏSSÂgQfi ^ SSi
    YOU.
    ïâbeLZ
    Connections Weight percent PVC K60 27.2 Ca / Zn stabilizer 3.4 Epoxy resin 1.03 Organic phosphite 0.2 Plasticizer 9.00 PVC grafted with polybutyric crystalline 29.0 EVA-CC copolymer 13.6 Nuclear schii impact modifier 0 Polymeric processing aid 0
    BE2017 / 5143
    Additives (bioclden / kiei) 10.07 UV stabilizer 3.8
    In Comparative Example 1, the compounds listed in Label 7 were mixed to obtain a composition. This was processed
    S for the production of a waterproofing membrane. The results obtained for the suction membrane are shown in table 8 below.
    labsLS
    Test Results Rack 230% Tensile strength 12.2 N / mm 2 Cold fracture -25 ° C Splintering - Surface -
    io
    As illustrated, the membrane has an elongation at break of 236%, a tensile strength of 12.2 N / µm 2 , a cold fracture lower than -25 ° C, a negative splintering test and the surface is negative, which means several important defects were observed on the membrane after its production.
    VergslUkeiid voöftxrejd 2 ïâtell.9
    Connections Weight percent PVC K60 (S3150) 30.7 Ca / Zn stabilizer 3.1 Epoxy resin 1.33 Organic phosphite 0.2 Plasticizer 9.1 PVC grafted with polybutyl acrylate 0 EVA-CO copolymer 35.24
    BE2017 / 5143
    Nuclear schii impact modifier 7.5 Polymers technical shell fabric 2.80 Additleven (biocides / bottle) 5.37 UV stabilizer 4
    In Verbene Example 2, the Verbindungen mentioned in Table 9 were mixed! to obtain a composition. It was processed to produce a waterproofing membrane. The results obtained for such membrane are shown in Table 10 below.
    mrib.io
    Test Results Cold fracture • 20 ° C Verspiänteräng - Surface ·
    As illustrated in Table 10, the membrane has a cold break below -20 ° C, a negative fragmentation test, and the surface is negative, that is, major defects were observed on the membrane after its production.
    While the preferred embodiments of this invention have been described for illustrative purposes, those skilled in the art will appreciate that various modifications, additions or substitutes are possible without departing from the scope and spirit of the invention as set forth in the appended claims.
    BE2017 / 5143
    权利要求:
    Claims (4)
    [1]
    CONCLUSIONS
    1, A waterproofing membrane composition, containing:
    5 - Polyvinyl chloride (PVC);
    at least one core schii impact modifier; at least one polymeric processing aid, characterized in that it further contains:
    at least one PVC and polyacrylates containing thermoplastic
    0 egg stomer; and at least one poislr copolymer containing at least ethylene vinyl acetate (EVA) or at least ethylene N-butyryryrate (EBA) and a polar group selected from the group consisting of hydroxyl, alkoxy, carbonyl (-CO), carboxylic acid , carboxylic anhydride,
    Ether, ester, carbonic esters, epoxy, suiphonyi, nitrile, amide, silane and mixture requirement thereof.
    [2]
    The composition of claim 1, wherein the at least one core shell impact modifier has a rubber content of at least 90 weight,
    The composition according to claim 1 or claim 2, wherein the at least one core-schi impact modifier is selected from the group consisting of methacrylate-butadiene-styrene copolymers (MBS), acrylonitrile: 5-butadiene-styrene copolymers (ABS), acrylic core / foam polymers (AIM) and a combination thereof,
    [3]
    A composition according to any of the previous claims, wherein the at least one polymeric processing aid is an acrylic10 polymer.
    [4]
    The composition of claim 4, wherein the acrylic copolymer is an acrylic copolymer having a Tg preferably less than 90 ° C, preferably less than 80 ° C, more preferably less than 70 ° C, even more preferably
    15 isger dso 60 ° C.
    BE2017 / 5143
    Ο « The composition according to claim 5, wherein said copolymer contains fresh acrylic polymer methyl methacrylate units and at least one other acrylic monomer. ίζ * ν8,• The composition of claim 4, wherein the acrylic polymer and acrylic terpolymer is ; containing methyl methacrylate monomer units, butyl acrylate monomer units and styrene monomer units. Composition according to claim 1, containing from 5 to SO% by weight, preferably between 10 and 40% by weight, more preferably from 15 to 37% by weight PVC, Composition according to any of the previous claims, containing from 0 to 10% by weight of a stabilizer in the liquid state, especially Ba-Zn stabilizer, the weight percentage being defined relative to the total weight of the composition. 10.> 0 Composition according to any of the previous claims,containing from 5 to 40 weight percent, preferably from 5 to3 (3 weight percent, more preferably from 8 to 25 weight percent, stillmore preferably from 9 to 20 wt.%, advantageously lessthan 20 weight percent, of the at least one polar copolymer containing EVA-CO or EBA-CO, defined relative to the total weight of the composition, 11.30 The composition of any of the preceding claims, wherein the at least one core schii impact modifier is present in aamount from 2 to 25 weight percent, more preferably from 4 to 25 weight percent20 weight percent, even more preferably from 5 to IS weight percent,defined relative to the total weight of the composition. 12. Composition according to any of the previous conclusions, 35 the at least one polymeric technical dust being present In an amount of from 2 to 25 weight percent, more preferably from 4up to 20% by weight, even more preferably from 5 to 15% by weight
    2
    BE2017 / 5143 percent, defined with respect to the total weight of the composition,
    13. Consistently notwithstanding anything from the previous conclusions,
    5 containing from 0 to 20 weight percent of a plasticizer, defined relative to the total weight of the composition
    Composition according to any of the preceding claims, containing from 0 to 25% by weight of a PVC and polyacrylates
    Contains thermoplastic egg elastomer, defined relative to the total weight of the composition.
    Synthetic roofing membrane, said synthetic membrane containing at least one reinforcing layer as well as at least one layer .5 made of the composition according to any of the preceding claims.
    BE2017 / 5143
    Waterproof membrane composite
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    同族专利:
    公开号 | 公开日
    DK3216831T3|2019-09-23|
    EP3216831A1|2017-09-13|
    SI3216831T1|2019-11-29|
    BE1024673A1|2018-05-17|
    EP3216831B1|2019-06-12|
    引用文献:
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    US3780140A|1971-08-06|1973-12-18|Du Pont|Ethylene/carbon monoxide polymer compositions|
    EP0342283A1|1988-05-18|1989-11-23|Rohm And Haas Company|Thermoplastic and thermoset polymer compositions|
    EP1152033A1|2000-05-03|2001-11-07|Rohm And Haas Company|Polymeric compositions and processes for providing weatherable film and sheet|
    WO2015160579A1|2014-04-16|2015-10-22|Arkema Inc.|Use of high rubber impact modifiers in thermoplastic formulations|
    DE3542694A1|1985-12-03|1987-06-04|Wacker Chemie Gmbh|FLEXIBLE TO SOFT SHAPED BODIES BASED ON VINYL CHLORIDE ACRYLIC ACID ESTER GRAFT COPOLYMER|
    DE3714182A1|1987-04-29|1988-11-10|Alkor Gmbh|PLASTIC RAIL OR PLASTIC FILM|
    USH1437H|1994-03-04|1995-05-02|Spelthann Heinz H|Grafted copolymers|
    US6133367A|1997-06-17|2000-10-17|E. I. Du Pont De Nemours And Company|Ethylene vinyl acetate blends|
    US7572862B2|2005-02-08|2009-08-11|Arkema Inc.|Reduced melt viscosity rigid polyvinylchloride composition|
    US9085679B2|2009-02-26|2015-07-21|Arkema Inc.|Composite polymer modifiers|
    FR2948673B1|2009-07-28|2011-12-30|Arkema France|COMPOSITIONS OF PVC RESINS|
    WO2011041195A1|2009-09-30|2011-04-07|Arkema Inc.|Acrylic process aid for vinyl foam extrusion|CN108912538B|2018-06-20|2020-12-29|苏州华苏塑料有限公司|Weather-resistant 7000-hour lead-free polyvinyl chloride waterproof coiled material and preparation method thereof|
    法律状态:
    2018-07-25| FG| Patent granted|Effective date: 20180522 |
    2020-12-23| MM| Lapsed because of non-payment of the annual fee|Effective date: 20200331 |
    优先权:
    申请号 | 申请日 | 专利标题
    EP16159206.8|2016-03-08|
    EP16159206|2016-03-08|
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