Roofing element comprising at least one composition including at least one halogenated thermoplastic polymer and at least one rubber powder

Abstract

The present invention relates to a composition comprising: a) at least one halogenated thermoplastic polymer; b) 10 to 40% by mass of at least one rubber powder relative to the total mass of the composition.

Description

Description Title of the invention: Composition comprising at least one halogenated thermoplastic polymer and at least one powder of rubber

[0001] — The present invention relates to compositions, in particular for elements of roofing, such as slate, and more particularly to compositions comprising a halogenated thermoplastic polymer and a powder. Technical field

[0002] = In the construction of structures, especially buildings, the roof of the structure must be able to protect the interior of the structure from the environment exterior, but also to provide a desired aesthetic appearance. The roof of the structure must therefore be made up of elements presenting in particular properties of weather resistance.

[0003] = Today, various materials have been used to achieve these objectives, such as slate tiles or fiber cement tiles, etc.

[0004] = We know in particular of so-called “natural” slate tiles cut from a shale rock. However, these slate tiles are relatively heavy, do not have satisfactory resistance properties and their aesthetic appearance is not not necessarily pleasant.

[0005] Thus, the compositions of the prior art lead to the production of slates which have high densities.

[0006] Compositions are therefore sought which make it possible to obtain roofing elements, such as a slate, which overcome at least the disadvantages mentioned above.

[0007] — The applicant has discovered that a particular composition makes it possible to obtain roofing elements, such as slate, with advantageous properties, particularly in terms of density, fire resistance and shine. Statement of the invention

[0008] The present invention therefore relates to a composition comprising:

[0009] — a) at least one halogenated thermoplastic polymer:

[0010] = b) from 10 to 40% by mass of at least one rubber crumb relative to the total mass of the composition.

[0011] The composition according to the invention makes it possible in particular to obtain elements of roofing, such as slate, with advantageous properties, particularly in terms of density, fire resistance, or even shine.

[0012] — A roofing element having a lower density than a roofing element of the prior art makes it possible to provide a benefit on the mass. This is an advantage very interesting at a time when lighter materials are being sought. Indeed, a lighter material allows for a reduced weight on the frame, thus offering greater longevity on existing buildings or allowing for lighter frames on new buildings. A reduction in mass also leads to a reduction in the overall cost of building structures and also positive environmental impacts (helping to comply with the RE2020 regulations). Good fire resistance is obviously fundamental in a building structure. Improved gloss also provides aesthetic benefits. Reducing gloss allows for matte products that offer aesthetic benefits and comfort by avoiding glare. Any interval of values ​​designated by the expression "between a and b" represents the domain of values ​​from more than a to less than b (i.e., excluding the limits a and b), while any interval of values ​​designated by the expression "from a to b" means the domain of values ​​from a to b (i.e., including the strict limits a and b). Other characteristics and advantages of the invention will appear more clearly on reading the description and examples which follow. The expression "at least one" is equivalent to the expression "one or more". Furthermore, the term "pce", well known to those skilled in the art, means, within the meaning of this patent application, part by weight per hundred parts of elastomers, within the meaning of the preparation of the composition before cooking. The rubber crumb itself has a composition whose ingredients can be expressed in pce, the term pce designating the quantity in parts by weight per hundred parts of elastomers, within the meaning of the specific composition of the rubber crumb. On this basis, the term "pepth" means, within the meaning of the present patent application, part by weight per hundred parts by weight of halogenated thermoplastic polymers. When a “majority” compound is referred to, it is understood within the meaning of the present invention that this compound is the majority among the compounds of the same type in a given composition, that is to say that it is the one which represents the largest quantity by mass among the compounds of the same type and in particular more than 50% by mass, preferably more than 75% by mass. Thus, for example, a majority polymer is the polymer representing the largest mass relative to the total mass of the polymers in a given composition. In the same way, a so-called majority filler is that representing the largest mass among the fillers of a given composition. For example, in a system comprising a single polymer, this is the majority within the meaning of the present invention; and in a system comprising two polymers, the majority polymer represents more than half of the mass of polymers. On the contrary, a “minority” compound is a compound that does not represent the largest mass fraction among compounds of the same type. The compounds mentioned in the description may be of fossil or bio-sourced origin. In the latter case, they may be partially or totally derived from biomass or obtained from renewable raw materials derived from biomass. This includes polymers, plasticizers, fillers, etc. Furthermore, the compounds mentioned in the description may be derived from recycling. For example, a material, such as powder, may come from used tires or more generally from used materials. Another material, such as polyvinyl chloride, may come from used products, for example those from carpentry, shutters, pipes, etc. Halogenated thermoplastic polymer As indicated previously, the composition according to the invention comprises at least one halogenated thermoplastic polymer. For the purposes of the present invention, the term thermoplastic polymer means a polymer having a glass transition temperature, or a melting temperature in the case of semi-crystalline polymers, greater than or equal to 80°C, preferably varying from 80°C to 250°C, more preferably varying from 80°C to 200°C, and in particular varying from 80°C to 180°C. Indeed, in the case of a semi-crystalline polymer, a melting temperature higher than the glass transition temperature can be observed. In this case, the melting temperature is taken into account for the above definition and not the glass transition temperature. It is clear that a thermoplastic polymer within the meaning of the present invention is different from a thermoplastic elastomer. For the purposes of the present invention, the term halogenated thermoplastic polymer means a thermoplastic polymer as defined above, comprising units derived from one or more monomers, at least one of which comprises at least one halogen atom, such as fluorine, chlorine, bromine, iodine, preferably fluorine and chlorine, more preferably chlorine. The average molecular mass of a halogenated thermoplastic polymer is preferably understood to mean the weight-average molecular mass (Mw). Preferably, the halogenated thermoplastic polymer(s) consist of more than 75% by mass, preferably more than 85% by mass, more preferably more than 95% by mass, better still 100% by mass, of units derived from one or more monomers comprising at least one halogen atom. Preferably, the monomer(s) comprising at least one halogen atom are chosen from vinyl tetrafluoride, vinyl fluoride, vinylidene fluoride, ethylene chlorotrifluoride, vinyl chloride, superchlorinated vinyl chloride, vinylidene chloride, and mixtures of these monomers, and more preferably the monomer comprising at least one halogen atom is vinyl chloride. Advantageously, said halogenated thermoplastic polymer(s) are present in a mass content of at least 50% by mass, preferably at least 60% by mass, more preferably 60 to 90% by mass relative to the total mass of the composition. The composition according to the invention may optionally comprise one or more thermoplastic polymers other than the halogenated thermoplastic polymers described above. Examples of such polymers may include acrylonitrile, butadiene, and styrene copolymers (ABS copolymers), ethylene and vinyl acetate copolymers (EVA), and blends thereof. When present in the composition, the non-halogenated thermoplastic polymers preferably represent a mass rate of less than or equal to 30% by mass, more preferably from 0 to 15% by mass relative to the total mass of the composition. More preferably, the composition comprises as thermoplastic polymer only one or more halogenated thermoplastic polymers according to the invention as described above. Advantageously, said halogenated thermoplastic polymer has a weight-average molecular weight (Mw) ranging from 50,000 to 250,000 g / mol, preferably from 70,000 to 200,000 g / mol. Rubber powder As indicated previously, the composition according to the invention comprises from 10 to 40% by mass of at least one rubber crumb relative to the total mass of the composition. In the following, the expressions “rubber crumb”, “powder”, “rubber crumb composition” and “powder composition” are equivalent. The crumbs come in the form of granules, possibly formed into a rubber slab. Most often, rubber crumbs come from grinding or micronizing cooked rubber compositions already used for a first application, for example in tires, they are a product of material recycling. Preferably the crumbs come in the form of microparticles. For the purposes of the present invention, the term “microparticles” means particles which have a size, namely their diameter in the case of spherical particles or their largest dimension in the case of anisometric particles, of a few tens or hundreds of microns. Preferably, the rubber crumb is a composition comprising at least one elastomer and at least one filler. They may also include all ingredients used in rubber compositions such as plasticizers, antioxidants, vulcanization additives, etc. The powders may be commercially available. According to a particular embodiment, tire recycling may be used. The powder itself, if not directly purchased commercially, may be obtained using grinding or micronization techniques known to those skilled in the art. The elastomer can be chosen from diene elastomers, alone or in a mixture. By filler is meant any type of filler, well known to those skilled in the art. Preferably, the filler is any type of reinforcing filler known for its ability to reinforce a rubber composition, for example an organic filler such as carbon black, a reinforcing inorganic filler such as silica or alumina, optionally in the presence of a coupling agent, or mixtures thereof, for example a blend of these two types of filler. According to a preferred embodiment of the invention, the powder comprises as filler a reinforcing filler, preferably the reinforcing filler is chosen from carbon blacks. According to a more preferred embodiment, the reinforcing filler consists of a carbon black or a mixture of carbon blacks. Suitable carbon blacks are all carbon blacks, including HAF, ISAF, SAF, FF, FEF, GPF and SRF types conventionally used in rubber compounds for tires (so-called tire grade blacks). According to a preferred embodiment of the invention, the powder contains between 5 and 80% by mass of filler, more preferably between 10% and 75% by mass, very preferably between 15% and 70% by mass, better still from 20 to 60% by mass, and better still from 20 to 50% by mass relative to the total mass of the powder. The powder may contain all the other usual additives that are included in a rubber composition. Among these usual additives, we can cite vulcanization additives, non-reinforcing fillers such as chalk, kaolin, protective agents. These additives may also be found in the powder in the form of residue or derivative, since they may have reacted during the stages of manufacturing the composition or crosslinking the composition from which the powder is derived, or they may have evolved during use in the case of powder derived from end-of-life product. The crumbs can be simple ground rubber / micronisates, without any further treatment. It is also known that these crumbs can undergo treatment in order to modify them. This treatment can consist of a chemical modification of functionalization or devulcanization. It can also be a thermomechanical, thermochemical or biological treatment. According to a first, preferred embodiment of the invention, it is possible to use a powder which has not undergone any modification by thermal and / or mechanical, and / or biological and / or chemical treatment. Preferably also according to this first embodiment, the powder has an average particle size (D50) of between 50 and 800 um, preferably between 200 and 600 um. According to a second embodiment of the invention, it is possible to use a powder which has a morphology modified by thermal and / or mechanical, and / or biological and / or chemical treatment. Grinding can be carried out using various technologies, including cryogenic impact micronization technologies that allow the production of small particles on rubber materials. Commercial equipment such as the CUM150 mills from Netzsch or the CW250 mills from Alpine can be used. Advantageously, the rubber powder is present at a mass rate ranging from 10 to 35% by mass, preferably from 15 to 35% by mass relative to the total mass of the composition. Other possible additives The compositions in accordance with the invention optionally also comprise various additives, such as, for example, mineral or organic fillers, such as chalk, kaolin, wood powder, etc., pigments, such as carbon black, titanium dioxide, mineral pigments such as metal oxides or organic pigments, mineral or organic flame retardants, stabilizers, protective agents such as antioxidants, photoprotective agents, such as anti-UV agents, rheological additives such as plasticizing agents, lubricants, mineral powder, etc. According to a preferred embodiment, the composition further comprises at least one additive, preferably chosen from pigments, such as carbon black, mineral powders and mixtures thereof. Advantageously, the additive is present at a mass rate ranging from 0.2 to 20% by mass relative to the total mass of the composition. Preparation of the compositions The compositions are manufactured in suitable mixers usually used for the production of compositions comprising a halogenated thermoplastic polymer. There are two stages, the first, called "dry blend", consists of mixing the polymer powders and the additives in a first hot tank (at a temperature between 80 and 120°C) then continuing the mixing and ensuring cooling in a cold tank (room temperature). The mixture obtained is then introduced into an extruder heated between 130 and 200°C allowing a rod to be obtained at the outlet of the die which is then cooled and granulated to provide granules of the composition. The introduction of the powder can be carried out either in the “dry tank mixing” stage, with all the products in the hot tank, or introduced into the feed hopper of the extruder. When using recycled halogenated thermoplastic polymer, it can be introduced either in the 'dry tank mixing' stage or during extrusion. Another method of implementation consists of introducing all the constituents in a single extrusion step. When using halogenated polymer exclusively from recycling, the single extrusion step will be preferred with introduction into the hopper of the recycled PVC, the powder, and the various additives. In this embodiment, the additives can be introduced in the form of a masterbatch supported in a halogenated thermoplastic polymer base, such as a PVC base. A final method of production consists of using an internal Haake-type mixer or a calender heated between 130°C and 190°C. The different components are introduced into the mixer simultaneously or successively. Mixing is carried out for a period of 1 min to 5 min. The present invention also relates to a roofing element, such as a slate, comprising at least one composition according to the invention. The following examples illustrate the invention without, however, limiting it. Examples In the examples, the rubber crumbs are characterized as indicated below. Particle size measurement Particle size (especially D50) can be measured using a laser granulometry system such as the Malverne Mastersizer 3000. The measurement is carried out in a liquid state, diluted in alcohol after a preliminary ultrasound treatment of 1 min 10 sec to ensure particle dispersion. The measurement is carried out in accordance with ISO-13320-1. Measurement of carbon black mass fraction and ash The measurement of the mass fraction of carbon black is carried out by thermogravimetric analysis (TGA) according to the NF T-46-07 standard, on a device from the company Mettler Toledo model "TGA / DSCI". Approximately 20 g of sample are introduced into the thermal analyzer, then subjected to a thermal program from 25 to 400°C under an inert atmosphere (pyrolyzable phase) then from 400 to 750°C under an oxidizing atmosphere (oxidizable phase). The mass of the sample is measured continuously throughout the thermal program. The black rate corresponds to the loss of mass measured during the oxidizable phase relative to the initial sample mass. The ash rate corresponds to the residual mass at the end of the test relative to the initial sample mass. Fire test The test consists of placing a sample of the product in a closed chamber at an angle of 45° to the horizontal and exposing it to thermal radiation (30kW / m°?) on their lowest surface. The test lasts 20 minutes. The dimensions of the sample are as follows: length 40 cm, width 25 cm, thickness 4 mm. The test is carried out according to the NF P 92-501 standard. The ignition and extinction times of the faces are recorded as well as the changes in flame heights during the test. The parameter q is calculated according to the equation of the test standard: q = (100 x Sum of flame heights (cmn)) / (time of first ignition (s)) * square root (sum of effective combustion times (s)). The M classification is determined according to the value of q in accordance with the NF P 92-507 standard: MO: incombustible; M! : non-flammable fuel q < 2.5; M2: hardly flammable fuel 2.5 < q< 15; M3: medium flammable fuel 15 M4: easily flammable fuel q > 50; NC: not classified, test stopped before 20 minutes due to the chamber catching fire. Gloss measurement The measurement is carried out using an Erichsen Picogloss 560MC gloss meter at an angle of 60°. The surface of a 25 cm by 40 cm specimen is divided into 40 squares of 5 cm on each side. A gloss measurement is taken at the center of each square in the direction parallel to the width and in the direction parallel to the length of the sample. A total of 80 measurements per composition are carried out in order to obtain statistical accuracy of the gloss. Density measurement Density is measured using a helium pycnometer according to DIN 66137. It consists of measuring the volume occupied by a sample of given mass ​in a chamber using a gas. The mass volume (or density) is calculated from the measured volume and the mass of the sample. Example 1 1. Preparation of the compositions The compositions are manufactured by introducing all the constituents into a 250 cm³ Banbury-type internal mixer. Mixing is carried out with paddle rotation speeds of 50 rpm, with a tank temperature of 165°C. Mixing is stopped when the material temperature reaches 190°C. The material is then removed from the mixer and cooled, then re-integrated into the mixer for a new identical mixing step up to a temperature of 190°C. A third similar mixing step is carried out. Comparative composition C1 and composition C2 according to the invention were prepared on the basis of the ingredients as described in Tables 1 and 2 below. In Table 1, the contents are expressed in % by mass. In Table 2, the contents are expressed in pepth. [Tables 1] [Composition (% by mass) [El (comp) C2 (inv) Halogenated thermoplastic polymer ®_|87.7 61 Carbon black ® 8.8 6 Stabilizer 3.5 2.5 Powder | 30.5 (1): Polyvinyl chloride (PVC) polymer Lacovyl S110P marketed by the company Kemone; (3): Carbon black ASTM N234; (4): Naftosafe G WX 380 3-D stabilizer marketed by Chemson polymer-Additive AG; (5): MRP Microdync 830 TR powder marketed by the company Lchigh Technologies. [Tables 2] Composition (pcpth) (C1 (comp) |C2 (inv) Halogenated thermoplastic polymer _|100 100 Carbon black 10 10 Stabilizer US qe |Powder 8 | qs0 2. Sample preparation Then, each of the compositions was shaped to obtain a plate. 3. Results The results are collected in Table 3 below: [Tables 3] Composition C1 (comp) [C2 (inv) Density (g / em) |L4 1.3 Classification M Ml M2 Gloss # 3.6 It appears that the composition according to the invention C2 has a lower density and a lower gloss compared to the comparative composition CI. Thus, the composition according to the invention C2 makes it possible to obtain an improved density and gloss compared to those of the comparative composition C1. Indeed, the reduction in gloss makes it possible to offer an aesthetic benefit for applications aimed at obtaining matt products, such as building coverings (roofing elements, cladding, etc.). In addition, the mass benefit associated with the use of such a composition is interesting for applications requiring large volumes of material, such as building coverings (roof elements, cladding, etc.). Furthermore, the composition according to the invention C2 has an M2 classification, that is to say that the composition according to the invention C2 has a completely advantageous fire resistance and is completely suitable for applications such as the covering of buildings. Example 2 1. Preparation of the compositions The compositions are manufactured in the same way as previously, as described in Example 1. Comparative composition C3 and compositions C4 and CS according to the invention were prepared on the basis of the ingredients as described in Tables 4 and 5 below: [Tables 4] [Composition (% by mass) C3 (C4 (inv) |es (inv) | (comp) |Halogenated thermoplastic polymer 97 68 65.4 Carbon black S 2 2 [Halogenated thermoplastic polymer Carbon black © LS Stabilizer © Powder I (2): Polyvinyl chloride (PVC) polymer Vinika VRIN713001W001 marketed by the company MCPP. [Tables 5] [Composition (pepth) € |ca es (comp) |(Gnv) |(inv) Halogenated thermoplastic polymer ? |100 100 Carbon black © 3 3 3 Stabilizer | | 4 Powder © | 4 = 2. Sample preparation Then, each of the compositions was shaped to obtain a plate. 3. Results The results are collected in Table 6 below: [Tables 6] Composition C3 (comp) |C4 (inv) Density (g / cm) = 1.3 Classification M Ml M2 { Gloss = 3.6 { The same observations that were made for Example 1 apply here as well. It appears that the compositions according to the invention C4 and C5 have a lower density and a lower gloss compared to the comparative composition C3. Thus, the compositions according to the invention C4 and C5 make it possible to obtain an improved density and gloss compared to those of the comparative composition C3. In addition, the mass benefit associated with the use of such compositions is interesting. on applications requiring large volumes of material, such as building coverings (roofing elements, cladding, etc.). Furthermore, the compositions according to the invention C4 and C5 have an M2 classification, that is to say that the compositions according to the invention C4 and C5 have a fire resistance which is entirely advantageous and entirely suitable for applications such as the covering of buildings. Example 3 1. Preparation of the compositions The compositions are manufactured in the same way as previously, as described in Example 1. Comparative composition C6 and composition C7 according to the invention were prepared on the basis of the ingredients as described in Tables 7 and 8 below: [Tables 7] [Composition (% by mass) (C6 (comp) | C7 (inv) Halogenated thermoplastic polymer © [87.7 61 Carbon black ® 8.8 6 Stabilizer 3.5 2.5 Powder | 30.5 (6): Polyvinyl chloride (PVC) polymer Evervinyl ExtriGOM06NB marketed by the company Paprec; [Tables 8] Composition (pepth) C6 (comp) |C7 (inv) Halogenated thermoplastic polymer ® _|100 100 Carbon black © 10 10 Stabilizer '9 LS qe Powder | |50 2. Sample preparation Then, each of the compositions was shaped to obtain a plate. 3. Results The results are collected in Table 9 below: [Tables 9] Composition C6 (comp) |C7 (inv) Density (g / em) 1.4 1.3 Classification M Ml M2 Gloss > # The same observations that were made for examples 1 and 2 apply here as well. It appears that the composition according to the invention C7 has a lower density and a lower gloss compared to the comparative composition C6. Thus, the composition according to the invention C7 makes it possible to obtain an improved density and gloss compared to those of the comparative composition C6. In addition, the mass benefit associated with the use of such a composition is of interest in applications requiring large volumes of material, such as building coverings (roof elements, cladding, etc.). Furthermore, the composition according to the invention C7 has an M2 classification, that is to say that the composition according to the invention C7 has a fire resistance which is entirely advantageous and entirely suitable for applications such as the covering of buildings.

Claims

Claims

1. Composition comprising: (a) at least one halogenated thermoplastic polymer; (b) from 10 to 40% by mass of at least one rubber crumb per relative to the total mass of the composition.

2. Composition according to claim 1, characterized in that the halogenated thermoplastic polymers are made up of more than 75% by mass, preferably more than 85% by mass, more preferably of more than 95% by mass, better than 100% by mass, of units derived of one or more monomers comprising at least one atom of halogen.

3. Composition according to claim 2, characterized in that the monomers comprising at least one halogen atom are chosen among vinyl tetrafluoride, vinyl fluoride, vi- fluoride nylidene, ethylene chlorotrifluoride, vinyl chloride, superchlorinated vinyl chloride, vinylidene chloride, and mixtures thereof of these monomers, and more preferably the monomer comprising at least one halogen atom is vinyl chloride.

4. A composition according to any preceding claim, ca- characterized in that said halogenated thermoplastic polymer(s) are present in a mass rate of at least 50% by mass, of preferably at least 60% by mass, more preferably from 60 to 90% by mass relative to the total mass of the composition.

5. Composition according to any one of the preceding claims, ca- characterized in that said halogenated thermoplastic polymer has a weight average molecular mass Mw ranging from 50,000 to 250,000 g / mol, preferably 70,000 to 200,000 g / mol.

6. A composition according to any preceding claim, ca- characterized in that the rubber crumb is a composition comprising at least one elastomer and at least one filler.

7. Composition according to the preceding claim, characterized in that the elastomer is chosen from diene elastomers, alone or in blend.

8. Composition according to claim 6 or 7, characterized in that the filler is a reinforcing filler, preferably chosen from black of carbon.

9. Composition according to any one of claims 6 to 8, ca- characterized in that the mass rate of charge is between 5 and 80% in load mass, more preferably between 10% and 75% by mass, very preferably between 15% and 70% by mass, better from 20 to 60% in mass, and better still 20 to 50% in mass compared to the mass total powder.

10. | Composition according to any one of the preceding claims, ca- characterized in that the rubber crumb has a size average particle size (D50) between 50 and 800 um, of preferably between 200 and 600 um.

11. A composition according to any preceding claim, ca- characterized in that the rubber crumb is present at a rate mass ranging from 10 to 35% by mass, preferably from 15 to 35% by mass mass relative to the total mass of the composition.

12. Roofing element, such as a slate, comprising at least one com- position as defined in any one of the preceding claims previous.