MXPA01003562A - Novel rheology regulators such as ground natural calcium carbonates optionally treated with a fatty acid or salt and their use - Google Patents

Abstract

The invention concerns the selection of an ultrafine natural calcium carbonate, optionally treated with one or several fatty acids or one or several salts or mixtures thereof, and its use as rheology regulator for polymer compositions. The BET specific surface area according to ISO standard 4652 is 14 to 10 m2/g, and the oil absorption is higher than 16 measured according to the ISO 787-V standard (Rub-out method). The use of said ultrafine calcium carbonate enhances the conditions for mixing the constituents and manufacturing as well as the properties of the end product.

Description

NEW REGULATORS OF RHYTHMIA OF THE TYPE OF NATURAL CALCIUM CRUSHED, EVENTUALLY TREATED WITH A FATTY ACID OR ITS SALT AND USE OF THE SAME The present invention concerns the technical sector of putties or mastics, plaster or plaster, adhesives, plastisols, or even rubbers. It is known, in the field of polymer compositions loaded or not, for example, that the silane-terminated polyurethanes are used as putty or mastic or as moisture-curable adhesives. In the presence of moisture, the terminal silane groups suffer in a known manner a hydrolysis and condensation reaction. Then a stable siloxane (Si-O-Si) network is formed. Such ucts have numerous applications in various industrial fields, such as the transport and construction industry. They have sought, then, more and more sophisticated forms, mainly of the "monocomponent" type, and capable of being applied in diverse substrates that pose lems that are increasingly difficult to solve. The composition of this type of formulations comprises one or several fillers that can be one or several calcium carbonates usually qualified as "fines".

Ref: 128799 According to the invention, it has been discovered that, surprisingly, the selection of a natural calcium carbonate crushed of a high fineness, which will be described below, or of that calcium carbonate, also treated as described later , allows to reach an unequal set of satisfactory erties for the final uct. Particularly noteworthy is a good adaptability to adhesion on numerous types of substrates, such as certain difficult plastics, including in those to those without a previous priming or "sealer" layer, a reduction in the amount of polymer required (and consequently a reduction in the cost of the materials), or even a significant reduction of the mixing time (which can reach a factor of half in each stage, which evidently represents a great economic interest). It is even more surprising to note that this remarkable imement of a set of erties of the final uct is not effected, as the person skilled in the art foresaw logically, to the detriment of the final mechanical erties, or of erties such as resistance to chemical agents or to UV rays or analogous erties conventionally requested of such agents. Plastisol type formulations based on polyvinyl chloride (PVC) are also known.

It is noted that a plastisol designates a suspension of one or more PVC resins in a liquid plasticizer, as well as adjuvants such as mineral fillers, stabilizers, mineral and / or organic pigments, blowing agents, adhesion accelerators, fluidizers and others. After thermal gelation, the plastisol acquires the appearance of a more or less flexible compact mass. One of the mineral fillers usually used, consists of a synthetic calcium carbonate obtained by chemical means (precipitated calcium carbonate: PCC) as for example the uct Winnofil SPT Premium, Zeneca. According to the invention, it is osed to use, as the rheology-regulating mineral material, a crushed natural calcium carbonate, of great fineness, in the presence or absence of dispersing agent. This natural calcium carbonate is selected from chalk or gypsum, calcite, marble, alone or as a mixture, or between the same calcium carbonates treated with the aid of at least one fatty acid, or its salt, or its mixture and preferably with the aid of stearic acid or its salt such as in particular calcium, magnesium, zinc stearate and most preferably with the aid of stearic acid or its calcium salt, as described in more detail below.

The uct, rheology regulator, according to the invention is characterized in that it is a natural calcium carbonate, with a specific surface of the order of 14 to 30 m2 / g., preferably from 16 to 24 m2 / g, and very preferably in the order of 20 m2 / g determined according to the method B.E.T. ISO 4652. This carbonate is optionally treated with at least one fatty acid, or its salt, or its mixture, acid which is an acid containing from 10 to 24 carbon atoms, and more especially stearic acid or its salt such as in particular, calcium, magnesium and zinc stearate and very preferably with the aid of stearic acid or its calcium salt, preferably in a proportion of 0.01% to 5% by weight and more preferably 1% to 4% by weight. % in weigh. It will be noted herein that stearic acid is understood as being industrial grade stearic acids composed primarily of 50% to 70% octadecanoic acid and 30% to 50% hexadecanoic acid.

An original advantage of the product according to the invention is that the product is a calcium carbonate which fulfills a rheology regulator function. This function is usually attributed to the polymers and to the additives contained in the polymeric formulation, such as, for example, the viscosity depressants and the applicant has been surprised to see it satisfied by a product of the natural mineral filler material type of great fineness. The product selected according to the invention consists of a natural calcium carbonate comminuted very finely in the presence or not of a dispersed agent and optionally treated with at least one fatty acid, or its salt, or its mixture. Another of its characteristics resides in its intake of oil that is higher than 16, determined according to ISO 787-V (Rubout method). A surface-specific calcium carbonate of 19 to 26 m2 / g has been described in patent EP 0 795 588. According to this document, it is known as a pigment that provides gloss and opacity in the paper field. This field of application is totally different. For the rest, such a function is totally different from that of a rheology regulator action, and nothing would suggest either the function set forth by the invention, or the fact that this new application could lead to a surprising set of properties that present a great economic interest. The invention also concerns the use, as a rheology regulator for the preparation of putties or plasters or pastes, of adhesives, plastisols or even rubbers, of the natural calcium carbonates crushed with a very great fineness, possibly treated with the aid of less a fatty acid or its salt mainly of calcium, magnesium, or zinc or its mixture. This acid, which is an acid containing from 10 to 24 carbon atoms, is more particularly stearic acid or its salt, such as in particular calcium stearate, magnesium stearate, zinc stearate and very preferably stearic acid or its calcium salt. The treatment is preferably carried out in a proportion of 0.01% to 5% by weight and more preferably 1% to 4% by weight of at least one fatty acid, or its salt, or its mixture. The invention also concerns the use of dispersions or suspensions, in an organic medium, of said calcium carbonates, treated or untreated, as a rheology regulator for the preparation of putties or plasters or pastes, adhesives, plastisols, or even of rubbers The invention finally concerns the polymeric compositions of plastisols, putties or plasters, of elastomer or of rubber containing, as a rheology regulator, the said natural calcium carbonates ground in a high fineness, possibly treated with the aid of at least one fatty acid, or its salt, or its mixture. Other features and advantages of the invention will be better understood by reading the description and examples that follow. These examples would not represent any limiting aspect of the invention. In the examples, the products have the following characteristics: PRODUCT A: Pre-existing load on the material, constituted by a natural calcium carbonate of chalk or gypsum type, crushed and dried, untreated, with an average grain diameter of 0.67. micrometers determined with the help of Sédigraph 5100 of the company Micromeritics, with a specific surface of 11 M2 / g determined according to the BET method No. 150 4652. PRODUCT B: Rheology regulator according to the invention, consisting of a natural calcium carbonate of chalk or gypsum type, crushed and dried, untreated, with a mean grain diameter of 0.60 micrometers determined with the help of Sedigraph 5100 ) to company "Micromeritics, with a specific surface area of 19.5 m2 / g determined according to the BET method, ISO 4652 standard and oil intake equal to 18.75 determined according to ISO 787-V (Rub-out method). PRODUCT C: Regulator rheology according to the invention constituted of natural calcium carbonate of the urgonian calcite type, crushed by wet and dried, untreated, with a mean grain diameter of 0.44 micrometers determined with the help of the Sedigraph 5100 from the company Micromeritics, with a specific surface area of 16.5 m2 / g determined according to the B.E.T. standard 150 4652 and oil intake equal to 20 determined according to ISO 787-V (Rub-out method). PRODUCT D: Regulator of rheology according to the invention, constituted of a natural calcium carbonate of chalk or gypsum type, crushed in wet and dried way, treated by the application of 3% by weight of stearic acid, of average diameter of grain of 0.59 micrometer determined with the help of Sédigraph 5100 of the company "Micromeritics", of specific surface, after treatment, equal to 16 m2 / g determined according to the BET method ISO 4652 standard and oil intake, after treatment, equal to 16.3 determined according to the standard 150 787-V (Rub-out method). PRODUCT E: Theology regulator according to the invention, consisting of a natural calcium carbonate of the urgonian calcite type, crushed by wet and dried, untreated with a mean grain diameter of 0.58 micrometers determined with the help of the Sédigraph 5100 from the company Micromeritics , of specific surface of 14.4 m2 / g determined according to the BET method ISO 4652 standard and oil intake equal to 17.9 determined according to ISO 787-V (Rub-out method).

PRODUCT F: Regulator of rheology according to the invention, constituted of a natural calcium carbonate of the chalk or gypsum type, crushed by wet and drying, treated with the aid of 1% by weight of stearic acid, resulting in a granulometry equal to 96% < 1 micrometer and 39% < 0.2 micrometer determined with the help of the Sádigraph 5100 of the company Micromeritics of specific surface, after treatment, equal to 28 m2 / g determined according to the method B.E.T. ISO 4652 standard and oil intake, after treatment, equal to 19.5 determined according to ISO standard 787-V (Rub-out method). PRODUCT G: Regulator of rheology according to the invention, constituted by a natural calcium carbonate of chalk type, crushed by wet and dried, untreated, with a specific surface of 22 m2 / g determined according to the method B.E.T. ISO 4652 standard and oil intake equal to 19.4 determined according to ISO 787-V (Rub-out method). PRODUCT H: Pre-existing load on the material, consisting of a precipitated calcium carbonate marketed by the company Zeneca, under the name of Winnofil SPT ™. PRODUCT I: Pre-existing load on the material, consisting of a natural calcium carbonate of chalk or gypsum type, crushed by wet process and dried, treated with the aid of 1% stearic acid, with an average diameter equal to 1.4 micrometers determined with the aid of Sedigraph 5100 of the company Micromeritics, and of specific surface equal to 6 m2 / g determined according to the BET method norm ISO 4652. PRODUCT J: Pre-existing load in the material constituted of a natural calcium carbonate of chalk or gypsum type, crushed by wet and drying process, treated by application of 1% in weight of stearic acid, of equal average diameter to 1 micrometer determined with the help of the Sedigraph 5100 from the company Micromeritics, and with a specific surface area equal to 10 m2 / g determined according to the BET method ISO 4652 standard. PRODUCT K: Pre-existing load on the material, consisting of a treated precipitated calcium carbonate, marketed by the Solvay company under the name of Socal U1S2. EXAMPLE 1: This example concerns the use of calcium carbonates as regulators of -reology for the preparation of plastisols. It was verified in these tests, the replacement of the synthetic calcium carbonate obtained by precipitation, pre-existing in the material, or precipitated calcium carbonate (PCC) by the specific natural calcium carbonate, according to the invention. In a plastisol type formulation based on PVC (polyvinyl chloride) that does not contain calcium carbonate, it was sought to compare the influence of the substitution of 50% to 100% of the mineral charge usually used, namely a precipitated calcium carbonate. by a crushed natural calcium carbonate of a high fineness, according to the invention. For this, it is mixed with 75 g of non-loaded plastisol, the calcium carbonate to be verified in a 7 cm diameter vessel and homogenized with the spatula. The formation of the dispersion of the mixture is then carried out for 2 minutes with a laboratory mixing equipment "Pendraulik" ™ LD50, the diameter of the dispersion formation disk is 5 cm, the disk rotation speed is 2700 rpm / min. (manual adjustment in position 3). When the formation of the dispersion was completed, the determination of the viscosity was made with the help of the "Rheo at 120" ™ equipment, determination equipment according to DIN 125 standard, at 20 'C. Test no.

This essay illustrates the pre-existing matter and applies 20 g. of a precipitated calcium carbonate marketed by the company Zeneca under the name of Winnofil SPT ™ (product H) and 5 g of natural calcium carbonate sold under the name Juraperle ™ BS, by the company Jura eiss. Test no.2: This test illustrates the pre-existing matter and applies 13 g. of a precipitated calcium carbonate marketed by the company Zeneca under the name of Winnofil SPT ™ (product H) and 12 g of product A according to the invention. Test no. 3: This test illustrates the invention and applies 25 g. of a pro-gas B according to the invention. Test No. 4: This test illustrates the pre-existing matter and applies 20 g of a precipitated calcium carbonate marketed by the company Zeneca with the name of Wínnofil SPT ™ (product H). Test no. 5: This essay illustrates the pre-existing matter and applies 10 g. of a precipitated calcium carbonate marketed by the company Zeneca under the name of Winnofd SPT ™ (product H) and 15 g of the product D according to the invention. Test no. 6: This test illustrates the invention and applies 10 g. of a precipitated calcium carbonate marketed by the company Zeneca under the name of Winnofil SPT ™ (product H) and 15 g of the product C according to the invention. Test no. 7: This test illustrates the invention and applies 13 g. of a precipitated calcium carbonate marketed by the company Zeneca under the name of Winnofil SPT ™ (product H) and 12 g of the product E, according to the invention. Test no. 8: This test illustrates the invention and applies 10 g. of a precipitated calcium carbonate marketed by the company Zeneca under the name of Winnofil SPT ™ (product H), 5 g of natural calcium carbonate sold under the name Juraperle ™ BS, by the company Juraweiss and 10 g of the product D according to the invention. Test no.9: This test illustrates the invention and applies 10 g. of a precipitated calcium carbonate marketed by the company Zeneca under the name of Winnofil SPT ™ (product H), 5 g of natural calcium carbonate sold under the name Juraperle ™ BS, by the company Juraweiss and 10 g of the product E according to the invention. Test no. 10: This test illustrates the invention and applies, for a mixture with 72 g of plastisol, 10 g of a precipitated calcium carbonate marketed by the company Zeneca under the name of Winnofil SPT ™ (product H), 5 g of calcium carbonate natural sold under the name of Juraperle ™ BS, by the company Juraweiss and 13 g of the product E according to the invention. The results of the viscosity determinations as a function of the displacement speed according to DIN 125 at 20 ° C are combined in the following tables la and Ib below.

TABLE C O M P O s I C I N R e o L O G 1 A Table Ib C O M P O s I C I N R E O L O G I A The reading of the table shows that the use of calcium carbonate, according to the invention, makes it possible to adjust the rheological behavior of the plastisol composition, also when 100% of the precipitated calcium carbonate has been replaced by the calcium carbonate according to the invention . EXAMPLE 2 This example concerns the study of the classic mechanical properties conferred by the product F according to the invention, whether natural ground chalk in order to obtain a specific surface area of 28 m2 / g, to mixtures with plasticized PVC base, in comparison with mixtures loaded with well-known natural calcium carbonates pre-existing in the art. For each of the tests, the following mixture was made: PVC "SOLVIC 239 D" marketed 100 by the company Solvay Dioctyl phthalate (Jayflex ™ DOP by Exxon) 50 Dibasic sulphate of lead 1 Tribasic sulphate of lead 2 Load to verify 80 Preparation of the composition: The dry mixes are prepared with the "GUEDU" adiabatic mixer at 100 ° C for a period of 15 minutes, the mixtures are then gelled in cylinders at 150 ° C with the cylinder mixer This operation was carried out for all mixes in 12 minutes, then 90 x 90 x 2 mm plates were molded at 160 ° C after the preheating for 3 minutes and adjusted under pressure for 2 minutes before of cooling with the help of a compression press The tests necessary for the determination of the mechanical properties were stamped or cut out in those plates The different calcium carbonates verified are: Test no. 11: This test illustrates the pre-existing material and applies a chalk or natural plaster treated with 1% stearic acid with a specific surface area of 6 m2 / g determined according to the B.E.T method. ISO 4652 standard (product I). Test no. 12: This test illustrates the pre-existing matter and applies a chalk or natural plaster treated with 1% stearic acid of specific surface area of 10 m2 / g determined according to the method B.E.T. ISO 4652 standard (product J). Test no. 13: This test illustrates the invention and applies the product F according to the invention.

The mechanical properties are appreciated, by the dynamometric tests (resistance to rupture, elongation at rupture, module 100%) carried out by application of the Instron ™ equipment according to ISO 37, at a temperature of 23 ° C and for a speed of traction of 10 cm / min. The tear strength ASTM-C is determined according to the method of ISO-R-34 and the Shore C hardness according to the method of ISO 868. The results of these determinations of mechanical properties are combined in Table II. then. Table II it is observed that the mechanical properties obtained are excellent and are superior to those obtained with crushed natural calcium carbonates but with a specific surface outside the field of the invention.

The invention then allows to optimize the formulations according to the privileged mechanical property. EXAMPLE 3: This example concerns the use of calcium carbonates as rheology regulators for the preparation of the elastomer based on natural and synthetic rubber. This example seeks to appreciate the influence of the specific surface of a natural chalk crushed according to the invention on the properties of the mixture based on natural and synthetic rubbers, in comparison with a precipitated calcium carbonate pre-existing in the material. For which, it was carried out for each one of the essays. 14 and 15, the following mixture: Natural rubber (smoked leaf, RSS grade 1) 100 SBR rubber (Styrene-butadiene, Cariflex ™ 1502 from Shell) 40 Zinc oxide (Snow quality) from "Old Mountain" 5 Stearic acid 2 Sulfur 1.5 N-cyclohexyl 2 benzothiazyl sulfenamide (Vulcafor-TM CBS from Vulnax) 1.0 Disulfide tetramethyl-turam (Bayer's Vulkacit ™ DTMT) 0.5 Calcium carbonate to be verified 100.0 Test no. 14: This test illustrates the pre-existing matter and applies a precipitated calcium carbonate marketed by the company Solvay under the name Socal U1S2 (product K). Test no. 15: This test illustrates the invention and applies the product F according to the invention. The two tests were carried out in the following manner: A pure rubber masterbatch is prepared by successively incorporating various ingredients except calcium carbonate, according to the usual technique of the person skilled in the art, into a cylinder mixer set at a temperature, mixed for 10 minutes (friction 1/4) at 60 ° C. On this master mix, two samples were taken in which the calcium carbonates to be verified were incorporated, by mixing at 60 ° C for 12 minutes. After the determination of the optimum vulcanization at 155 ° C with the help of the Monsanto rheometer, plaques were molded and vulcanized in this optimum, to effect the determination of the mechanical properties according to the same operative mode as that of the preceding tests. The results of the mechanical properties are combined in Table III, below. Table III It is noted that the product according to the invention reduces the application time (optimum vulcanization), as well as the tear resistance properties. Tests are also carried out nos. 16, 17 and 18 by the application of the following formulation: SBR rubber (Styrene-butadiene, Cariflex ™ 1502 from Shell) 40 Natural rubber (RSS quality 1 smoked sheet) 60 Zinc oxide (Snow quality) from "Old Mountain" 5 Stearic acid 2 Sulfur 2 N-cyclohexyl 2 benzothiazyl sulfenamide (Vulcafor ™ CBS from Vulnax) 0.9 Accelerator diortololuguanidine (Vulcafor "DOTG from Vulnax) 0.3 Calcium carbonate to be tested 100.0 Test No. 16: This test illustrates the pre-existing in the material and applies a precipitated calcium carbonate marketed by the company Solvay under the name of Socal U1S2 (product K) Test no.17: This test illustrates the pre-existing in the matter and applies a calcium carbonate chalk type or plaster, crushed by wet process and dried, treated, with a mean diameter equal to 1.4 micrometers determined with the help of Sédigraph 5100 from the company Micromeritics, and with a specific surface area equal to 10 m2 / g determined according to the BET norm method to 150 4652 (product J). Test no. 18: This test illustrates the invention and applies the product G according to the invention. On this master mix, manufactured in the same operating mode as in the previous test, three samples were taken in which the calcium carbonates to be verified were incorporated, by mixing at 60 ° C for 12 minutes. After the determination of the vulcanization optima, plates were molded and vulcanized at this optimum, to effect the determination of the mechanical properties according to the same operative mode as that of the preceding tests. The results of the mechanical properties were combined in Table IV below.

TABLE IV It is observed that the product according to the invention improves the application time (Optimal vulcanization) and mostly the mechanical properties. FJEMPLO 4: A second series of tests (tests nos. 19 and 20) was carried out on a natural rubber loaded at 40 per load of mineral charge and with a base formula: Natural rubber (smoked sheet quality RSS 1) 100 Coumaron resin 60/70 5.6 Rosin Resin 3.0 Zinc Oxide (Snow Quality) from "Old Mountain" 40.0 Stearic Acid 0.5 Oil 4.3 Benzothiazyl Disulfide Accelerator (Vulfor ™ Vulnax MBTS) 1.0 Diphenylguanidine Accelerator (Vulcafor ™ DPG from Vulnax) 0.36 Calcium carbonates to be checked They are: Essay no. 19: A precipitated calcium carbonate (product K) for this test that illustrates the pre-existing matter. Test no. 20: A natural calcium carbonate according to the invention (product G) for this test, which illustrates the invention. The results of the mechanical properties, determined with the same operating procedure as for the following tests, were combined in the following Table V. Table V It is observed that the product according to the invention allows to obtain results of equivalent mechanical properties, likewise, replacing in its entirety the calcium carbonate precipitated by a natural calcium carbonate.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects or products to which it refers.

Claims (18)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. Use as a rheology regulator of a calcium carbonate, characterized in that it is a natural calcium carbonate, crushed with a great fineness, surface specific in the order of 14 to 30 m2 / g. preferably of the order of 16 to 24 m2 / g and most preferably of the order of 20 m2 / g determined according to the method B.E.T. ISO 4652.
2. 2. Use as a rheology regulator of a calcium carbonate according to claim 1, characterized in that it is a natural calcium carbonate, crushed, of a high fineness, with a specific surface area of 14.4 m2 / g. determined according to the method B.E.T. ISO 4652.
3. 3. Use as a rheology regulator of a calcium carbonate according to claim 1, characterized in that it is a natural calcium carbonate, crushed, of a high fineness, with a specific surface area of 16 m2 / g. determined according to the method BET-norm ISO 4652.
4. 4. Use as regulator of rheology of a calcium carbonate according to claim 1, characterized in that it is a calcium carbonate natura, crushed, of a high fineness, with a specific surface area of 16.5 m2 / g. determined according to the method B.E.T. ISO 4652 standard.
5. 5. Use as a rheology regulator of a calcium carbonate according to claim 1, characterized in that it is a natural calcium carbonate, crushed, of a high fineness, with a specific surface area of 22 m2 / g. determined according to the method B.E.T. ISO 4652 standard.
6. 6. Use as a rheology regulator of a calcium carbonate according to claim 1, characterized in that it is a natural calcium carbonate, crushed with a high fineness, with a specific surface area of 28 m2 / g. determined according to the method B.E.T. ISO 4652.
7. 7. Use as a rheology regulator of a calcium carbonate according to any of claims 1 to 6 characterized in that it is a natural calcium carbonate, treated with the aid of at least one fatty acid containing 10 to 24 carbon atoms or their salts, chosen from the salts of calcium, magnesium, zinc or their mixture and more particularly with the help of stearic acid or its calcium salt in a proportion of 0.01% to 5% by weight.
8. 8. Use as a rheology regulator of a calcium carbonate according to claim 7, characterized in that it is a natural calcium carbonate treated with the aid of at least one fatty acid containing from 10 to 24 carbon atoms or its salt selected from the group consisting of salts of calcium, magnesium, zinc or their mixture and more particularly with the aid of stearic acid or its calcium salt in a proportion of the order of 1% to 4% by weight.
9. 9. Use as a rheology regulator of a calcium carbonate according to any of claims 1 to 8, characterized in that it has an oil intake that is greater than 16 determined according to ISO 787-V (Rub-out method).
10. 10. Use of a rheology regulator according to any of claims 1 to 9, for the preparation of mastics, adhesives, or even plastisols.
11. 11. Use of a rheology regulator according to any of claims 1 to 9, for the preparation of rubbers.
12. 12. Use, as regulator of rheology, of the dispersions or suspensions, in an organic medium, of a crushed natural calcium carbonate of a high fineness according to any of claims 1 to 9, for the preparation of putties or, plaster or plaster , adhesives 0 still plastisols.
13. 13. Use, as regulator of rheology, of the dispersions or suspensions, in an organic medium, of a crushed natural calcium carbonate of a high fineness according to any of claims 1 to 9, for the preparation of rubbers.
14. 14. Plastisol characterized in that it comprises a carbonate used as a rheology regulator according to any of claims 1 to 9.
15. 15. Rubber, characterized in that it comprises a carbonate used as a rheology regulator, according to any of claims 1 to 9.
16. 16. Filler or plaster or plaster, or adhesive characterized in that it comprises a carbonate used as a rheology regulator according to any of the claims 1 to 9.
17. 17. Putty or plaster or plaster, or adhesive according to claim 16, characterized in that it also comprises a polyurethane of terminal silane groups and a plasticizer of the phthalate type.
18. 18. Putty or, plaster or plaster, or adhesive according to any of claims 16 and 17, characterized in that it also comprises one or more additives selected from, the fumed silica as a thixotropic agent, a whiteness agent such as Ti02, UV stabilizers, agents which favor adhesion, catalysts such as dibutyltin dilaurate, dehydrating agents such as a silane.