EP1525351B1 - Method for the treatment of architectural fabrics by means of impregnation with an elastomeric cross-linkable silicone composition - Google Patents

Description

The invention relates to the treatment of fibrous materials (in particular flexible supports such as woven supports or nonwoven supports), by a silicone elastomer composition vulcanizable by hydrosilylation (polyaddition), in particular of the two-component type (known as RTV-2). .

More specifically, the invention relates to the production of architectural silicone membranes obtained by impregnating an architectural textile, particularly but not limited to a glass fabric or a fabric of synthetic fibers such as polyester, by means of the silicone composition-especially RTV2-type referred to above.

The invention also relates to architectural silicone membranes obtained by impregnating an architectural textile, in particular but not limited to a glass fabric, by means of the silicone composition - especially RTV2- type referred to above.

• d'abris, de structures mobiles, de bâtiments textiles, de cloisons, de portes souples, de bâches, de tentes, de stands ou de chapiteaux ;
• de mobiliers, de bardages, d'écrans publicitaires, de brise-vent ou panneaux filtrants ;
• de protections solaires, de plafonds et de stores.

By " architectural textile " is meant a fabric or non-woven and more generally any fibrous support intended after coating the confection:

• shelters, mobile structures, textile buildings, partitions, soft doors, tarpaulins, tents, stands or marquees;
• furniture, cladding, advertising screens, windbreaks or filter panels;
• sun protection, ceilings and blinds.

The treatment of architectural textiles, using liquid silicone compositions crosslinkable elastomers, is conventionally achieved by coating or impregnation, when the compositions are emulsions or solutions.

The silicone coating is defined as the action of coating a textile, using a crosslinkable liquid silicone composition, and then cross-linking the coated film on the support, so as to produce a coating intended in particular to protect it to give it particular qualities, for example to give it characteristics of hydrophobicity / oleophobicity, waterproofing or improved mechanical properties or even to change the appearance.

Impregnation is defined as the action of penetrating a very fluid fluid based on crosslinkable silicone inside a fibrous support (core penetration) and then crosslink the silicone to give the textile properties of the type mentioned above.

In practice, silicone elastomer coatings on architectural textiles have many advantages related to the intrinsic characteristics of silicones. These In particular, composites have good flexibility, good mechanical strength and improved fire behavior.
Moreover, unlike traditional elastomers, silicones give them, among other things, an appropriate protection because of their hydrophobicity and their excellent resistance to chemical, thermal and climatic aggressions as well as a long life. However, in the emerging field of silicone composites for textile architecture, the method of depositing silicones by coating may have shortcomings. Indeed, the architectural fabrics exposed to bad weather must not have any effect of capillary rise from the edges, which would be detrimental to their aesthetics and their life span. However, the coating does not represent an effective technique for the protection of fibrous materials against the phenomenon of capillary rise.

To overcome this, it was conceivable to use the textile impregnation technique, by means of liquid silicone compositions, for example of the RTV-2 type, crosslinkable elastomers.

Until now, however, the only liquid silicone compositions known for impregnating textiles are fluid silicone solutions or emulsions.

In fact, there existed before the invention a technical prejudice according to which the liquid silicone compositions consisting of silicone oils, for example of the RTV-2 type, could not be used for textile impregnation.

By way of illustration, mention may be made EP0646672A1 which discloses a coated fabric for the manufacture of "Air Bag" airbags. The liquid silicone coating composition, crosslinkable elastomer by polyaddition, is obtained by mixing a portion A and a portion B. This silicone coating composition comprises 50% by weight of pyrogenic silica, 25% by weight of a vinyl-end polydimethylsiloxane of viscosity 20000 mPa.s, about 12% by weight of a vinyl-end polydimethylsiloxane of viscosity 4000 mPa.s, 9.5% by weight of aluminum hydrate, 3% by weight weight of a methylhydrogenpolysiloxane of viscosity 50 mPa.s, 0.07% of ethynylcyclohexanol and 0.073% by weight of platinum with catalyst and optionally an adhesion promoter based on epoxyalkoxysilane and / or vinyl trimethoxysilane. The viscosity of the silicone coating composition A + B according to D1 is very much greater than 7000 mPa.s at 25 ° C., which renders it unfit for textile impregnation.

Notwithstanding this, the inventors have sought to develop a treatment process at least by impregnation of architectural textiles, by application of a liquid silicone oil-based composition (s), crosslinkable elastomer, said method to have in particular to specifications to allow obtaining architectural textiles treated heart and surface, so as to have improved properties in terms of mechanical reinforcement, water repellency, waterproofing, appearance, fireproofing and especially resistance to capillary rise.

Another objective sought by the inventors is the manufacture of architectural silicone membranes formed by composites based on architectural textiles and silicone, which membranes have good mechanical properties and resistance to capillary rise, these composites being capable of being produced. by impregnation according to the process of the invention.

These objectives, among others, have been achieved by the inventors who have discovered, quite surprisingly, and despite the aforementioned technical prejudice, that a liquid silicone composition, the liquid phase of which is essentially or even exclusively formed by a or more crosslinkable silicone oil (s), especially cold, elastomer, could be used in a treatment process by impregnating fibrous supports, to give them mechanical properties and properties of resistance to capillary rise very satisfactory.

• -Ii = entier positif-
  application sur un textile architectural d'une composition silicone liquide réticulable en élastomère, comprenant:
  1. (a) au moins un polyorganosiloxane (POS) présentant, par molécule, au moins deux groupes alcényles, de préférence en C₂-C₆ liés au silicium ;
  2. (b) au moins un polyorganosiloxane présentant, par molécule, au moins trois atomes d'hydrogène liés au silicium ;
  3. (c) une quantité catalytiquement efficace d'au moins un catalyseur, de préférence composé d'au moins un métal appartenant au groupe du platine ;
  4. (d) éventuellement au moins un promoteur d'adhérence ;
  5. (e) éventuellement une charge minérale ;
  6. (f) éventuellement au moins un inhibiteur de réticulation ;
  7. (g) éventuellement au moins une résine polyorganosiloxane ;
  8. (h) et éventuellement des additifs fonctionnels pour conférer des propriétés spécifiques ;
• -IIi = entier positif-
  réticulation de la composition de silicone ;
• -III-
  éventuellement au moins une autre séquence opératoire comprenant les étapes Ii ≥ 2 et IIi ≥ 2 (i étant un entier positif) répondant à la même définition que celle donnée ci-dessus pour les étapes Ii et IIi ;

caractérisé en ce que

• → l'étape Ii=1 est une étape d'imprégnation à coeur du textile architectural à l'aide d'une composition silicone liquide :
  • 
    présentant:
    • * avant réticulation une viscosité dynamique comprise entre 1000 et 7000 mPa.s, à 25°C, et plus préférentiellement comprise entre 2000 et 5000 mPa.s à 25°C avant réticulation
    • * et après réticulation complète par une cuisson en étuve ventilée de 30 minutes à 150°C, au moins l'une des propriétés mécaniques suivantes :
      • une dureté Shore A au moins égale à 2, de préférence comprise entre 5 et 65 ;
      • une résistance à la rupture au moins égale à 0,5 N.mm^-1, de préférence au moins égale à 1,0 N.mm^-1 et plus préférentiellement au moins égale à 2 N.mm^-1 ;
      • une élongation à la rupture au moins égale à 50 %, de préférence au moins égale à 100 % et plus préférentiellement au moins égale à 200 %,
  • 
    et étant par ailleurs fluide et obtenue en ayant recours ni à une dilution, ni à une solubilisation, ni à une émulsification,
• → la membrane silicone architecturale ainsi obtenue ayant une remontée capillaire de moins de 20 mm, de préférence de moins de 10 mm et plus préférentiellement encore égale à 0, la remontée capillaire étant mesurée selon un test T conduit comme suit :
  • on découpe une bande de 2 x 20 cm du composite matériau fibreux silicone,
  • on prépare un bac contenant une encre colorée (par exemple de l'encre pour stylo plume),
  • on suspend verticalement la bande de matériau fibreux découpée au-dessus du bac d'encre de manière à faire affleurer la bande sur l'encre,
  • on définit le niveau 0 comme étant la ligne de ménisque de l'encre sur la bande,
  • la bande de composite est laissée en place jusqu'à ce que le front de remontée de l'encre s'équilibre,
  • on mesure la hauteur (H) en millimètres correspondant à la différence entre le niveau 0 et le niveau de remontée maximal de l'encre le long de la bande,

la remontée capillaire étant définie par la distance H.From which it follows that the invention relates first of all to a process for producing an architectural silicone membrane weighing between 400 and 1500 g / m ² , by impregnating an architectural textile with at least a silicone, comprising the following essential steps:

• -Ii = positive integer-
  application on an architectural textile of a crosslinkable liquid silicone elastomer composition, comprising:
  1. (a) at least one polyorganosiloxane (POS) having, per molecule, at least two alkenyl groups, preferably C ₂ -C _{6 groups} bonded to silicon;
  2. (b) at least one polyorganosiloxane having, per molecule, at least three silicon-bonded hydrogen atoms;
  3. (c) a catalytically effective amount of at least one catalyst, preferably composed of at least one platinum group metal;
  4. (d) optionally at least one adhesion promoter;
  5. (e) optionally a mineral filler;
  6. (f) optionally at least one crosslinking inhibitor;
  7. (g) optionally at least one polyorganosiloxane resin;
  8. (h) and optionally functional additives to impart specific properties;
• -IIi = positive integer-
  crosslinking the silicone composition;
• -III
  optionally at least one other operating sequence comprising the steps Ii ≥ 2 and IIi ≥ 2 (i being a positive integer) corresponding to the same definition as that given above for steps Ii and IIi;

characterized in that

• Step Ii = 1 is a step of impregnating the architectural fabric with a liquid silicone composition:
  • 
    with:
    • before crosslinking a dynamic viscosity of between 1000 and 7000 mPa.s at 25 ° C., and more preferably between 2000 and 5000 mPa.s at 25 ° C. before crosslinking
    • * and after complete crosslinking by cooking in a ventilated oven for 30 minutes at 150 ° C, at least one of the following mechanical properties:
      • a Shore A hardness of at least 2, preferably between 5 and 65;
      • a breaking strength at least equal to 0.5 N.mm ^-1 , preferably at least 1.0 N.mm ^-1 and more preferably at least equal to 2 N.mm ^-1 ;
      • an elongation at break of at least 50%, preferably at least 100% and more preferably at least 200%,
  • 
    and being otherwise fluid and obtained using neither dilution, solubilization nor emulsification,
• → the architectural silicone membrane thus obtained having a capillary rise of less than 20 mm, preferably less than 10 mm and more preferably still equal to 0, the capillary rise being measured according to a T test conducted as follows:
  • a strip of 2 × 20 cm of the silicone fibrous material composite is cut,
  • a tray containing a colored ink (for example ink for a fountain pen) is prepared,
  • the strip of fibrous material cut above the ink tray is suspended vertically so as to make the strip surface flush with the ink,
  • level 0 is defined as the meniscus line of the ink on the strip,
  • the composite strip is left in place until the rising edge of the ink equilibrates,
  • measuring the height (H) in millimeters corresponding to the difference between the level 0 and the level of maximum rise of the ink along the strip,

the capillary rise being defined by the distance H.

To the inventors' knowledge, such fluid compositions of reactive silicone oils capable of vulcanizing by polyaddition have never been used in a process for impregnating fibrous material.

All the viscosities referred to in the present application correspond to a dynamic viscosity quantity at 25 ° C., ie the dynamic viscosity which is measured, in a manner known per se, at a speed gradient of shear sufficiently low that the viscosity measured is independent of the speed gradient.

The general techniques for the impregnation of architectural textiles are well known to those skilled in the art: scraping, in particular by squeegee on cylinder, squeegee in the air and scrape on carpet, or by padding, that is to say say by squeezing between two rolls, or by roll licker, rotating frame, reverse roll "reverse roll", transfer, spraying.
One or both sides of the textile material can be impregnated, preferably by padding. The drying and crosslinking is then carried out, preferably by hot air or infra-red, especially from 30 seconds to 5 minutes, at a crosslinking temperature without exceeding the degradation temperature of the support.
Padding represents a particularly suitable technique for the process of the invention.

According to a preferred embodiment of the process according to the invention, at least one step III is provided, in which the liquid silicone application stage Ii ≥ 2 is a coating using a silicone composition crosslinkable liquid made of elastomer.
The fact of carrying out a treatment combining at least one impregnation and at least one silicone coating is a pledge of quality for architectural textiles whose properties are sought to be modified, in particular resistance to capillary rise, without prejudice to the other mechanical properties. water repellency, fire resistance, appearance.

The fluidity of the crosslinkable liquid silicone coating composition of step Ii ≥ 2 is identical to or different from that of the impregnation stage Ii = 1.
Advantageously, the fluidity of the silicone coating liquid is less than that of the silicone impregnating liquid.

The silicone oil compositions, including the impregnating fluid compositions, used in the process according to the invention comprise a mixture of polyorganosiloxanes (a) and (b).

• W est un groupe alcényle,
• Z est un groupe hydrocarboné monovalent, exempt d'action défavorable sur l'activité du catalyseur et choisi parmi les groupes alkyles ayant de 1 à 8 atomes de carbone inclus, éventuellement substitués par au moins un atome d'halogène, et ainsi que parmi les groupes aryles,
• a est 1 ou 2, b est 0, 1 ou 2 et a + b est compris entre 1 et 3,
• éventuellement au moins une partie des autres motifs sont des motifs de formule moyenne :
  
          W_c SiO_(4-c)/2     (a.2)
  
  dans laquelle W a la même signification que ci-dessus et c a une valeur comprise entre 0 et 3.

The polyorganosiloxanes (a) used in the present invention preferably have a unit of formula:

W _a Z _b SiO _{(4- (a + b)) / 2} (a.1)

in which :

• W is an alkenyl group,
• Z is a monovalent hydrocarbon group, which has no adverse effect on the activity of the catalyst and is selected from alkyl groups having from 1 to 8 carbon atoms inclusive, optionally substituted by at least one halogen atom, and as well as from aryl groups,
• a is 1 or 2, b is 0, 1 or 2 and a + b is 1 to 3,
• optionally at least some of the other units are units of average formula:
  
  W _c SiO _{(4-c) / 2} (a.2)
  
  wherein W has the same meaning as above and ca a value between 0 and 3.

The polyorganosiloxane (a) may be very predominantly formed of units of formula (a.1) or may contain, in addition, units of formula (a.2). Similarly, it can have a linear structure. Its degree of polymerization is preferably between 2 and 5,000.

W is generally chosen from methyl, ethyl and phenyl radicals, at least 60 mol% of the radicals W being methyl radicals.

Examples of siloxyl units of formula (a.1) are the vinyldimethylsiloxane unit, the vinylphenylmethylsiloxane unit and the vinylsiloxane unit.

Examples of siloxyl units of formula (a.2) are SiO _4/2 , dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, methylsiloxane and phenylsiloxane units.

Examples of polyorganosiloxanes (a) are dimethylvinylsilyl-terminated dimethylpolysiloxanes, methylvinyldimethylpolysiloxane copolymers with trimethylsilyl ends, methylvinyldimethylpolysiloxane copolymers with dimethylvinylsilyl ends, cyclic methylvinylpolysiloxanes.

The dynamic viscosity η _d of this polyorganosiloxane (a) is between 0.01 and 200 Pa.s, preferably between 0.01 and 100 Pa.s.

Preferably, the POS (a) comprises at least 98% siloxyl units D: -R ₂ SiO _2/2 with R corresponding to the same definition as W or Z, this percentage corresponding to a number of units per 100 silicon atoms .

• L est un groupe hydrocarboné monovalent, exempt d'action défavorable sur l'activité du catalyseur et choisi parmi les groupes alkyles ayant de 1 à 8 atomes de carbone inclus, éventuellement substitués par au moins un atome d'halogène, et ainsi que parmi les groupes aryles ;
• d est 1 ou 2, e est 0, 1 ou 2 et d + e a une valeur comprise entre 1 et 3 ;
• éventuellement, au moins une partie des autres motifs étant des motifs de formule moyenne :
  
          L_gSiO_(4-g)/2     (b.2)
  
  dans laquelle L a la même signification que ci-dessus et g a une valeur comprise entre 0 et 3.

With regard to the silicone oil compositions according to the invention, the preferred compositions of polyorganosiloxane (b) comprise the siloxyl unit of formula:

H _d L _e SiO _{(4- (d + e)) / 2} (b.1)

in which :

• L is a monovalent hydrocarbon group, which has no adverse effect on the activity of the catalyst and is selected from alkyl groups having from 1 to 8 carbon atoms inclusive, optionally substituted by at least one halogen atom, and as well as from aryl groups;
• d is 1 or 2, e is 0, 1 or 2 and d + ea is 1 to 3;
• optionally, at least a portion of the other units being units of average formula:
  
  L _g SiO _{(4-g) / 2} (b.2)
  
  where L has the same meaning as above and g has a value between 0 and 3.

As examples of polyorganosiloxane (b), mention may be made of poly (dimethylsiloxane) (methylhydrogensiloxy) α, ω dimethylhydrogensiloxane.

The polyorganosiloxane (b) may be formed solely of units of formula (b.1) or in addition comprises units of formula (b.2).

The polyorganosiloxane (b) may have a linear, branched, cyclic or lattice structure. The degree of polymerization is greater than or equal to 2. More generally, it is less than 100.

The dynamic viscosity η _d of this polyorganosiloxane (b) is between 5 and 1000 mPa.s, preferably between 10 and 100 mPa.s.

Group L has the same meaning as group Z above.

Examples of units of formula (b.1) are: H (CH ₃ ) ₂ SiO _1/2 , HCH ₃ SiO _2/2 , H (C ₆ H ₅ ) SiO _2/2.

The examples of units of formula (b.2) are the same as those given above for the units of formula (a.2).

• les diméthylpolysiloxanes à extrémités hydrogénodiméthylsilyle,
• les copolymères à motifs (diméthyl)-(hydrogénométhyl)polysiloxanes à extrémités triméthylsilyle,
• les copolymères à motifs diméthyl-hydrogénométhylpolysiloxanes à extrémités hydrogénodiméthylsilyle,
• les hydrogénométhylpolysiloxanes à extrémités triméthylsilyle,
• les hydrogénométhylpolysiloxanes cycliques,
• les résines hydrogénosiloxaniques comportant des motifs siloxyles M : R₃SiO_1/2, Q : SiO_4/2 et/ou T : RSiO_3/2, éventuellement D : -R₂SiO_2/2, avec R = H ou répondant à la même définition que L.

Examples of polyorganosiloxane (b) are:

• dimethylpolysiloxanes with hydrogenodimethylsilyl ends,
• trimethylsilyl endblocked (dimethyl) - (hydrogenomethyl) polysiloxane copolymers,
• copolymers containing dimethylhydrogenomethylpolysiloxane units with hydrogenodimethylsilyl ends,
• trimethylsilyl endblocked hydrogenomethylpolysiloxanes,
• cyclic hydrogen methylpolysiloxanes,
• the hydrogensiloxane resins comprising siloxyl units M: R ₃ SiO _1/2 , Q: SiO _4/2 and / or T: RSiO _3/2 , optionally D: -R ₂ SiO _2/2 , with R = H or the same definition as L.

As other examples of monovalent Z or L hydrocarbon groups that may be present in the POS (a) and (b) mentioned above, mention may be made of: methyl, ethyl; n-propyl; i-propyl; n-butyl; i-butyl; t-butyl; chloromethyl; dichloromethyl; α-chloroethyl; α, β-dichloroethyl; fluoromethyl; difluoromethyl; α, β-difluoroethyl; 3,3,3-trifluoropropyl; trifluorocyclopropyl; 4,4,4-trifluorobutyl; hexafluoro-3,3,5,5,5,5 pentyl; β-cyanoethyl, γ-cyanopropyl; phenyl; p-chlorophenyl; m-chlorophenyl; 3,5-dichlorophenyl; trichlorophenyl; tetrachloro-phenyl; o-, p- or m-tolyl; α, α, α-trifluorotolyl; xylyl (2,3-dimethylphenyl, 3,4-dimethyl-phenyl).
These groups may be optionally halogenated, or may be chosen from cyanoalkyl radicals.
Halogens are, for example, fluorine, chlorine, bromine and iodine, preferably chlorine or fluorine.
The POS (a) and (b) may consist of mixtures of different silicone oils.

Preferably, the proportions of (a) and (b) are such that the molar ratio of the silicon-bonded hydrogen atoms in (b) to the silicon-bonded alkenyl radicals in (a) is between 0.4 and 10.

According to one variant, the silicone phase of the composition comprises at least one polyorganosiloxane resin (g), comprising at least one alkenyl residue in its structure, and this resin has a weight content of alkenyl group (s) of between 0.1 and 20% by weight and, preferably, between 0.2 and 10% by weight.
These resins are branched organopolysiloxane oligomers or polymers well known and commercially available. They are preferably in the form of siloxane solutions. They have, in their structure, at least two different units chosen from those of formula R ₃ SiO _0.5 (M-unit), R ₂ SiO (D-unit), RSiO _1.5 (T-unit) and SiO ₂ (Q-unit ), at least one of these patterns being a T or Q pattern.
The radicals R are identical or different and are chosen from linear or branched C ₁ -C ₆ alkyl radicals, C ₂ -C ₄ alkenyl phenyl radicals and 3,3,3-trifluoropropyl radicals. There may be mentioned, for example, as R alkyl radicals, methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals, and as R radicals alkenyls, vinyl radicals.
It should be understood that in the resins (g) of the aforementioned type, a portion of the radicals R are alkenyl radicals.
Examples of oligomers or branched organopolysiloxane polymers that may be mentioned include MQ resins, MDQ resins, TD resins and MDT resins, the alkenyl functions that may be carried by the M, D and / or T units. resins which are particularly suitable, mention may be made of vinylated MDQ or MQ resins having a weight content of vinyl groups of between 0.2 and 10% by weight, these vinyl groups being borne by the M and / or D units.
This structural resin is advantageously present in a concentration of between 10 and 70% by weight relative to all the constituents of the composition, preferably between 30 and 60% by weight and, more preferably, between 40 and 60% by weight. in weight.

The polyaddition reaction is well known to those skilled in the art. It is also possible to use a catalyst in this reaction. This catalyst may especially be chosen from platinum and rhodium compounds. In particular, it is possible to use platinum complexes and an organic product described in the patents. US-A-3 159 601 , US-A-3 159 602 , US-A-3,220,972 and European patents EP-A-0 057 459 , EP-A-0 188 978 and EP-A-0 190 530 the platinum and organosiloxane complexes described in the patents US-A-3,419,593 , US-A-3,715,334 , US-A-3,377,432 and US-A-3,814,730 . The most preferred catalyst is platinum. In this case, the amount by weight of catalyst (c), calculated as the weight of platinum-metal, is generally between 2 and 400 ppm, preferably between 5 and 100 ppm based on the total weight of the polyorganosiloxanes (a) and (b). ).

• (d.1) au moins un organosilane alcoxylé répondant à la formule générale suivante :
  
  dans laquelle :
  • R¹, R², R³ sont des radicaux hydrogénés ou hydrocarbonés identiques ou différents entre eux et représentant l'hydrogène, un alkyle linéaire ramifié en C₁-C₄ ou un phényle éventuellement substitué par au moins un alkyle en C₁-C₃ ;
  • A est un alkylène linéaire ou ramifié en C₁-C₄ ;
  • G est un lien valenciel ;
  • R⁴ et R⁵ sont des radicaux identiques ou différents et représentent un alkyle en C₁-C₄ linéaire ou ramifié ;
  • x' = 0 ou 1
  • x = 0 à 2,
  ledit composé (d.1) étant de préférence du vinyltriméthoxysilane (VTMS) ;
• (d.2) au moins un composé organosilicié comprenant au moins un radical époxy, ledit composé (d.2) étant de préférence du 3-Glycidoxypropyltiméthoxysilane (GLYMO) ;
• (d.3) au moins un chélate de métal M et/ou un alcoxyde métallique de formule générale M (OJ)_n, avec n = valence de M et J = alkyle linéaire ou ramifié en C₁ - C₈, M étant choisi dans le groupe formé par : Ti, Zr, Ge, Li, Mn, Fe, Al, Mg, ledit composé (d.3) étant de préférence du titanate de tert.butyle.

In an advantageous embodiment of the method according to the invention, it is possible to use an adhesion promoter. This adhesion promoter may for example comprise:

• (d.1) at least one alkoxylated organosilane having the following general formula:
  
  in which :
  • R ¹ , R ² and R ³ are hydrogenated or hydrocarbon radicals which are identical to or different from each other and represent hydrogen, a linear C ₁ -C ₄ branched alkyl or a phenyl optionally substituted with at least one C ₁ -C alkyl ₃ ;
  • A is linear or branched C ₁ -C ₄ alkylene;
  • G is a valencial link;
  • R ⁴ and R ⁵ are the same or different radicals and represent a linear or branched C ₁ -C ₄ alkyl;
  • x '= 0 or 1
  • x = 0 to 2,
  said compound (d.1) preferably being vinyltrimethoxysilane (VTMS);
• (d.2) at least one organosilicon compound comprising at least one epoxy radical, said compound (d.2) being preferably 3-glycidoxypropyltimethoxysilane (GLYMO);
• (d.3) at least one metal chelate M and / or a metal alkoxide of general formula M (OJ) _n , with n = valence of M and J = linear or branched C ₁ -C ₈ alkyl, M being chosen in the group consisting of: Ti, Zr, Ge, Li, Mn, Fe, Al, Mg, said compound (d.3) being preferably tert.butyl titanate.

$$\left(\mathrm{d}.2\right)\ge \mathrm{10,}$$

$$\left(\mathrm{d}.3\right)\le 80.$$

The proportions of (d.1), (d.2) and (d.3), expressed in% by weight relative to the total of the three, are preferably as follows: $$\left(\mathrm{d}.1\right)\ge 10$$

$$\left(\mathrm{d}.2\right)\ge 10$$

$$\left(\mathrm{d}.3\right)\le 80.$$

Moreover, this adhesion promoter (d) is preferably present in a proportion of 0.1 to 10%, preferably 0.5 to 5% and more preferably still 1 to 2.5% by weight relative to all the constituents of the composition.

It is also possible to provide a load (e) which will preferably be mineral. It may consist of products chosen from siliceous materials (or not).

As for siliceous materials, they can act as reinforcing or semi-reinforcing filler.

The reinforcing siliceous fillers are chosen from colloidal silicas, silica powders of combustion and precipitation or their mixture.

These powders have an average particle size generally less than 0.1 μm and a BET specific surface area greater than 50 m ² / g, preferably between 100 and 300 m ² / g.

Semi-reinforcing siliceous fillers such as diatomaceous earth or ground quartz can also be used.

In the case of non-siliceous mineral materials, they can be used as semi-reinforcing mineral filler or stuffing. Examples of these non-siliceous fillers that can be used alone or in a mixture are carbon black, titanium dioxide, aluminum oxide, hydrated alumina, expanded vermiculite, zirconia, zirconate, unexpanded vermiculite, calcium carbonate, zinc oxide, mica, talc, iron oxide, barium sulphate and slaked lime. These fillers have a particle size generally of between 0.01 and 300 μm and a BET surface area of less than 100 m ² / g.

In a practical but nonlimiting manner, the filler employed is a silica.

The filler may be treated using any suitable compatibilizing agent and in particular hexamethyldisilazane. For more details in this regard, one can refer for example to the patent FR-B-2 764 894 .

In terms of weight, it is preferred to use an amount of filler of between 5 and 30, preferably between 7 and 20% by weight relative to all the constituents of the composition.

• polyorganosiloxanes, avantageusement cycliques et substitués par au moins un alcényle, le tétraméthylvinyltétrasiloxane étant particulièrement préféré,
• la pyridine,
• les phosphines et les phosphites organiques,
• les amides insaturés,
• les maléates alkylés
• et les alcools acétyléniques.

Advantageously, the silicone elastomer composition further comprises at least one retarder (f) of the addition reaction (crosslinking inhibitor) chosen from the following compounds:

• polyorganosiloxanes, advantageously cyclic and substituted by at least one alkenyl, tetramethylvinyltetrasiloxane being particularly preferred,
• pyridine,
• phosphines and organic phosphites,
• unsaturated amides,
• the alkylated maleates
• and acetylenic alcohols.

• R est un radical alkyle linéaire ou ramifié, ou un radical phényle ;
• R' est H ou un radical alkyle linéaire ou ramifié, ou un radical phényle ;
• les radicaux R, R' et l'atome de carbone situé en α de la triple liaison pouvant éventuellement former un cycle ;
• le nombre total d'atomes de carbone contenu dans R et R' étant d'au moins 5, de préférence de 9 à 20.

These acetylenic alcohols, (cf. FR-B-1,528,464 and FR-A-2,372,874 ), which form part of the preferred hydrosilylation reaction heat blockers, have the formula:

R - (R ') C (OH) - C ≡ CH

formula in which:

• R is a linear or branched alkyl radical, or a phenyl radical;
• R 'is H or a linear or branched alkyl radical, or a phenyl radical;
• the radicals R, R 'and the carbon atom located in α of the triple bond possibly forming a ring;
• the total number of carbon atoms contained in R and R 'being at least 5, preferably 9 to 20.

• l'éthynyl-1-cyclohexanol 1 ;
• le méthyl-3 dodécyne-1 ol-3 ;
• le triméthyl-3,7,11 dodécyne-1 ol-3 ;
• le diphényl-1,1 propyne-2 ol-1 ;
• l'éthyl-3 éthyl-6 nonyne-1 ol-3 ;
• le méthyl-3 pentadécyne-1 ol-3.

Said alcohols are preferably chosen from those having a boiling point greater than 250 ° C. Examples that may be mentioned include:

• ethynyl-1-cyclohexanol 1;
• 3-methyl-1-dodecyn-3-ol;
• trimethyl-3,7,11-dodecyn-1-ol;
• 1,1-diphenylpropyne-2-ol;
• 3-ethyl-6-ethyl-1-nonyne-3-ol;
• 3-methylpentadecyn-1-ol-3.

These α-acetylenic alcohols are commercial products.

Such a retarder (f) is present at a maximum of 3000 ppm, preferably at 100 to 2000 ppm relative to the total weight of the organopolysiloxanes (a) and (b).

As regards the functional additives (h) that may be used, they may be covering products such as, for example, pigments / dyes or stabilizers.

• il se présente en deux parties A et B distinctes destinées à être mélangées pour former la composition en ce que l'une de ces parties A et B comprend le catalyseur (c) et une seule espèce (a) ou (b) de polyorganosiloxane; et
• la partie A ou B contenant le polyorganosiloxane (b) est exempte de composé (d.3) du promoteur (d).

In the process according to the invention, it is also possible to use a two-component precursor system for the composition. This two-component system is characterized in that:

• it is in two separate parts A and B to be mixed to form the composition in that one of these parts A and B comprises the catalyst (c) and a single species (a) or (b) of polyorganosiloxane; and
• part A or B containing the polyorganosiloxane (b) is free of compound (d.3) of the promoter (d).

Thus, the composition may, for example, consist of part A comprising compounds (d.1) and (d.2) while part B contains compound (d.3).

To obtain the bicomponent silicone elastomer composition A-B.

In the case where a filler is used, it is advantageous to first prepare a primary mash by mixing a mineral filler, at least a portion of the POS (b), as well as at least a portion of the polyorganosiloxane (a). ).

This mashing serves as a base for obtaining, on the one hand, a part A resulting from the mixture of the latter with the polyorganosiloxane (b) optionally a crosslinking inhibitor and finally the compounds (d.1) and (d.2) of the promoter. (d). Part B is made by mixing a portion of the mash referred to above and polyorganosiloxane (a), catalyst (Pt) and compounds (d.3) of the promoter (d).

The viscosity of the parts A and B and their mixture can be adjusted by varying the amounts of the constituents and by choosing the polyorganosiloxanes of different viscosity.

In the case where one or more functional additives (h) are used, they are distributed in parts A and B according to their affinity with the content of A and B.

Once the parts A and B are mixed together, they form a ready-to-use silicone elastomer composition (RTV-2), which can be applied to the support by any suitable impregnation means (eg padding) and optionally any suitable impregnation means (eg squeegee or cylinder).

The crosslinking of the liquid silicone (fluid) composition applied to the architectural textile to be impregnated, or even to be coated, is generally activated for example by heating the impregnated architectural textile, even coated, at a temperature of between 50 and 200 ° C., taking into account obviously, the maximum resistance of the support to heat is taken into account.

Another object of the invention is constituted by an architectural silicone membrane that can be obtained by the method according to the invention ( architectural textile / silicone composite):
This composite membrane is characterized in that it is impregnated in the core of crosslinked silicone elastomer obtained from a liquid silicone composition, as defined above in the context of the description of the process according to the invention, this composition being otherwise fluid and obtained using neither dilution, solubilization nor emulsification.

Advantageously, the architectural fabric used in the constitution of this membrane is formed by a fabric, a nonwoven, a knit or more generally any fibrous support selected from the group of materials comprising: glass, silica, metals, ceramics , silicon carbide, carbon, boron, basalt, natural fibers such as cotton, wool, hemp, flax, man-made fibers such as viscose, or cellulosic fibers, synthetic fibers such as polyesters, polyamides, polyacrylics, chlorofibers, polyolefins, synthetic rubbers, polyvinyl alcohol, aramids, fluorofibres, phenolics ...

The invention also relates to an architectural silicone membrane (architectural textile composite / crosslinked silicone elastomer ) that can be obtained by the method according to the invention or from the aforementioned two-component system, characterized by a capillary rise of less than 20 mm, preferably less than 10 mm and more preferably still equal to 0, the capillary rise being measured according to a T test.

Advantageously, the architectural silicone membrane corresponding to a coated architectural textile as defined above or obtained by the method described above, constitutes a membrane of choice for the interior or exterior architecture or the sun protection, in particular because of its low capillary rise. or even zero. such a membrane has a weight of between 400 and 1500 g / m ²

Description of figures

• The figure 1 is a snapshot of a section of a silicone composite based on fibrous material.
• The figure 2 is a diagram representing the results of a comparative T test of capillary rise, carried out on three bands of tissue α (control) and βa, βb (Example I.7).

The examples which follow are intended to illustrate particular embodiments of architectural silicone membranes according to the invention, without limiting it to these simple particular modes.

EXAMPLE I Preparation, Impregnation and Properties of a Silicone Oil Composition According to the Invention I.1- Preparation

• 96,6 parties d'une résine M M(Vi) D(Vi) DQ contenant env. 0.6% de Vi
• 11 parties de poly (diMe)(Mehydrogénénosiloxy) α,ω diMehydrogéno siloxy, de viscosité 25 mPa.s et contenant 20% de SiH
• 0,025 partie d'éthynylcyclohexanol
• 1 partie de vinyltriméthoxysilane
• 1 partie de 3-glycidoxypropyltriméthoxysilane
• 0,4 partie de titanate de butyle
• 0,022 partie de catalyseur de réticulation au platine Karstedt.

In a reactor at ambient temperature, the following proportions (parts by weight) are gradually mixed:

• 96.6 parts of an MM (Vi) D (Vi) DQ resin containing approx. 0.6% of Vi
• 11 parts of α, ω diMehydrogenosiloxy, poly (diMe) (Mehydrogenenosiloxy), with a viscosity of 25 mPa.s and containing 20% of SiH
• 0.025 parts of ethynylcyclohexanol
• 1 part of vinyltrimethoxysilane
• 1 part of 3-glycidoxypropyltrimethoxysilane
• 0.4 parts of butyl titanate
• 0.022 parts of Karstedt platinum crosslinking catalyst.

Note: Me is a methyl radical.

I.2- Properties of the composition thus prepared - Viscosity:

The viscosity of the composition prepared using a Brookfield viscometer is measured: Viscosity = 2.3 Pa.s

- Reactivity:

The reactivity of the bath is appreciated by measuring its gel time in a GelTimer GelNorm marketed by OSI: Reactivity at 70 ° C = 30 min

I.3- Impregnation

• I.3-a polyester fabric of 200 g / m ² is impregnated with the composition by means of a laboratory calender.
  The conditions of the impregnation are as follows:
  • diameter of cylinders 10 cm (width 25cm)
  • scroll speed 1 m / min
  • applied pressure 20kg / cm
  • squeezing rate 35%
• I.3-b A glass fabric of 300 g / m ² is impregnated with the composition by means of a laboratory calender.
  The conditions of the impregnation are as follows:
  • diameter of cylinders 10 cm (width 25cm)
  • scroll speed 1 m / min
  • applied pressure 22 kg / cm
  • squeeze rate 30%

I.4- Cross-linking

The silicone composition deposited is crosslinked by placing the architectural (composite) membrane resulting from test I.3-a or I.3-b in a ventilated oven at 150 ° C. for 1 min.

I.5- Mechanical properties of the impregnated silicone elastomer after crosslinking

The mechanical properties of use are established according to the standards of the trade on the basis of pion of 6mm of thickness for the hardness and plate test of 2mm of thickness for the experiments in rupture. Crosslinking is made complete by cooking in a ventilated oven for 30 minutes at 150 ° C. Shore A hardness = 33 Tear resistant = 3.9 MPa Elongation at break = 140%

I.6- Impregnation control

The penetration of the composition into the tissue is observed by Scanning Electron Microscopy.

The cliché of the figure 1 shows a sectional view of the composite obtained from Example I.3-a. The corresponding scale is displayed on the image. It demonstrates the quality of the impregnation by revealing the compactness of the resulting composite. This picture shows the quality of the impregnation obtained by the process object of the invention. The absence of fluidizing or emulsifying solvent makes it possible to avoid the formation of solvent pockets in the matrix of the crosslinked silicone composition.

I.7- Resistance to capillary rise Analytical procedure:

The capillary rise is given by the rise height of a liquid with which the end of a composite strip is in contact, according to a T test.

The T test is conducted as follows:

• a strip of 2 × 20 cm of the silicone fibrous material composite is cut,
• a tray containing a colored ink (for example ink for a fountain pen) is prepared,
• the strip of fibrous material cut above the ink tray is suspended vertically so as to make the strip surface flush with the ink,
• level 0 is defined as the meniscus line of the ink on the strip,
• the composite strip is left in place until the rising edge of the ink equilibrates,
• the height (H) is measured in millimeters corresponding to the difference between the level 0 and the level of maximum ascent of the ink along the strip.

The capillary rise is defined by the distance H.

Resistance to capillary rise is inversely proportional to H.

Results

• la bande témoin α de gauche correspond à une bande découpée d'un matériau fibreux non imprégné et enduit de 200g/m² d'élastomère silicone, sur chaque face ;
• la bande βa du centre correspond à une bande découpée d'un composite selon l'invention, c'est-à-dire réalisé à partir d'un matériau fibreux à base de polyester, imprégné selon l'invention, puis enduit de 120g/m² d'élastomère silicone sur chaque face ;
• la bande βb de droite correspond à une bande découpée d'un composite selon l'invention, c'est-à-dire réalisé à partir d'un matériau fibreux à base de verre, imprégné selon l'invention, puis enduit de 100g/m² d'élastomère silicone sur chaque face

The schemas of the figure 2 represent comparatively the trace of such capillary rise for three strips of fabric:

• the control strip α of the left corresponds to a cut strip of a non-impregnated fibrous material and coated with 200 g / m ² of silicone elastomer, on each side;
• the band βa of the center corresponds to a cut strip of a composite according to the invention, that is to say made from a fibrous material based on polyester, impregnated according to the invention, then coated with 120 g / m ² silicone elastomer on each side;
• the straight βb band corresponds to a cut strip of a composite according to the invention, that is to say made from a fibrous material based on glass, impregnated according to the invention, then coated with 100 g / m ² silicone elastomer on each side

The strips (β) of the architectural silicone membrane (composite) according to the invention have a zero capillary rise, while the control band (α) has a capillary rise over more than 100 mm.

It is thus clearly seen that the impregnation according to the invention prevents the recovery which is made on the entire sample in its absence.

It has been shown a formulation capable of satisfying the compromise of low viscosity suitable for impregnating textiles and of sufficient mechanical properties for the characteristics of the composite. It will be noted that the properties achieved make it possible to classify the product in the range of elastomers; in particular elongation and hardness are typical of this class.

With such a composition, the level of impregnation of the textile is excellent which limits the capillary rise by infiltration along the fibers of the fabric which would be poorly sheathed by the hydrophobic polymer.

EXAMPLE II Compositions of Fluid Silicone Oils According to the Invention

The examples below demonstrate that with very fluid compositions such as those presented, a wide range of hardness of the elastomers can be covered while maintaining reasonable mechanical properties.

The compositions presented are as in the first example prepared cold by simple mixing. Nevertheless their preparation is done so as to have two parts, A and B, which are associated with each other in the ratio 100 A / 10 B, just before their use.

Tables (I) and (II) below describe these compositions and the properties they develop. TABLE I 2-1 2-2 2-3 Part A Resin MM ^vi D ^vi DQ grading 0.6% Vi, consisting of 17% M 0.5% Mvi, 75% D, 1.5% D ^vi , 6% Q 92 90 45 Poly diMe Me Vi siloxane α, ω-vinylated at 2.5% Vi and 0.4 Pa.s 0 0 45 Tetra Me, tetra Vi tetrasiloxane 0 2 0 Poly di Me di Me hydrogen α, ω-SiH at 7.5% SiH and 0.3 Pa.s 8 13 0 Poly di Me hydrogenated αω Me ₃ with a viscosity of 0.02 Pa.s 0 0 8 Tri methoxysilane gamma methacryloxypropyl 1 1 1 Tri methoxysilane gamma glycidoxypropyl 1 1 1 ethynylcyclohexanol 250 ppm 250 ppm 250 ppm Part B Resin MM ^vi D ^vi DQ grading 0.6% Vi, consisting of 17% M 0.5% Mvi, 75% D, 1.5% D ^vi , 6% Q 96 96 38 Poly diMe Me Vi siloxane α, ω-vinylated at 2.5% Vi and 0.4 Pa.s 0 0 58 Tetrabutyl orthotitanate 4 4 4 Catalyst of Karstedt with 10% platinum 215 ppm 215 ppm 215 ppm Hardness Shore A 40 45 67 Tear resistant MPa 3.6 4.5 0.8 Elongation at break % 150 100 15 Viscosity A mPa.s 2760 in 2040 2950 Viscosity B mPa.s 4150 4190 2480 Viscosity A + B mPa.s 3400 2250 2920 TABLE II 3-1 3-2 3-4 3-3 Part A 25% suspension of reinforcing silica in α-vinylated PDMS with a viscosity of 1.5 Pa.s 35 35 35 35 PDMS αω vinylated viscosity 1.5 Pa.s 55 55 35 37 PDMS αω vinylated viscosity 100 Pa.s 5 5 5 12 Poly diMe Me Vi siloxane α, ω-vinylated at 2.5% Vi and 0.4 Pa.s 0 0 18 9 Poly di Me di Me hydrogen α, ω-SiH at 7.5% SiH and 0.3 Pa.s 1.1 2.3 5 3.8 PDMS αω SiH at 5% SiH 4.2 0 0 0 Tri methoxysilane gamma methacryloxypropyl 1 1 1 1 Tri methoxysilane gamma glycidoxypropyl 1 1 1 1 ethynylcyclohexanol 500 ppm 500 ppm 500 ppm 400 ppm Part B 25% suspension of reinforcing silica in α-vinylated PDMS with a viscosity of 1.5 Pa.s 40 40 40 40 PDMS αω vinylated viscosity 1.5 Pa.s 56 56 56 56 Tetrabutyl orthotitanate 4 4 4 4 Catalyst of Karstedt with 10% platinum 215 ppm 215 ppm 215 ppm 215 ppm Hardness Shore A 8 30 49 42 Tear resistant MPa 0.76 1 1.5 2.25 Elongation at break % 250 170 65 135 Viscosity A mPa.s 2910 3800 2580 4330 Viscosity B mPa.s 3400 3400 3400 3280 Viscosity A + B mPa.s 3270 4190 2870 4760

Claims (9)

1. A method for the preparation of an architectural silicone membrane having a weight of between 400 and 1500 g/m², by impregnation of an architectural textile with at least one silicone, comprising the following essential stages:

   -Ii = positive integer-
   application to an architectural textile of a liquid silicone composition which can be crosslinked into an elastomer, comprising

   (a) at least one polyorganosiloxane (POS) having, per molecule, at least two alkenyl, preferably C₂-C₆, groups linked to the silicon;

   (b) at least one polyorganosiloxane having, per molecule, at least three hydrogen atoms linked to the silicon;

   (c) a catalytically effective quantity of at least one catalyst, preferably composed of at least one metal belonging to the platinum group;

   (d) optionally, at least one adhesion promoter;

   (e) optionally, a mineral filler;

   (f) optionally, at least one crosslinking inhibitor;

   (g) optionally, at least one polyorganosiloxane resin; and

   (h) optionally, functional additives in order to impart specific properties;

   - Iii = positive integer-
   crosslinking of the silicone composition;

   -III-
   optionally at least one other operating sequence comprising stages Ii ≥ 2 and Iii ≥ 2 (i being a positive integer) corresponding to the same definition as that given above for stages Ii and IIi;

   characterized in that

   - stage Ii=1 is a stage of impregnation right to the core of the architectural textile using a liquid silicone composition

   

   having:

   * a dynamic viscosity of between 1000 and 7000 mPa.s, at 25°C, and more preferably of between 2000 and 5000 mPa.s at 25°C before crosslinking,

   * and, after complete crosslinking by curing in a fan oven for 30 minutes at 150°C, at least one of the following mechanical properties:

   - a Shore A hardness of at least 2, preferably between 5 and 65,

   - a tensile strength of at least 0.5 N.mm^-1, preferably of at least 0.1 N.mm^-1 and more preferably of at least 2 N.mm^-1,

   - an elongation at break of at least 50%, preferably of at least 100% and more preferably of at least 200%,

   

   and furthermore being fluid and obtained without having recourse either to dilution or to dissolution or to emulsification,

   - the architectural silicone membrane thus obtained having a capillary rise of less than 20 mm, preferably of less than 10 mm and more preferably still equal to 0, the capillary rise being measured according to a T test carried out as follows:

   - a strip measuring 2 × 20 cm of the fiber/silicone composite is cut;

   - a tank containing a colored ink (for example fountain pen ink) is prepared;

   - the cut strip of fibrous material is suspended above the ink bath so as to make the strip flush with the ink;

   - the 0 level is defined as the meniscus line of the ink on the strip;

   - the composite strip is left in place until the rising front of ink is in equilibrium;

   - the height (H) in millimeters, corresponding to the difference between the 0 level and the maximum rise level of the ink along the strip, is measured,

   the capillary rise being defined by the distance H.
2. The method as claimed in claim 1, characterized in that the impregnation stage comprises a padding.
3. The method as claimed in either of claims 1 and 2, characterized in that it comprises at least one stage III, in which stage Ii≥2 for application of liquid silicone is a coating using a liquid silicone composition which can be crosslinked into an elastomer.
4. The method as claimed in any one of claims 1 to 3, characterized in that the polyorganosiloxane (a) chosen has units of formula:
   
           W_aZ_bSiO_(4-(a+b))/2     (a.1)
   
   in which:

   - W is an alkenyl group;

   - Z is a monovalent hydrocarbon group, which has no unfavorable effect on the activity of the catalyst and chosen from alkyl groups having from 1 to 8 carbon atoms inclusive, optionally substituted with at least one halogen atom, and from aryl groups;

   - a is 1 or 2, b is 0, 1 or 2 and a + b is between 1 and 3; and

   - optionally, at least one portion of the other units are units of average formula:
   
           W_cSiO_(4-c)/2     (a.2)
   
   

   in which W has the same meaning as above and c has a value between 0 and 3.
5. The method as claimed in any one of claims 1 to 4, according to which the polyorganosiloxane (b) contains siloxyl units of formula:
   
           H_dL_eSiO_(4-(d+e))/2     (b.1)
   
   in which:

   - L is a monovalent hydrocarbon group, which has no unfavorable effect on the activity of the catalyst and chosen from alkyl groups having from 1 to 8 carbon atoms inclusive, optionally substituted with at least one halogen atom, and from aryl groups;

   - d is 1 or 2, e is 0, 1 or 2 and d + e has a value between 1 and 3;

   - optionally, at least one portion of the other units being units of average formula:
   
           L_gSiO_(4-g)/2     (b.2)
   
   

   in which L has the same meaning as above and g has a value between 0 and 3.
6. The method as claimed in any one of claims 1 to 5, characterized in that the proportions of (a) and of (b) are such that the molar ratio of the hydrogen atoms linked to the silicon in (b) to the alkenyl radicals linked to the silicon in (a) is between 0.4 and 10.
7. The method as claimed in any one of claims 1 to 6, in which the adhesion promoter comprises:

   (d.1) at least one alkoxylated organosilane satisfying the following general formula:

   

   in which:

   - R¹, R², R³ are hydrogenated or hydrocarbon radicals, which are the same or differ from one another and represent hydrogen, a C₁-C₄ linear branched alkyl or a phenyl optionally substituted with at least one C₁-C₃ alkyl;

   - A is a C₁-C₄ linear or branched alkylene;

   - G is a valency bond;

   - R⁴ and R⁵ are radicals, which are identical or different and represent a linear or branched C₁-C₄ alkyl;

   - x' = 0 or 1; and

   - x = 0 to 2,

   said compound (d.1) being preferably vinyltrimethoxysilane (VTMS);

   (d.2) at least one organosilicone compound comprising at least one epoxy radical, said compound (d.2) being preferably 3-glycidoxypropyltrimethoxysilane (GLYMO); and

   (d.3) at least one metal M chelate and/or a metal alkoxide of general formula M(OJ)_n, where n = valency of M and J = C₁-C₈ linear or branched alkyl, M being chosen from the group formed by: Ti, Zr, Ge, Li, Mn, Fe, Al and Mg,

   said compound (d.3) preferably being tert-butyl titanate.
8. The method as claimed in any one of claims 1 to 7, in which the adhesion promoter is present in an amount of 0.1 to 10% by weight relative to all of the constituents.
9. The method as claimed in any one of claims 1 to 8, characterized in that the coated architectural fabric which is a constituent is formed by a fibrous support chosen from the group of materials comprising: glass, silica, metals, ceramic, silicon carbide, carbon, boron, basalt, natural fibers, such as cotton, wool, hemp, flax; artificial fibers, such as viscose or cellulose fibers; synthetic fibers, such as polyesters, polyamides, polyacrylics, "chlorofibres", polyolefins, synthetic rubbers, polyvinyl alcohol, aramides, "fluorofibres" and phenolics.

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