EP2134898A1 - Verfahren zur herstellung eines fasermaterials/silikonverbundstoffes und besagtes fasermaterial/silikonverbundstoff - Google Patents

Verfahren zur herstellung eines fasermaterials/silikonverbundstoffes und besagtes fasermaterial/silikonverbundstoff

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Publication number
EP2134898A1
EP2134898A1 EP08735781A EP08735781A EP2134898A1 EP 2134898 A1 EP2134898 A1 EP 2134898A1 EP 08735781 A EP08735781 A EP 08735781A EP 08735781 A EP08735781 A EP 08735781A EP 2134898 A1 EP2134898 A1 EP 2134898A1
Authority
EP
European Patent Office
Prior art keywords
silicone composition
fibers
silicone
composition
coated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08735781A
Other languages
English (en)
French (fr)
Inventor
Alain Pouchelon
Francis Lafaysse
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Elkem Silicones France SAS
Original Assignee
Bluestar Silicones France SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bluestar Silicones France SAS filed Critical Bluestar Silicones France SAS
Publication of EP2134898A1 publication Critical patent/EP2134898A1/de
Withdrawn legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/128Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31551Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31609Particulate metal or metal compound-containing
    • Y10T428/31612As silicone, silane or siloxane
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane

Definitions

  • the invention relates to a process for obtaining a fiber material / crosslinked silicone elastomer composite and said fiber material / crosslinked silicone elastomer composite.
  • This type of composite may be used more particularly in the field of textile architecture, in which composites comprising a fibrous support, such as a polymer or glass fabric, coated on each of its faces, are used. an elastomeric silicone coating, which can itself be coated with a layer of varnish.
  • the silicone coating is defined as the action of coating a fibrous support, in particular a textile, with 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 cross-linking the silicone to give the support properties of the type mentioned above.
  • silicone elastomer coatings on textile substrates have many advantages related to the intrinsic characteristics of silicones. These composites have in particular 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.
  • silicone elastomers particularly effective in the field of textile architecture, in which the textile-polymer composites are subject to a wide and restrictive set of specifications that encompasses both the mechanical characteristics of the composite and its resistance to various external aggression and its durability.
  • the hydrophobic nature of silicones is favorable the impermeability properties and the protection of the fibers of the textile core of the composite, in order to avoid problems of capillary rise in the textile core of the composite.
  • 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.
  • the coating as it is practiced does not represent an effective technique for the protection of fibrous materials vis-à-vis the phenomenon of capillary rise. Indeed, the textile threads must be particularly well coated to be protected. To overcome this, it has been proposed to use the technique of core impregnation of fibrous materials, by means of fluid liquid silicone compositions, such as that described in European Patent Application EP 1 525 277, of RTV-2 type. crosslinkable elastomer.
  • this fluid composition requires a core impregnation step which is a sometimes delicate elementary operation and which involves a process with the afferent material which forces the impregnation within the fibers of the support textile, such as padding. .
  • the limitations on the fluidity of the impregnating product are the mechanical properties it develops when it is crosslinked. Indeed, in respect of the crosslinking chemistry of elastomers, the mechanical properties achieved are generally related to the molar mass of the precursor polymers in the composition, that is to say their viscosity; low viscosities (low molar masses) do not allow important mechanical characteristics such as high elongation and good tearing. This leads to a limitation that involves the use of other processes such as dilution with solvents; this last process itself being limited for reasons of environment and safety on the dispensing machines.
  • the impregnation process has disadvantages with respect to the cohesion of the impregnated textile on leaving the element of the machine where the impregnating fluid elastomer is applied. This can result in distortions of the fabric that will be detrimental to the quality of the finished article.
  • the inventors have therefore sought to develop a novel process for obtaining a fiber material / crosslinked silicone elastomer composite offering an alternative to known methods for solving the problem of capillary rise in composites intended more particularly for textile architecture.
  • Another essential objective of the present invention is to provide a process for obtaining a composite which preserves the cohesion of the coated fibrous material so as not to adversely affect the quality of the final product.
  • Another essential objective of the present invention is to provide a process for obtaining a fibrous material / silicone composite which limits the risk of delamination and which guarantees good adhesion between the different silicone layers.
  • the viscosities indicated correspond to a dynamic viscosity quantity measured at 25 ° C., using a BROOKFIELD viscometer, according to the AFNOR NFT 76 106 standard of May 1982.
  • the second composition is very fluid and is applied on the face of a fibrous support, the other side is already coated with a silicone elastomer, obtained from a more viscous composition.
  • This first already coated surface provides the fibrous support a good cohesion, so that the application of the second composition, very fluid, is greatly facilitated: there is no deformation due to the softening of the fibrous support due to its wetting at heart by the very fluid composition.
  • the first coated surface is an impermeable layer that prevents the second composition, very fluid, to flow through the fibrous support.
  • the first and second silicone compositions are respectively applied to each of the faces of the fibrous support.
  • the first and second Silicone compositions are each mechanically anchored in the fibrous support, so that the risks of delamination between the different layers applied are limited.
  • At least one further coating and crosslinking step 5) is provided after step 4).
  • the additional coating and curing step 5) consists in coating the coated face in step 3) and crosslinked in step 4) with a third liquid silicone composition, crosslinkable in elastomer and having before crosslinking a dynamic viscosity of between 5,000 and 200,000 mPa.s at 25 ° C; and crosslinking said coated composition.
  • This third silicone composition may be identical or different from the first silicone composition.
  • a treatment combining at least one silicone coating of each of the faces of the fibrous support with a viscous silicone composition and at least one coating with a more fluid silicone composition, penetrating into the fibers, according to the process of the invention, is a guarantee of quality. for the fibrous material whose properties are sought to be modified, in particular resistance to capillary rise, without prejudice to other mechanical properties, water repellency, fire resistance, appearance.
  • squeegee in particular squeegee on cylinder, squeegee in the air, and squeegee on carpet, roller liner, inverse roller "reverse roll", transfer, spray.
  • the coating of steps 1, 3 and 5 is carried out using a doctor blade.
  • drying and crosslinking preferably by hot air or infrared, for example between 30 s and 5 min, are carried out at a crosslinking temperature not exceeding the degradation temperature of the fibrous support, for example a temperature between 50 and 200 ° C.
  • liquid silicone compositions used in the present invention may be crosslinkable compositions by addition reaction, condensation, dehydrogenocondensation, radical or UV, or mixed systems combining these different types of reaction.
  • liquid silicone compositions used in the present invention are polyaddition-crosslinkable compositions (hydrosilylation), in particular of the two-component type (known as RTV-2), and comprise:
  • A at least one polySi-alkenyl (preferably ⁇ Si-vinyl) polyorganosiloxane (POS);
  • B at least one polyorganosiloxane (POS) with ⁇ Si-H motifs;
  • the polyorganosiloxane POS (A) preferably has units of formula:
  • W is an alkenyl group, preferably a C 2 -C 6 alkenyl; and more preferably still a vinyl,
  • Z is a monovalent hydrocarbon group, which has no adverse effect on the activity of the catalyst and is chosen from alkyl groups having from 1 to 8 atoms of carbon included, optionally substituted by at least one halogen atom, and as well as aryl groups, a is 1 or 2, b is 0, 1 or 2 and a + b is 1, 2 or 3, and optionally other units of average formula:
  • alkenyl is meant an unsaturated hydrocarbon chain, linear or branched, substituted or unsubstituted, having at least one olefinic double bond, and more preferably a single double bond.
  • the "alkenyl” group has 2 to 8 carbon atoms, more preferably 2 to 6.
  • This hydrocarbon chain optionally comprises at least one heteroatom such as O, N, S.
  • alkenyl groups are vinyl, allyl and homoallyl groups; vinyl being particularly preferred.
  • Alkyl denotes a saturated, cyclic, linear or branched hydrocarbon-based chain, optionally substituted (eg by one or more alkyls), preferably from 1 to 10 carbon atoms, for example from 1 to 8 carbon atoms, better still 1 to 4 carbon atoms.
  • alkyl groups include methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, n-pentyl, isoamyl and 1,1-dimethylpropyl.
  • aryl refers to an aromatic hydrocarbon group having 6 to 18 carbon atoms, monocyclic or polycyclic and preferably monocyclic or bicyclic. It should be understood that, in the context of the invention, a polycyclic aromatic radical is understood to mean a radical having two or more aromatic rings, fused (ortho-condensed or ortho and peri-condensed) to each other, that is to say presenting, two by two, at least two carbons in common.
  • aryl there may be mentioned e.g. phenyl, xylyl and tolyl radicals.
  • POS (A) may be a mixture of several oils that meet the same definition as the POS (A).
  • the POS (A) may be formed only of units of formula (A. 1) or may further contain units of formula (A.2).
  • the POS (A) may be a linear polymer whose diorganopolysiloxane chain consists essentially of siloxy units D or D V
  • a POS (A) may be present in one of the liquid silicone compositions used in the invention, for example the first and possibly the third silicone compositions.
  • at least 60% of the Z groups represent methyl radicals.
  • Silicon units Q is however not excluded in the proportion of at most 2% (these percentages expressing the number of units T and / or Q for 100 silicon atoms).
  • siloxyl units of formula (IA) are the vinyldimethylsiloxyl, vinylphenylmethylsiloxyl, vinylmethylsiloxyl and vinylsiloxyl units.
  • siloxyl units of formula (A.2) are the SiO 4/2 , dimethylsiloxyl, methylphenylsiloxyl, diphenylsiloxyl, methylsiloxyl and phenylsiloxyl units.
  • POS (A) examples are dimethylvinylsilyl-terminated dimethylpolysiloxanes, trimethylsilyl-terminated methylvinyldimethylpolysiloxane copolymers, dimethylvinylsilyl-terminated methylvinyldimethylpolysiloxane copolymers and cyclic methylvinylpolysiloxanes.
  • the POS (A) may be a polyorganosiloxane resin.
  • Such a POS (A) may be present in one of the liquid silicone compositions used in the invention, for example the second silicone composition.
  • This polyorganosiloxane resin comprises at least one alkenyl residue in its structure, and 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. weight.
  • These resins are branched organopolysiloxane oligomers or polymers well known and commercially available. They are preferably in the form of siloxane solutions. They comprise, in their structure, at least two different patterns chosen from the motifs M, D, T and Q, at least one of these patterns being a T or Q pattern.
  • radicals R are identical or different and are chosen from linear or branched C 1 -C 6 alkyl radicals, C 2 -C 4 alkenyl radicals, phenyl radicals, trifluoroalkyl radicals and
  • R alkyl radicals methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals
  • R radicals alkenyls, vinyl radicals alkenyls, vinyl radicals
  • radicals R are alkenyl radicals.
  • oligomers or branched organopolysiloxane polymers examples 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 a composition, preferably between 30 and 60% by weight and, more preferably, between 40 and 60% by weight. % in weight.
  • the different POS (A) used in the invention are marketed by the silicone manufacturers or can be manufactured by operating according to already known techniques.
  • the POS (B) is the crosslinking POS, and is preferably of the type comprising those containing the siloxyl unit of formula:
  • 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 + e is 1, 2 or 3; and optionally other siloxyl units of average formula:
  • the polyorganosiloxane (B) may be formed solely of units of formula (B.1) or may further comprise units of formula (B.2).
  • the polyorganosiloxane (B) may have a cyclic or branched linear branched structure.
  • Group L has the same meaning as group Z above.
  • siloxyl units of formula (B.1) are:
  • siloxyl units of formula (B.2) are the same as those indicated above for the examples of siloxyl units of formula (A.2).
  • polyorganosiloxanes (B) are linear and cyclic compounds such as:
  • the POS (B) may optionally be a mixture of a dimethylpolysiloxane end-hydrogenodimethylsilyl and a polyorganosiloxane bearing at least 3 functions SiH (hydrogen siloxyl).
  • the POS (A) and (B) are selected according to their viscosity and the required viscosity of the first or second silicone composition.
  • the proportions of the polyorganosiloxanes (A) and (B) in the first silicone composition, and optionally of the third composition are such that the molar ratio of the number of silicon-bonded hydrogen atoms in the polyorganosiloxane (B) to the number of silicon-bonded alkenyl radicals in the polyorganosiloxane (A) is between 1 and 7.
  • the proportions of (A) and (B) in the second silicone composition may be such that the molar ratio of silicon-bonded hydrogen atoms in (B) to silicon-bonded alkenyl radicals in (A) is between 0 , 5 and 7.
  • the second silicone composition it is preferably rich in reactive groups so that the number of reactive groups remaining after crosslinking is sufficient to allow the adhesion of a possible subsequent coated composition.
  • the proportions of (A) and (B) in the second silicone composition may be such that the molar ratio of the silicon-bonded hydrogen atoms in (B) to the silicon-bonded alkenyl radicals in (A) is less than 1 and the content of said second composition in ⁇ Si-alkenyl units (preferably ⁇ Si)
  • the second composition may comprise at least one hyperalenylated (preferably hypervinylated) POS (A), rich in ⁇ Si-alkenyl units according to the characteristics indicated above.
  • step 4) an incomplete crosslinking of the second silicone composition by providing an underdosing of crosslinking POS (B).
  • the second silicone composition may also comprise two different crosslinking systems (for example thermal and UV), a single mechanism being activated at the time of crosslinking the second silicone layer.
  • the second silicone composition also has the particular feature that it is able to penetrate well into the fibers of a fibrous material, so as to coat them well, then to crosslink so as to form a composite 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.
  • the polyaddition reaction proper to the crosslinking mechanism of the composition used in the invention is well known to those skilled in the art. It is also possible to use a catalyst (C) in this reaction.
  • This catalyst (C) may especially be chosen from platinum and rhodium compounds.
  • EP-AO 190 530 platinum and organosiloxane complexes described in US-A-3,419,593, US-A-3,715,334, US-A-3,377,432 and US-A-3,814,730.
  • the generally preferred catalyst is platinum.
  • the amount by weight of catalyst (C), calculated as the weight of platinum-metal is generally between 2 and
  • the adhesion promoter (D) comprises:
  • R 1, R 2, R 3 are hydrogenated or hydrocarbon radicals that are identical to or different from each other and represent hydrogen, a linear or branched C 1 -C 4 alkyl or a phenyl optionally substituted with at least one C 1 -C 3 alkyl; ;
  • A is linear or branched C 1 -C 4 alkylene
  • VTMS vinyltrimethoxysilane
  • (d.2) at least one organosilicon compound comprising at least one epoxy radical, said compound (d.2) being preferably 3-glycidoxypropyltrimethoxysilane (GLYMO);
  • proportions of (d.l), (d.2) and (d.3), expressed in% by weight relative to the total of the three, are preferably as follows:
  • 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 first, second or third silicone 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).
  • 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 ⁇ m and a BET specific surface area greater than 50 m 2 / g, preferably between 100 and 300 m 7 g.
  • siliceous fillers such as diatomaceous earth or ground quartz can also be used.
  • non-siliceous mineral materials they can be used as semi-reinforcing mineral filler or stuffing.
  • 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 ⁇ m and a BET surface area of less than 100 g / cm 3.
  • the filler employed is a silica.
  • the filler may be treated using any suitable compatibilizing agent and in particular hexamethyldisilazane.
  • suitable compatibilizing agent for more details in this regard, reference may be made, for example, to patent FR-B-2 764 894.
  • a quantity of filler of between 5 and 30, preferably between 7 and 20% by weight relative to all the constituents of the composition.
  • Crosslinking inhibitors (F) are also well known. They are conventionally chosen from the following compounds:
  • polyorganosiloxanes advantageously cyclic and substituted by at least one alkenyl, tetramethylvinyltetrasiloxane being particularly preferred,
  • - R is a linear or branched alkyl radical, or a phenyl radical
  • R - R ' is H or a linear or branched alkyl radical, or a phenyl radical
  • radicals R, R 'and the carbon atom located alpha of the triple bond may optionally form a ring;
  • the total number of carbon atoms contained in R and R ' being at least 5, preferably from 9 to 20.
  • Said alcohols are preferably chosen from those having a boiling point
  • alpha-acetylenic alcohols are commercial products.
  • Such an inhibitor (F) is present at a maximum of 3000 ppm, preferably at 100 to 2000 ppm relative to the total weight of organopolysiloxanes (A) and (B).
  • the functional additives (G) may be covering products such as, for example, pigments / dyes, stabilizers or additives to improve the fire resistance.
  • the viscosity of the various silicone compositions used in the present invention can be adjusted to achieve the required values by varying the amounts of the constituents and in particular choosing polyorganosiloxanes (A) and (B) of suitable viscosities.
  • the compositions used in the present invention can be solvent-free and obtained from components of suitable viscosity.
  • the compositions may also be diluted so as to achieve the required viscosities before crosslinking for each coating step according to the invention.
  • the second silicone composition may be without solvent or obtained by dilution or solubilization in a solvent so that the second liquid silicone composition has in the diluted state before crosslinking a viscosity of less than or equal to 2000 mPa.s.
  • the solvent may be a reactive solvent, such as an alpha olefin, for example.
  • silicone compositions used in the invention are advantageously presented in the form of an at least two-component system, the mixture of which is capable of rapidly crosslinking by hot polyaddition.
  • the ingredients are then distributed in the different parts according to the rules of those skilled in the art; in particular the catalyst is separated from the component which comprises the hydrogensiloxanes.
  • the fibrous support intended to be coated may be for example a fabric, a nonwoven material or a knit or more generally any fibrous support comprising fibers chosen from the group of materials comprising: glass, silica, metals, ceramics , silicon carbide, carbon, boron, basalt, natural fibers such as cotton, wool, hemp, flax, artificial fibers such as viscose, or cellulosic fibers, synthetic fibers such as polyesters, polyamides, polyacrylics, chlorofibres, polyolefins, synthetic rubbers, polyvinyl alcohol, aramids, fluorofibres, phenolics ...
  • the invention relates to a fibrous material / crosslinked silicone elastomer composite
  • a fibrous material / crosslinked silicone elastomer composite comprising at least one fibrous support, as defined above, one face of which is coated with at least one first crosslinked silicone elastomer obtained from a first liquid silicone composition, as defined above, and the other side of which is coated with at least one second crosslinked silicone elastomer, penetrating into the fibers of the support, and obtained from a second silicone composition liquid, as defined above.
  • said face coated with at least one second silicone elastomer penetrating the fibers of the support is itself coated with a third crosslinked silicone elastomer, obtained from a third liquid silicone composition, as defined above. above.
  • a composite is 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.
  • the composite according to the invention can be used more particularly as an architectural textile.
  • architectural textile is meant a fabric or non-woven and more generally any fibrous support intended after coating the confection:
  • the fibrous material / crosslinked silicone elastomer composites according to the invention can also be used as flexible raw materials for the manufacture of air bags used for the protection of the occupants of a vehicle, in English "air bag", the glass braids (sheaths) made of thermal glass and dielectric glass for electrical wire), conveyor belts, fireproof or thermal insulation fabrics, compensators (flexible sealing sleeves for piping), clothes ...
  • air bags used for the protection of the occupants of a vehicle
  • the glass braids sheaths
  • compensators flexible sealing sleeves for piping
  • 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 test T.
  • the test T is conducted as follows: a strip of 2 ⁇ 20 is cut out cm of the textile / silicone composite, - a tray containing a colored ink (for example fountain pen ink) is prepared, the composite strip cut above the ink tray is suspended vertically so as to be flush with the strip on the ink, the 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.
  • a colored ink for example fountain pen ink
  • the capillary rise is defined by the distance H.
  • an assembly of the corresponding composites is prepared by bonding with a silicone elastomer rubber RHODORSIL MF 345 L ®, marketed by Bluestar Silicones, which is a silicone rubber ready to employment.
  • the elastomer glue is placed between two composite sheets so as to obtain, after vulcanization, a glue joint 5 cm wide by approximately 0.5 mm thick.
  • the vulcanization is carried out in a press at 180 ° C. for 2 minutes.
  • specimens 50 mm wide were cut. These specimens are evaluated using a dynamometer in a peel experiment at 50 mm / min performed in a so-called 180 ° geometry.
  • a glass fabric made with yarns of approximately 10 ⁇ m and a weight per unit area of approximately 250 g / m 2 is used as fiber support.
  • the composite of the invention comprises a fibrous support, one side of which is coated with a first crosslinked silicone elastomer obtained from a first liquid silicone composition, and the other side of which is coated with a second elastomer crosslinked silicone, penetrating into the fibers of the support and obtained from a second liquid silicone composition.
  • a RHODORSIL silicone elastomer TCS 7534® sold by Bluestar Silicones a self-adhering polyaddition vulcanizable elastomer, presented in two components, is used.
  • TCS 7534® A + B For the first silicone composition, undiluted TCS 7534® A + B is used. The viscosity of the first silicone composition is 45 Pa.s.
  • TCS 7534® A + B diluted with 30 parts of xylene per 100 parts of elastomer is used. The viscosity of the second silicone composition is 1.5 Pa.
  • one side of the glass fabric is coated with a doctor blade with the first silicone composition, aiming at a deposited weight of 200 g / m 2 .
  • the first silicone composition is crosslinked at 150 ° C. in 2 min.
  • the other side of the glass fabric is coated with the second silicone composition.
  • the second silicone composition is crosslinked at 150 ° in 2 min.
  • the resulting deposit is of the order of 100 g / m 2 .
  • the composition TCS 7534® A + B diluted with 30 parts of xylene per 100 parts of elastomer on the glass fabric, is first deposited by calendering impregnation.
  • calendering impregnation we use a laboratory calender equipped with 2 cylinders with a diameter of 100 mm and a length of 250 mm.
  • One cylinder is made of steel, the other of rubber.
  • the impregnation bath is fed into the air gap of the cylinders simultaneously with the fabric to be impregnated.
  • the cylinders are pressurized on each other and the rotational speed is about
  • composition is crosslinked. Then, one of the faces of the fabric was coated with the Mathis coating machine with the composition undiluted TCS 7534® A + B. The composition is crosslinked.
  • a composite is prepared by reversing the steps of the process according to the invention, that is to say starting with steps 3) and 4, then steps 1) and 2).
  • steps 3) and 4 steps 1 and 2
  • one of the faces of the fabric is coated with the doctor by means of the Mathis coating machine with the composition TCS 7534® A + B diluted with 30 parts of xylene per 100 parts of elastomer.
  • the composition is crosslinked.
  • the other side of the fabric was then squeezed with the undiluted TCS 7534® A + B composition.
  • the composition is crosslinked.
  • a composite was prepared by squeezing, by means of the Mathis coating machine, only one side of the fabric with the undiluted TCS 7534® A + B composition. Then the composition is crosslinked.
  • the coating application of the second silicone composition which is more fluid, is greatly facilitated by the good cohesion of the fabric provided by the elastomer deposited in surface coating with the first silicone composition, which is more viscous. There is no more deformations due to softening of the tissue due to its wetting heart by the second silicone composition, more fluid, to apply.
  • the elastomer obtained from the first silicone composition forms an impermeable layer which prevents the second, more fluid silicone composition from flowing through the fabric.
  • the composite of the invention comprises a fibrous support, one side of which is coated with a first crosslinked silicone elastomer obtained from a first liquid silicone composition, and the other side of which is first coated with silicone.
  • a second crosslinked silicone elastomer penetrating into the fibers of the support and obtained from a second liquid silicone composition then coated with a third crosslinked silicone elastomer obtained from a third liquid silicone composition.
  • the undiluted RHODORSIL TCS 7534® A + B silicone elastomer is used (viscosity 45 Pa.s), as described in Example 1.
  • the second liquid silicone composition which is more fluid, is a siloxane resin silicone composition, and which comprises:
  • This second liquid silicone composition has a viscosity of 1 Pa.s.
  • the amount of crosslinker is such that the crosslinking reaction is incomplete.
  • the second silicone composition has, after crosslinking, a sufficient number of reactive groups to allow adhesion of the third, subsequently coated silicone composition.
  • One of the faces of the glass fabric is first coated with the doctor blade, by means of the Mathis coating machine, with the first silicone composition.
  • the weight deposited is 200 g / m 2 .
  • the first silicone composition is crosslinked at 150 ° C. in 2 min.
  • the second silicone composition is coated by means of the Mathis coating machine.
  • the second silicone composition is crosslinked at 130 ° C. in 1 min.
  • the resulting deposit is of the order of 50 g / m 2 .
  • a third silicone layer is applied to the second crosslinked silicone composition by doctor coating using the Mathis coating machine. The weight deposited is 200 g / m 2 .
  • the third silicone composition is crosslinked to
  • Example 2.1 is reproduced but using, for the second, more fluid silicone layer, 5 parts of crosslinking agent SILCOLEASE CROSSLINKER 96A®.
  • the crosslinker being in excess, the second silicone composition is completely crosslinked and no longer has a reactive group available to allow adhesion of the subsequently applied third silicone layer.
  • the capillary rise is eliminated thanks to the fluidity of this second silicone composition which penetrates well into the fibers of the fabric.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP08735781A 2007-04-03 2008-04-03 Verfahren zur herstellung eines fasermaterials/silikonverbundstoffes und besagtes fasermaterial/silikonverbundstoff Withdrawn EP2134898A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0754245A FR2914657A1 (fr) 2007-04-03 2007-04-03 Procede d'obtention d'un composite materiau fibreux/silicone et ledit composite materiau fibreux/silicone
PCT/EP2008/054039 WO2008122574A1 (fr) 2007-04-03 2008-04-03 Procede d'obtention d'un composite materiau fibreux/silicone et ledit composite materiau fibreux/silicone

Publications (1)

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EP2134898A1 true EP2134898A1 (de) 2009-12-23

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US (1) US20100178517A1 (de)
EP (1) EP2134898A1 (de)
JP (1) JP2010523831A (de)
CN (1) CN101680162A (de)
FR (1) FR2914657A1 (de)
WO (1) WO2008122574A1 (de)

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PT2462275T (pt) * 2009-08-04 2016-08-26 Dsm Ip Assets Bv Fibras revestidas de elevada resistência
CN104911920B (zh) * 2010-04-29 2018-10-19 3M创新有限公司 电子束固化的硅化纤维幅材
EP2576030B1 (de) 2010-06-02 2017-03-01 University Of Calcutta Verfahren zur vernetzung von celluloseethern unter milden bedingungen
CN102041688B (zh) * 2010-11-01 2012-11-14 高文源 一种防水透气有机硅合成革及其制造方法
DE102011050893B4 (de) * 2011-06-07 2016-01-14 Telair International Gmbh Frachtcontainer und Verfahren zur Herstellung eines Frachtcontainers
JP6518590B2 (ja) * 2012-11-12 2019-05-22 ダウ シリコーンズ コーポレーション 膨張可能な安全装置のためのシリコーンエラストマー及びトップコートを有する可撓性熱シールド
CA2888358C (en) 2012-11-12 2021-03-16 Dow Corning Corporation Flexible heat shield with silicone elastomer and a topcoat for inflatible safety devices
CN104531708B (zh) * 2014-11-24 2017-04-19 西南大学 棉花纤维特异表达启动子tb17p1及其应用
FR3053975B1 (fr) * 2016-07-15 2018-08-17 Universite Claude Bernard Lyon 1 Materiau composite silicone pour la fabrication de replique de tissu vasculaire
CN106700438A (zh) * 2016-12-08 2017-05-24 广西北海浩邦新能源科技有限公司 一种新型环保塑料及其制备方法
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KR102268405B1 (ko) * 2018-01-29 2021-06-24 주식회사 엘지에너지솔루션 이차 전지용 절연판 및 그의 제조 방법
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FR2914657A1 (fr) 2008-10-10
WO2008122574A1 (fr) 2008-10-16
US20100178517A1 (en) 2010-07-15
CN101680162A (zh) 2010-03-24
JP2010523831A (ja) 2010-07-15

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