Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, 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
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, 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
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, 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
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial 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
  • D06N3/125—Artificial 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 polyamides
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, 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
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial 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
  • D06N3/128—Artificial 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B60—VEHICLES IN GENERAL
  • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
  • B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
  • B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
  • B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
  • B60R21/23—Inflatable members
  • B60R21/235—Inflatable members characterised by their material
  • B60R2021/23504—Inflatable members characterised by their material characterised by material

Definitions

• the general field of the invention is that of silicone coating compositions, in particular those of the bicomponent or multicomponent type, the composition of the invention being useful for the protection of an inflatable bag frictional bag.
• crosslinkable by polyaddition, hydrosilylation or radical reactions to produce a thin layer elastomer.
• These crosslinked compositions are suitable, inter alia, as a coating, for example of protection or mechanical reinforcement of different substrates of textile material such as for example fibrous, woven, knitted or nonwoven supports.
• Such silicone coatings are generally obtained by coating the substrate then hardening resulting from the polyaddition of the unsaturated groups (alkenyls, eg Si-Vi) of a polyorganosiloxane on hydrogens of the same or of another polyorganosiloxane.
• unsaturated groups alkenyls, eg Si-Vi
• an explosive tablet initiates the combustion of an additional charge, then that of the solid fuel; it turns into gas (for example nitrogen) and inflates the cushion.
• gas for example nitrogen
• these are formed by a canvas of synthetic fiber, for example polyamide, covered on at least one of these faces with a layer of an elastomer of the chloroprene type.
• the airbag (or airbag) is an airbag made of polyamide fabric, folded and tight.
• the silicone compositions easily supplanted the chloroprenes in this application, as it has been found that the latter do not satisfactorily meet all of the abovementioned specifications.
• These silicone compositions have therefore found an important outlet in the coating of flexible materials - woven, knitted or non-woven - used for the manufacture of individual occupant protection bags for vehicles, also called "airbags". This is how the present invention relates to the application of silicones in the manufacture of such protective bags.
• the front airbags can be adaptive and deploy in proportion to the severity of the impact. They can be supplemented with side airbags and curtains.
• the presence of such a layer or such a protective coating is dictated by the fact that the gases released by the gas generator in the event of an impact, are extremely hot and contain incandescent particles capable of damaging the nylon bag. ® .
• the internal protective elastomer layer must therefore be particularly resistant to high temperatures and mechanical stresses. It is also important that this elastomeric coating is in the form of a film, uniform and perfectly adherent to the support of synthetic fabric, forming the walls of the "airbag". However, when the deposition of silicone increases, an increase in the coefficient of friction is observed, that is to say a degradation of the sliding properties of the airbag.
• these known silicone compositions comprise: - (A) a polydiorganosiloxane having at least two alkenyl groups per molecule, - (B) a polyorganohydrogensosiloxane having at least two hydrogen atoms bonded to silicon in each molecule , - (C) a platinum group metal catalyst, - (D) an adhesion promoter consisting of an epoxy-functional organosilicon compound, - (E) an inorganic filler, the amount of which by weight is defined relative to the amount polyorganosiloxane (A), - (F) a polyorganosiloxane resin, and optionally - (G) a compound useful as a crosslinking inhibitor.
• this reference only presents solutions for obtaining homogeneous and adhesive films for airbag coatings and is silent when the problem cited above is resolved.
• these silicone compositions comprise: - (A) a polydiorganosiloxane having at least two alkenyl groups per molecule,
• EP-A-0 681 014 describes a silicone composition, applicable in particular as an internal "airbag” coating and having for this purpose good properties, in particular in terms of fire and temperature resistance, mechanical properties, resistance with aging, adhesion and uniformity of surface, adhesion to textile substrates being more particularly sought after.
• the solution proposed by this invention consists in using: - a silicone coating composition consisting in the mixture formed of: (1) at least one polyorganosiloxane having, per molecule, at least two C2-C6 alkenyl groups linked to silicon, (2) at least one polyorganosiloxane having, per molecule, at least two hydrogen atoms bonded to silicon, (3) a catalytically effective amount of at least one catalyst, composed of at least one metal belonging to the group of platinum, (4) an adhesion promoter, (5) optionally a mineral filler, (6) optionally at least one crosslinking inhibitor, and (7) optionally at least one polyorganosiloxane resin, Composition in which the adhesion promoter is constituted exclusively by the association at least ternary of the following ingredients: - (4-1) at least one alkoxylated organosilane containing, per molecule, at least one C2-C6 alkenyl group, - (4-2) at least one organosilicon compound comprising at least one epoxy radical, and
• French Patent No. 2,765,884 describes a silicone composition comprising as a mixture: (1) at least one polyorganosiloxane having, per molecule, at least two alkenyl groups, of C2-C6 bonded to silicon, (2) at least one polyorganosiloxane having , per molecule, at least two hydrogen atoms bonded to silicon, (3) a catalytically effective amount of at least one catalyst, composed of at least one metal belonging to the platinum group, (4) an adhesion promoter , (5) optionally a reinforcing system which can be at least one polyorganosiloxane resin and / or at least one reinforcing filler, (6) optionally at least one crosslinking inhibitor, and (7) hollow organic or mineral microspheres.
• These expandable organic microspheres comprising a polymeric wall containing a liquid or a gas.
• the expansion of these microspheres is caused by heating beyond the softening point of the polymer and at a temperature sufficient to vaporize the liquid or suitably expand the gas which may be, for example, an alkane such as isobutane or isopentane.
• the polymers used in its walls are prepared from vinyl chloride, vinylydene chloride, acrylonitrile, methyl methacrylate or styrene monomers or from acrylonitrile / methacrylonitrile or acrylonitrile / vinylidene chloride copolymers.
• one of the essential objectives of the invention is to provide a method for improving the coefficient of friction of a woven, knitted or coated nonwoven fibrous support. These supports treated by the method according to the invention are useful in particular for applications in the field of safety air bags for vehicles, or airbags.
• a second objective of the invention is to provide a silicone composition for crosslinking by polyaddition or free radical reactions useful in particular for applications in the field of safety air bags for vehicles, or airbags, having after crosslinking and coating on a fabric, optimal sliding properties, that is to say having a good coefficient of friction.
• a third objective of the invention is to provide a crosslinkable silicone coating composition for "airbag", which is easy to implement and apply and which, moreover, is economical.
• a final objective is to provide a woven, knitted or nonwoven fibrous support coated on one or two faces with a silicone elastomer according to the invention which is particularly useful in the field of airbags.
• the present invention taken in a first object, relates to a method for improving the coefficient of friction of a woven, knitted or coated nonwoven fibrous support, comprising the following steps: a) the preparation of a silicone composition coating (A) crosslinkable comprising: (1) components (a-1) or (a-2): - (a-1) corresponding to at least one polyorganosiloxane capable of crosslinking by the action of a catalyst to base of at least one organic peroxide, and - (a-2) corresponding to a mixture of polyorganosiloxane capable of crosslinking by polyaddition reactions comprising: - at least one polyorganosiloxane (I) having, per molecule, at least two alkenyl groups , in C2-C6 bonded to silicon, and - at least one polyorganosiloxane (II) having, per molecule, at least two hydrogen atoms bonded to silicon, (2) an effective amount of crosslinking catalyst consisting: when (a- 1) is
• step b) optionally at least one crosslinking inhibitor (VI), b) the application of at least 10 g / m 2 on one or two sides of a woven, knitted or nonwoven fibrous support of the silicone coating composition (A) prepared in step a), and c) crosslinking of the deposit formed at step b) to form an elastomer by heating to a temperature which can reach 210 ° C. or by electromagnetic radiation, in particular by infrared radiation.
• the presence of the particles of the resin (III) comprising at least one (co) polyamide have the effect of increasing the roughness of the coating, which results in a reduction in the coefficient of friction without deteriorating the mechanical properties of the fabric.
• the particles of the resin (III) comprise at least one (co) polyamides selected from the group consisting of: polyamide-6, polyamide-6.6, polyamide-4, polyamide-11, polyamide- 12, polyamides 4-6, 6-10, 6-12, 6- 36, 12-12, their copolymers and mixtures.
• the particles of the resin (III) comprise polyamide-12.
• the particles of the resin (III) are spherical in shape.
• the (co) polyamide particles will preferably have an average diameter of between 5 and 100 ⁇ m and in particular between 10 and 50 ⁇ m.
• these particles are present up to 40% by weight, preferably at a rate of 1 to 30% by weight, and even more preferably at a rate of 5 to 20% by weight relative to the total weight of the mixture.
• the polyorganosiloxane (ai) capable of crosslinking by the action of a catalyst based on at least one organic peroxide is advantageously a product having siloxy units of formulas:
• R a SiO _ - - 1 0-1) in which: - the symbols R 1 , identical or different, represent a hydrocarbon group having from 1 to 12 carbon atoms, preferably from 1 to 8 carbon atoms, optionally substituted, and - a is 1, 2 or 3.
• the symbols R 1 are chosen from: - methyl, ethyl, propyl, butyl, hexyl and dodecyl groups, - cycloalkyl groups such as, for example, cyclohexyl, - alkenyl groups such as, for example, vinyl, allyl, butenyl and hexenyl groups, - aryl groups such as, for example, phenyl, tolyl, aralkyl groups such as ⁇ -phenylprolyl, and - the groups mentioned above in which one or more hydrogen atoms are replaced by one or more halogen atoms, a cyano group or equivalent of a cyano group such as, for example, chloromethyl, trifluoropropyl or cyanoethyl.
• - cycloalkyl groups such as, for example, cyclohexyl
• - alkenyl groups such as, for example, vinyl, allyl, butenyl and
• the polyorganosiloxanes (a-1) are terminated at the chain end with trimethylsilyl, dimethylvinyl, dimethylhydroxysilyl, trivinylsilyl units.
• the polyorganosiloxanes (a-1) contain at least two alkenyl groups per molecule.
• organic peroxides useful according to the invention there may be mentioned benzoyl peroxide, bis (p-chlorobenzoyl) peroxide, bis (2,4-dichlorobenzoyie) peroxide, dicumyl peroxide, di-t peroxide -butyl, 2,5-dimethyl- 2,5-di (t-butylperoxy) hexane, t-butyl-perbenzoate, t-butylcumyl peroxide, halogen derivatives of the peroxides mentioned above such as peroxide of bis (2,4-dichlorobenzoyl), 1,6-bis (p-toluoylperoxycarbonyloxy) hexane, 1,6- bis (benzoylperoxy-carbonyloxy) hexane, 1,6-bis (p-toluoylperoxycarbonyloxy) butane and 1,6-bis (2,4-dimethylbenzoylper
• the polyorganosiloxane (I) of the silicone coating composition (A) used for the mode of crosslinking by polyaddition reactions comprises: (i) siloxy units of formula: (1-1) in which: - the symbols R 1 , an alkenyl group, preferably vinyl or allyl, - the symbols Z, identical or different, each represent a monovalent hydrocarbon group, free from any adverse action on the activity of catalyst and chosen from alkyl groups having from 1 to 8 carbon atoms inclusive, optionally substituted with at least one halogen atom, and also from aryl groups, - a is 1 or 2, b is 0, 1 or 2 and the sum a + b is equal to 1, 2 or 3, and optionally (ii) other siloxy units of formula: Zc SiO ⁇ 9 - (I-2) in which: - Z has the same meaning as above and c is 0, 1, 2 or 3.
• This polydiorganosiloxane (I) may have a viscosity at least equal to 200
• the polyorganosiloxane (I) can be formed only of units of formula (1-1) or can additionally contain units of formula (I-2). Likewise, it may have a linear, branched cyclic or network structure.
• Z is generally chosen from methyl, ethyl and phenyl radicals, at least 60 mol% (or by number) of the radicals Z being methyl radicals.
• Examples of siloxyl units of formula (1-1) are the vinyidimethylsiloxyl, vinylphenylmethylsiloxyl, vinylmethylsiloxyl and vinylsiloxyl units.
• siloxyl units of formula (I-2) are the Si0 4/2 , dimethylsiloxyl, methylphenylsiloxyl, diphenylsiloxyl, methylsiloxyl and phenylsiloxyl units.
• polyorganosiloxanes (I) are linear and cyclic compounds such as: dimethylpolysiloxanes with dimethylvinylsilyl ends, copolymers (methylvinyl) (dimethyl) polysiloxanes with trimethylsilyl ends, copolymers (methylvinyl) (dimethyl) polysiloxanes with dimethylvinylsyl vinyl ends .
• the polyorganosiloxane (II) comprises siloxyl units of formula: in which :
• the groups L which are identical or different, each represent a monovalent hydrocarbon group, free from any unfavorable action on the activity of the catalyst and chosen, preferably, an alkyl group having from 1 to 8 carbon atoms included, optionally substituted with at least one halogen atom, advantageously from the methyl, ethyl, propyl and 3,3,3-trifluoropropyl groups, an aryl group and, advantageously, an xylyl, tolyl or phenyl radical,
• - d is 1 or 2
• e is 0, 1 or 2
• the sum d + e is equal to 1, 2 or 3
• - optionally, at least part of the other motifs being motifs of average formula: (11-2) in which the groups L have the same meaning as above and g is equal to 0, 1, 2 or 3.
• the dynamic viscosity of this polyorganosiloxane (II) is at least equal to 10 mPa.s and, preferably, it is between 20 and 1000 mPa.s.
• the polyorganosiloxane (II) can only be formed of units of formula (11-1) or additionally comprise units of formula (II-2).
• the polyorganosiloxane (II) can have a linear, branched, cyclic or network structure.
• Group L has the same meaning as group Z above.
• Examples of units of formula (11-1) are H (CH 3) 2 SiO ⁇ / 2, HCH 3 Si0 2/2 and
• the examples of units of formula (II-2) are the same as those given above for the units of formula (I-2).
• Examples of polyorganosiloxane (II) are linear and cyclic compounds such as:
• Compound (II) can optionally be a mixture of a dimethylpolysiloxane with hydrogenodimethylsilyl ends and a polyorganosiloxane comprising at least 3 hydrogenosiloxyl groups.
• the ratio of the number of hydrogen atoms bonded to silicon in the polyorganosiloxane (II) to the total number of alkenyl unsaturated groups in the polyorganosiloxane (I) is between 0.4 and 10, preferably between 0.6 and 5 .
• the bases of silicone polyaddition compositions may contain only linear polyorganosiloxane (I) and (II) such as, for example, those described in the patents: US-A-3,220,972, US-A-3,697,473 and US- A-4 340 709 or contain both branched or networked polyorganosiloxane (I) and (II), such as those described in the patents: US-A-3,284,406 and US-A-3,434,366.
• linear polyorganosiloxane (I) and (II) such as, for example, those described in the patents: US-A-3,220,972, US-A-3,697,473 and US- A-4 340 709
• contain both branched or networked polyorganosiloxane (I) and (II) such as those described in the patents: US-A-3,284,406 and US-A-3,434,366.
• the crosslinking catalysts when (a-2) is used consists of at least one metal (or compound) from the platinum group which are also well known.
• the metals of the platinum group are those known under the name of platinoids, a designation which includes, in addition to platinum, ruthenium, rhodium, palladium, osmium and iridium.
• the compounds of platinum and rhodium are preferably used.
• the generally preferred catalyst is platinum.
• the quantity by weight of catalyst (III), calculated by weight of platinum-metal is generally between 2 and 400 ppm, preferably between 5 and 200 ppm based on the total weight of the polyorganosiloxanes (I) and (II ).
• the presence of the additive system (B) in the silicone coating composition (A) according to the invention makes it possible to control the combing resistance and the tear resistance of the coated woven, knitted or nonwoven fibrous support.
• the calcium carbonate does not need to undergo a compatibilization treatment (by heating or surface treatment) for its implementation in the system (B) and cannot therefore be assimilated to a simple semi-reinforcing filler.
• the resin (V) preferably comprises at least one alkenyl residue in its structure.
• the polyorganosiloxane resin (V) comprises siloxy units Q of formula Si0 / 2 .
• the polyorganosiloxane resin (V) comprises in its structure from 0.1 to 20% by weight of alkenyl group (s), preferably greater than 4% by weight, said structure having siloxyl units type M, identical or different, siloxy units of type (s) T, identical or different, and or Q and optionally siloxy units of type D.
• the polyorganosiloxane resin (V) comprises at least 2% by weight, and preferably at least 5% by weight of type Q siloxyl units.
• These resins (V) are well-known branched organopolysiloxane oligomers or polymers which are commercially available. They are in the form of solutions, preferably siloxane.
• R 3 SiOo, 5 unit M
• R 2 SiO unit D
• RSiO ⁇ ⁇ 5 unit T
• Si0 2 unit Q
• l at least one of these units being a T or Q unit.
• the radicals R are identical or different and are chosen from linear or branched C1-C6 alkyl radicals, C2-C4 phenyl alkenyl radicals, trifluoro-3,3 , 3 propyl, and hydroxyl groups.
• alkyl radicals R methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals
• alkenyl radicals R vinyl radicals.
• part of the radicals R are alkenyl radicals.
• oligomers or branched organopolysiloxane polymers that may be mentioned are MQ resins, MDQ resins, TD resins and MDT resins, the alkenyl functions being able to be carried by the M, D and / or T units.
• vinylated MDQ resins having a weight content of vinyl group of between 0.2 and 10% by weight.
• the crosslinkable silicone coating composition (A) according to the invention comprises a reinforcing filler
• this may be a silica with a BET specific surface of at least 50 m 2 / g.
• the fillers are advantageously treated by treatment with the various organosilicon compounds usually used for this use.
• organosilicon compounds can be organochlorosilanes, diorganocyclopolysiloxanes, hexaorganodisiloxanes, hexaorgano-disilazanes or diorganocyclopolysilazanes (French patents FR-A-1 126 884, FR-A-1 136 885, FR-A-1 236 505, English patent GB-A-1,024,234).
• the crosslinking silicone composition (A) according to the invention may also comprise a semi-reinforcing filler or conventional stuffing, for example diatomaceous earth or ground quartz.
• non-siliceous mineral materials can intervene as semi-reinforcing or tamping mineral fillers: carbon black, titanium dioxide, aluminum oxide, hydrated alumina, expanded vermiculite, non-vermiculite expanded, calcium carbonate having undergone a compatibilization treatment, zinc oxide, mica, talc, iron oxide, barium sulphate and slaked lime, etc.
• These fillers may be present at a rate of 5 to 30%, preferably 15 to 25% for reinforcing fillers and 5 to 40%, preferably 10 to 30% for semi-reinforcing or tamping fillers, compared to the total composition.
• the alkoxylated organosilane (IV.1) of the promoter (IV) has the following general formula:
• R6 is a linear or branched C1-C4 alkyl radical
• R7 is a linear or branched alkyl radical
• y is equal to 0, 1, 2 or 3
• X being defined by the following formula:
• - E and D which are identical or different radicals chosen from linear or branched C1-C4 alkyls, - z which is equal to 0 or 1, - R8, R9, R10 which are identical or different radicals representing l hydrogen or a linear or branched C1-C4 alkyl, and - R8 and R9 or R10 which may alternately constitute together and with the two carbons carrying the epoxy, an alkyl ring having from 5 to 7 members, or b) either from the products (IV.2b) constituted by epoxyfunctional polydiorganosiloxanes comprising: (i) at least one siloxyl unit of formula: G ⁇ S i ⁇ il ⁇ ⁇ f
• the preferred products are those whose metal
• M of the chelate and or of the alkoxide (IV.3) is chosen from the following list: Ti, Zr, Ge, Li or
• titanium is more particularly preferred. It can be associated, for example, with an alkoxy radical of the butoxy type.
• the adhesion promoter (IV) may be made up of: (IV.1) alone (IV.2) alone - (IV.1) + (IV.2) according to two preferred methods: (IV.1) x (IV .3) (IV.2) x (IV.3) and finally according to the most preferred method: (IV.1) + (IV.2) + (IV.3).
• an advantageous combination for forming the adhesion promoter is as follows:
• VTMO vinyltrimethoxysilane
• the weight proportions between (IV.1), (IV.2) and (IV.3) expressed in percentages by weight compared to the total of the three, are as follows: - ( IV.1)> 10, preferably between 15 and 70 and more preferably still between 25 and 65, - (IV.2) ⁇ 90, preferably between 70 and 15 and more preferably still between 65 and 25, and - (IV.3)> 1, preferably between 5 and 25 and more preferably still between 8 and 18 , it being understood that the sum of these proportions in (IV.1), (IV.2) and (IV.3) is equal to
• the weight ratio (IV.2): (IV.1) is preferably between 2: 1 and 0.5: 1, the 1: 1 ratio being more particularly preferred.
• the adhesion promoter (IV) is present in an amount of 0.1 to 10, preferably 0.5 to 5 and more preferably still 1 to 3% by weight relative to all of the constituents of the silicone composition. coating (A) crosslinkable.
• a crosslinkable silicone coating composition (A) is used in the process according to the invention which comprises a mixture formed of: (1) at least one polyorganosiloxane (I) having, per molecule , at least two alkenyl groups, in C2-C6 bonded to silicon, (2) at least one polyorganosiloxane (II) having, per molecule, at least two hydrogen atoms bonded to silicon, (3) a catalytically effective amount of at least one catalyst composed of at least one metal belonging to the platinum group, (4) at least one adhesion promoter (IV), (5) particles of at least one resin (III) comprising at least one ( co) polyamide (6) an additive system (B), the constituents of which are added sequentially or simultaneously, consisting of the mixture formed from: - at least one polyorganosiloxane resin (V) present up to 60% by weight relative to the total weight of the mixture and possibly mixed at least one polyorganosiloxane diluent, and - calcium carbonate
• acetylenic alcohols (Cf. FR-B-1 528 464 and FR-A-2 372 874), which are part of the preferred hydrosilylation reaction thermal 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 at ⁇ of the triple bond possibly being able to form a ring; the total number of carbon atoms contained in R' and R" being at least 5, preferably from 9 to 20.
• ⁇ -acetylenic alcohols there may be mentioned as examples: - 1-ethynyl-1-cyclohexanol; - 3-methyl-dodecy-1 ol-3; - trimethyl-3,7,11 dodécyne-1 ol-3; - diphenyl-1, 1 propyne-2 ol-1; - 3-ethyl-6-ethyl nonyne-1 ol-3; - 2-methyl-butyne-3 ol-2; - 3-methyl-pentadecyne-1 ol-3.
• diallylmaleate or derivatives of diallylmaleate are commercial products.
• Such a retarder (VI) is present at a rate of 3000 ppm at most, preferably at the rate of 100 to 1000 ppm relative to the total weight of the organopolysiloxanes (I) and (II).
• the crosslinkable silicone coating composition (A) according to the invention can be added with various conventional additives such as, for example, the dyes.
• the invention also relates to the crosslinkable silicone coating composition (A) as used in the method according to the invention and described above.
• the present invention relates to a two-component or multi-component precursor system (C) of the crosslinkable silicone coating composition (A) described above.
• a precursor system comprises at least two separate parts A and B, intended to be mixed to form the composition, one of these parts
• a or B comprising the catalyst and a single species (I) or (II) of polyorganosiloxane.
• a promoter system IV-1) (IV-2) and (IV-3)
• another characteristic of this precursor system is that its part A or B containing the polyorganosiloxane (II) is free of compounds ( IV-3) of the promoter (IV) and that its part A or B including the compound (IV-1) of the promoter (IV) does not include the catalyst (III).
• the viscosity of parts A and B and of their mixture together can be adjusted by varying the amounts of the constituents and by choosing polyorganosiloxanes of different viscosities.
• parts A and B form a ready-to-use silicone composition, which can be applied to the support by any suitable coating means (for example doctor blade or cylinder).
• a final deposited thickness after crosslinking will be aimed at between 25 and 300 ⁇ m, in particular between 50 and 200 ⁇ m. It is not necessary to have a uniform layer, because if the surface of the support is not regular, it can result in an irregular deposit.
• the compositions according to the invention are crosslinked thermally and / or by electromagnetic radiation (radiation of accelerated electrons or "electron beam").
• the compositions according to the invention can be used for coating or coating flexible supports, in particular woven, knitted or nonwoven fibrous textiles, and preferably woven, knitted or nonwoven supports made of synthetic fibers, advantageously of polyester or polyamide.
• the invention also relates to a woven, knitted or nonwoven fibrous support coated on one or two faces with an elastomer capable of being obtained: a) - by applying at least 10 g / m 2 to one or more two sides of a woven, knitted or nonwoven fibrous support of the crosslinkable silicone coating composition (A) described above or of the composition resulting from the mixture of parts A and B of the bicomponent or multicomponent system (B) described above, and - The crosslinking of the deposit formed in the previous step to form an elastomer by heating to a temperature up to 210 ° C, by electromagnetic radiation, or by infrared radiation, or b) by the process according to the invention described above.
• Another aspect of the invention relates to an airbag for the protection of a vehicle occupant, formed from a coated support according to the procedure of the invention described above.
• the invention also relates to the use of the bicomponent or multicomponent system.
• a silicone coating composition (A) crosslinkable according to the invention for coating woven, knitted or nonwoven fibrous support Preferably, these supports are intended to form air bags for the protection of vehicle occupants.
• the support is an open-textured fabric having a porosity> 10 l / dm 2 / min according to ISO 9237 standard.
• the coating or coating of at least one of the faces of the flexible support material, in particular textile (polyamide fabric for example) is useful for the manufacture of technical fabrics such as in particular the air bags for the individual protection of occupants of vehicles, in the event of an impact, tent fabrics, parachute fabrics and the like.
• the compositions or the method according to the invention prove to be remarkable not only for the coating of supports conventionally used in particular in the manufacture of airbags, but also for the coating of supports with open texture.
• support with open texture we mean supports with porosity> 10 l / dm 2 / min according to ISO 9237.
• the open texture in the case of a fabric, we can especially define the open texture as corresponding to a number of warp threads and weft per centimeter the sum of which is less than or equal to 36.
• fabrics particularly recommended in the context of the present invention mention will generally be made of fabrics whose weight in the uncoated state is less than 200 g / m 2 and in particular less than or equal to 160 g / m 2 . Mention may therefore be made of such fabrics, in particular of polyamide, having from 16 x 16 to 18 x 18 threads / cm, for example fabrics of 470 dtex (decitex) having these characteristics.
• substrates in particular fabrics, formed from technical textile fibers, that is to say textile fibers having improved properties compared to conventional fibers, for example increased toughness, in order to impart specific or reinforced properties depending on the applications of the support or coated fabric.
• the invention therefore also relates to such a flexible support, in particular textile, coated in accordance with the invention and can therefore have the characteristics and properties indicated above.
• the coating in question here may correspond to the deposition of a single layer on at least one of the faces of the flexible support material (primary coating). However, it may also be the deposition of a second layer or possibly a third layer on at least one of the faces of the support material already coated (secondary coating) to have the desired total thickness guaranteeing the best possible performance. waterproof material and favorable touch characteristics.
• the viscosity is measured using a BROOKFIELD viscometer according to the indications of standard AFNOR NFT-76-106 of May 82.
• Example 1 the viscosity is measured using a BROOKFIELD viscometer according to the indications of standard AFNOR NFT-76-106 of May 82.
• diluent a polydimethylsiloxane oil blocked at each end of the chains by a pattern (CHs ⁇ ViSiOo.s, having a viscosity of 60,000 mPa.s.
• IV adhesion promoters
• mixture composed of: - (IV-1) vinyltrimethoxysilane (VTMO), - (IV-2) glycidoxypropyltrimethoxysilane (GLYMO), and - (IV-3) butyl titanate Ti (OBu) 4 (TBT),
• V polyorganosiloxane of formula MM 'DD O containing 0.8% by weight of vinyl groups (Vi) and consisting of 27% by weight of units (CHs ⁇ SiOo.s, 0.15% by weight of units (CH3 ) 2 ViSiOo, 5.60% by weight of units (CHs ⁇ SiO, 2.4% by weight of units (CH 3 ) ViSiO and 9.6% by weight of units Si ⁇ 2 and a residue of OH groups.
• a composition is prepared from a two-component precursor: - A control composition (C-1) is obtained by mixing, at room temperature, 100 parts by weight of part A and 10 parts by weight of part B of a two-component system (see composition in Table 1). - A composition (1-1) according to the invention is obtained by mixing, at room temperature, of: - 125 parts by weight of part A-1 obtained by mixing 100 parts by weight of Part A of the C-1 composition and 25 parts by weight of beads Orgasol ® 2002 NAT3 ES3, and
• each mixture (C-1 and 1-1) is coated (variable coating rate, expressed in g / m 2 ) to form a deposit using doctor blades or cylinders on a polyhexamethyleneadipamide type 6.6 desized with a title of 235 decitex (dtex), and c) the resulting layer is crosslinked for 80 seconds at 180 ° C. in a MATHIS oven to obtain an elastomer.
• the results of the compared tests are shown in Tables II to IV.
• the friction coefficient (Ks) measurements are made according to standard NFQ 03-082.
• Table II represents the measurements of the coefficients of friction obtained by friction on a glass plate.
• Table III represents the measurements of the coefficients of friction obtained by friction of the sample of coated fabric on itself, coated side on coated side.
• Table I The friction coefficient (Ks) measurements are made according to standard NFQ 03-082.
• Table II represents the measurements of the coefficients of friction obtained by friction on a glass plate.
• Table III represents the measurements of
• composition 1-1 according to the invention leads to a lower coefficient of friction (COF) than that obtained with the control composition C-1 when the deposits are comparable in terms of quantity / unit area of the coated fabric.
• the crumple and abrasion resistance test (scrub test) (standard ISO 5981 A) reflects the adhesion and the aging resistance of the composition. This test consists in subjecting the fabric, on the one hand, to a shearing movement using two jaws pinching the two opposite edges of a test tube and moving in an alternating movement with respect to each other and, on the other hand, to abrasion by contact with a mobile support. Table IV.
• formula 1-1 makes it possible to preserve the properties of use of the fabric as obtained with formula C-1 while improving the coefficient of friction.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Dispersion Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Proteomics, Peptides & Aminoacids (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Paints Or Removers (AREA)
• Air Bags (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=34566266

Family Applications (1)

Country Status (5)

Families Citing this family (11)

Family Cites Families (4)

• 2003
  • 2003-12-01 FR FR0314064A patent/FR2862990B1/fr not_active Expired - Fee Related
• 2004
  • 2004-11-18 CN CNA2004800406700A patent/CN1906354A/zh active Pending
  • 2004-11-18 WO PCT/FR2004/002941 patent/WO2005066412A1/fr active Application Filing
  • 2004-11-18 KR KR1020067010762A patent/KR20060102344A/ko not_active Application Discontinuation
  • 2004-11-18 EP EP04805478A patent/EP1689927A1/de not_active Withdrawn

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events