EP2173939A2 - Composition elastomere silicone adhesive - Google Patents

Composition elastomere silicone adhesive

Info

Publication number
EP2173939A2
EP2173939A2 EP08786623A EP08786623A EP2173939A2 EP 2173939 A2 EP2173939 A2 EP 2173939A2 EP 08786623 A EP08786623 A EP 08786623A EP 08786623 A EP08786623 A EP 08786623A EP 2173939 A2 EP2173939 A2 EP 2173939A2
Authority
EP
European Patent Office
Prior art keywords
silicone
optionally
groups
composition
polyorganosiloxane
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Withdrawn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
EP08786623A
Other languages
German (de)
English (en)
French (fr)
Inventor
Alain Pouchelon
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 EP2173939A2 publication Critical patent/EP2173939A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/28—Non-macromolecular organic substances
    • C08L2666/52—Metal-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/54—Inorganic substances

Definitions

  • the general field of the invention is that of hot-vulcanizable silicone elastomer compositions (EVC) by reaction of a polyorganosiloxane capable of crosslinking by the action of a catalyst based on at least one organic peroxide, or a polyorganosiloxane comprising alkenyl groups with a polyorganohydrogensiloxane in the presence of a metal catalyst, preferably based on platinum.
  • EMC hot-vulcanizable silicone elastomer compositions
  • Such compositions are used, for example, for bonding silicone substrates based on fibrous materials, in particular flexible supports, such as woven supports or nonwoven supports, comprising at least one silicone coating obtained by coating or impregnation of at least one of their faces, using at least one liquid silicone composition at the time of this operation and crosslinkable elastomer.
  • Varnishes in particular silicone lacquers, can also be applied to such coatings. In these different cases, silicone complexes are then obtained.
  • These flexible supports with a two-dimensional nature are chosen in particular from textile fabrics optionally coated with a layer of silicone elastomer on which an anti-fouling varnish is optionally applied, such fabrics being capable of being used for the manufacture of: architectural textiles (textile architectural elements);
  • these flexible supports different from the architectural textiles may be, for example, those intended for the manufacture of, in particular:
  • the rubber used in the adhesive EVC is, for example, of the type M VI DD v 'M Vl ; with the following definition of siloxy units, M: (CH3) 3 Si0i / 2, M Vi: (CH 3) 2 ViSi0 ⁇ / 2, D:
  • This gum composition also comprises a free radical curing / crosslinking catalyst: 2,4-dichlorobenzoyl peroxide and a silica filler treated with THexaMethylDisilazane.
  • This crosslinkable material is used to produce adhesive tapes for example by rolling the silicone adhesive onto a peelable film. The strips are then placed in the area of overlap of the composite parts to be assembled. Then come under pressure (2 kg / 5 cm) and heating (180 0 C - 10 min). Another solution has been described in the international patent application
  • This document describes an assembly intermediate for joining two textile sheets each having a coating layer of a silicone-based polymer.
  • This bonding intermediate comprises, in a known manner, a composition based on an uncrosslinked silicone elastomer. To ensure its handling and protection. the bonding medium is also equipped with a release film positioned on one of its faces.
  • the bonding intermediate is in the form of a straight flat section of a strip based on the non-crosslinked silicone elastomer composition. This rectilinear section also comprises a translucent film present on the second face of the strip, that is to say the one opposite to that which receives the release film.
  • one of the essential objectives of the present invention is to provide a new silicone elastomeric composition, adhesive and hot crosslinkable performance for assembly of complex fiber / silicone parts.
  • Another object of the present invention is to provide a new silicone elastomer composition, adhesive and heat-curable, to ensure an assembly whose breakage stressed in peeling will be in a cohesive regime and with a strength that guarantees the integrity of the 'assembly.
  • Another object of the present invention is to provide a new silicone elastomeric composition, adhesive and heat-crosslinkable, performing both in platinum and peroxidic catalysis.
  • Another object of the present invention is to provide a new silicone elastomeric composition, adhesive and heat-curable, suitable for a conformation in strips.
  • crosslinking catalyst consisting of: when (a-1) is carried out with at least one organic peroxide (IV) and when (a-2) is carried out with at least one metal or metal compound of the group platinum (V), a polyorganohydrogensiloxane adhesion promoter comprising Si-H (VI) groups,
  • optionally one or more functional additives for conferring specific properties characterized in that on the one hand the nature and on the other hand the amount of said polyorganohydrogensiloxane (VI) adhesion promoter are chosen so that Si groups are H are in excess of the crosslinking reaction of the composition, so as to obtain a surface density potential of covalent Si- bonds with the silicone substrate to be bonded with at least one covalent bond Si- per 60 nm 2 , preferably at least one covalent bond Si- per 40 nm 2 .
  • VI polyorganohydrogensiloxane
  • the surface density potential of covalent Si-bonds with the silicone substrate to be bonded is defined by the area in nm 2 necessary to obtain at least one covalent bond Si- in the extreme surface layer of the material considered, calculated according to the nature and the amount of the polyorganohydrogensiloxane (VI) and the optionally alkenylated polyorganosiloxane gum (I) or (Y), and optionally polyorganosiloxane (II).
  • the monomolecular layer is 0.75 nm thick.
  • the nature and on the other hand the amount of said polyorganohydrogensiloxane (VI) adhesion promoter are chosen so that the excess of Si-H groups consecutive to the crosslinking reaction with the alkenyl groups polyorganosiloxane gum (I or I ') is at least 0.1% by weight of SiH (mass 29) relative to the ratio SiH: Si-alkenyl equal to 1: 1, per 100 g of said silicone composition, preferably at least 0.15% SiH per 100 g of said silicone composition, the gum polyorganosiloxane (I) then having per molecule at least two alkenyl groups preferably C2-C6 bonded to silicon.
  • the silicone composition is a crosslinkable composition with peroxide catalysis.
  • the polyorganosiloxane gum (I) capable of crosslinking by the action of a catalyst based on at least one organic peroxide is advantageously a product having siloxyl units of formulas:
  • R 1 represents a hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, optionally substituted, and
  • R 1 is chosen from: methyl, ethyl, propyl, butyl, hexyl and dodecyl groups,
  • cycloalkyl groups for example cyclohexyl
  • alkenyl groups for example vinyl, allyl, butenyl and hexenyl groups
  • aryl groups for example phenyl, tolyl or aralkyl groups such as phenylprolyl, and
  • a cyano group or the equivalent of a cyano group such as, for example, a chloromethyl, trifluoropropyl or cyanoethyl group.
  • the polyorganosiloxanes (I) are terminated at the end of the chain by trimethylsilyl, dimethylvinyl, dimethylhydroxysilyl and trivinylsilyl units.
  • (I) contain per molecule at least two alkenyl groups, preferably C2-
  • the polyorganosiloxane gum (I) has the same definition as the polyorganosiloxane gum (T) used in platinum catalysis and as described hereinafter.
  • the gum (I) has a very high molecular weight, for example between 300 000 and 800 000, preferably between 400 000 and 600 000.
  • the gum (I) has an average content of alkenyl groups, preferably vinyl, of between 0 and 2000 ppm, and preferably between 200 and 1000 ppm.
  • the gum (I) may be a mixture of several gums corresponding to the same definition as the gum (I).
  • gums (I) are the gums for which the dimethylpolysiloxane main chain, or the main chain of a dimethylsiloxane-methylphenylsiloxane or dimethylsiloxane-diphenylsiloxane or dimethylsiloxane-methylvinylsiloxane copolymer, is terminated by trimethylsiloxy, dimethylvinylsiloxy or methylphenylvinylsiloxy groups or silanols.
  • organic peroxides (IV) that are useful according to the invention, mention may be made of benzoyl peroxide, bis (p-chlorobenzoyl) peroxide, bis (2,4-dichlorobenzoyl) peroxide, dicumyl peroxide, peroxide of di-t-butyl, 2,5-dimethyl-
  • the silicone composition is a crosslinkable metal-catalyzed composition, preferably based on platinum.
  • the polyorganosiloxane gum (I 1 ) has units of formula:
  • W is an alkenyl group, preferably vinyl
  • Z is a monovalent hydrocarbon group, which has no adverse effect on the activity of the catalyst and is selected from alkyl groups having 1 to 8 carbon atoms inclusive, optionally substituted by at least one halogen atom, and also from the aryl groups, a is 1 or 2, b is 0, 1 or 2 and a + b is between 1 and 3, and optionally other units of average formula: wherein Z has the same meaning as above and ca a value between 0 and 3.
  • Z groups may be the same or different.
  • 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.
  • the gum (T) has a very high molecular weight, for example between 300 000 and 800 000, preferably between 400 000 and 600 000.
  • the gum (I 1 ) has an average content of alkenyl groups, preferably vinyl, of between 100 and 2000 ppm, and preferably between 200 and 1000 ppm.
  • the gum (T) may be a mixture of several gums corresponding to the same definition as the gum (I ').
  • the gum (F) may be formed solely of units of formula (IM) or may further contain units of formula (F.2).
  • the gum (F) is advantageously a linear polymer, whose diorganopolysiloxane chain consists essentially of siloxy units D or D ', and is blocked at each end by a siloxy unit M or M VI .
  • 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 (IM) are the vinyldimethylsiloxyl, vinylphenylmethylsiloxyl, vinylmethylsiloxyl and vinylsiloxyl units.
  • siloxyl units of formula (F.2) are SiO 4/2, dimethylsiloxy, methylphenylsiloxyl, diphenylsiloxyl, methylsiloxyl and phenylsiloxyl.
  • Examples of gums (F) are dimethylvinylsiloxy or dimethylallylsiloxy dimethylpolysiloxane gums, diphenylsiloxane copolymers, and dimethylsiloxanes with phenylmethylvinylsiloxy ends. methylvinylsiloxane-dimethylsiloxane copolymers with dimethylvinylsiloxy ends or silanols.
  • the polyorganosiloxane (II) 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 among alkyl groups having 1 to 8 carbon atoms inclusive, optionally substituted with at least one halogen atom, and as for the aryl groups, d is 1 or 2, e is 0, 1 or 2 and d + e has a value of between 1 and 3; and optionally other siloxyl units of average formula: where L has the same meaning as above and g has a value between 0 and
  • the dynamic viscosity of this polyorganosiloxane (II) is at least 5 mPa.s and is preferably between 5 and 100 mPa.s, and more preferably between 10 and 40 mPa. s.
  • 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 polyorganosiloxane (II) can be solely formed of units of formula (II.1) or in addition to having units of formula (II.2).
  • the polyorganosiloxane (II) may have a cyclic or a branched linear structure.
  • Group L has the same meaning as group Z above.
  • Examples of siloxyl units of formula (II.1) are:
  • siloxyl units of formula (II.2) are the same as those indicated above for the examples of siloxyl units of formula (I'.2).
  • polyorganosiloxanes (II) are linear and cyclic compounds such as:
  • the compound (II) may optionally be a mixture of a dimethylpolysiloxane with hydrogenodimethylsilyl ends and a polyorganosiloxane bearing at least 3 SiH (hydrogenosiloxyl) functional groups.
  • the polyorganohydrogensiloxane adhesion promoter comprising Si-H (VI) groups corresponds to the same definition as that described above for the polyorganosiloxane (II), the conditions specific to the adhesion promoter (VI) as defined herein. above applying otherwise.
  • the adhesion promoter (VI) must be sufficiently rich in Si-H to meet the claimed characteristics of the composition of the present invention.
  • the adhesion promoter (VI) can not be a random copolymer in which the hydrogen atoms are too far apart.
  • a single polyorganohydrogensiloxane may be used in an amount sufficient to act both as a crosslinking agent (II) and an adhesion promoter (VI), in order to meet the features of the present invention.
  • the adhesion promoter (VI) is polymethylhydrogensiloxane, with trimethylsilyl ends or with hydrogenodimethylsilyl ends.
  • this polymethylhydrogenosiloxane has a viscosity of between 5 and 100 mPa.s, more preferably still between 10 and 40 mPa.s. Its content of SiH groups is preferably between 10 and 45% by weight.
  • this polymethylhydrogensiloxane is used both as crosslinking POS (II) and as adhesion promoter (VI).
  • the adhesion promoter (VI) may also be a copolymer of methylhydrogensiloxane and of dimethylsiloxane with trimethylsilyl ends or with hydrogenodimethylsilyl ends.
  • This copolymer has a viscosity of between 10 and 500 mPa.s, preferably between 10 and 100 mPa.s, and more preferably between 10 and 40 mPa.s. Its content of SiH groups is preferably between 10 and 48% by weight.
  • this copolymer is used both as crosslinking POS (II) and as adhesion promoter (VI).
  • the proportions of polyorganohydrogensiloxane (VI), optionally alkenylated polyorganosiloxane gum (I) or (V), and optionally polyorganosiloxane (II) are such that Si-H groups (from polyorganohydrogensiloxane (VI) and optionally polyorganosiloxane (II) and optionally complementary adhesion promoter (VII)) are in excess of the crosslinking reaction of the composition , so as to obtain a surface density potential of covalent Si- bonds with the silicone substrate to be bonded with at least one covalent Si- bond per 60 nm 2 , preferably at least one covalent Si- bond per 40 nm 2 .
  • the proportions of polyorganohydrogensiloxane (VI), optionally alkenylated polyorganosiloxane gum (I) or (T), and optionally polyorganosiloxane (II) are such that the excess of Si-H groups (originating from polyorganohydrogensiloxane (VI ) and optionally polyorganosiloxane (II) and optionally complementary adhesion promoter (VII)) following the crosslinking reaction with the alkenyl groups of the polyorganosiloxane gum (I or T) is at least 0.1% by weight of SiH relative to the SiH: Si-alkenyl ratio equal to 1: 1, per 100 g of said silicone composition, preferably at least 0.15% SiH per 100 g of said silicone composition, the polyorganosiloxane gum (I) exhibiting then per molecule at least two alkenyl groups preferably C2-C6 bonded to silicon.
  • a standard polyaddition EVC product which is generally formulated at a SiH / SiVi ratio of 1.5, and which contains about 500 ppm of vinyl groups, then has an excess of 250 ppm of SiH groups, which accordingly represents an excess of 0.025% by weight of SiH.
  • the polyaddition reaction specific to the crosslinking mechanism of the composition of the invention is well known to those skilled in the art. It is also possible to use a catalyst (V) in this reaction.
  • This catalyst (V) may especially be chosen from platinum and rhodium compounds.
  • platinum complexes and an organic product described in US-A-3 159 601, US-A-3 159 602, US-A-3,220,972 and European patents can be used.
  • the most preferred catalyst is platinum.
  • the amount by weight of catalyst (V), calculated as weight of platinum-metal is generally between 2 and 400 ppm, preferably between 5 and 100 ppm based on the total weight of the POS (I 1 ) and ( II).
  • the reinforcing mineral filler (III) is selected from silicas and / or aluminas.
  • the reinforcing mineral filler (III) is selected from silicas having a specific surface area of between 100 and 300 m 2 / g, these silicas being optionally pretreated using at least one compatibilizing agent.
  • These silicas may be colloidal silicas, silicas prepared by the pyrogenic route (so-called combustion or smoke silicas) or by wet processes.
  • silicas of this type are commercially available products and are well known in the art of manufacturing silicone elastomers.
  • the chemical nature and the method of preparing the silicas capable of forming charge (III) are not important for the purpose of the present invention, provided that the silica is capable of exerting a reinforcing action in the finished elastomeric adhesive.
  • these silica powders have an average particle size generally close to or less than 0.1 ⁇ m and a BET specific surface area greater than 50 m 2 / g, preferably between 100 and 300 m 2 / g.
  • These silicas are optionally: pretreated with at least one compatibilizing agent chosen from the group of molecules that satisfy at least two criteria: o have a strong interaction with the silica at its hydrogen bonds with itself , and with the surrounding silicone gum; o itself, or its degradation products, easily removed from the final mixture by heating under vacuum or under a gas stream, and low molecular weight compounds are therefore preferred; and / or treated in situ: specifically with at least one untreated silica, and / or in a complementary manner using at least one compatibilizing agent of a similar nature to that used in pretreatment and such as defined above.
  • at least one compatibilizing agent chosen from the group of molecules that satisfy at least two criteria: o have a strong interaction with the silica at its hydrogen bonds with itself , and with the surrounding silicone gum; o itself, or its degradation products, easily removed from the final mixture by heating under vacuum or under a gas stream, and low molecular weight compounds are therefore preferred; and / or treated in situ: specifically with at least one untreated silica, and / or
  • the compatibilizing agent is chosen according to the treatment mode (pre-treatment or in situ), it may for example be selected from the group comprising:
  • polyorganocyclosiloxanes such as octamethylcyclosiloxane (D4), silazanes, preferably disilazanes, or mixtures thereof, hexamethyldisilazane (HMDZ) being the preferred silazane and capable of being combined with divinyltetramethyl disilazane,
  • D4 octamethylcyclosiloxane
  • silazanes preferably disilazanes, or mixtures thereof
  • HMDZ hexamethyldisilazane
  • polyorganosiloxanes having, per molecule, one or more silicon-bonded hydroxyl groups, amines such as ammonia or low molecular weight alkylamines such as diethylamine, organic acids of low molecular weight, such as formic or acetic acids,
  • the compatibilizer is preferably used in the presence of water.
  • reinforcing filler (III) In terms of weight, it is preferred to use a quantity of reinforcing filler (III) of between 5 and 30, preferably between 7 and 20% by weight relative to all the constituents of the composition.
  • a complementary filler (VIII), preferably non-reinforcing, is conceivable according to the present invention
  • non-reinforcing additional fillers mention may be made in particular of those selected from the group comprising colloidal silicas, silica powders for combustion and precipitation, diatomaceous earths, crushed quartz, carbon black, and dioxide.
  • These fillers (VIII) have a particle size generally of between 0.1 and 300 ⁇ m and a BET specific surface area of less than 100 m 2 / g.
  • the complementary adhesion promoter (VII) may for example comprise:
  • R 1, R 7 and R 3 are hydrogenated or hydrocarbon radicals that are identical to or different from each other and preferably represent hydrogen, a linear or branched C1-C4 alkyl or a phenyl radical; optionally substituted with at least one C 1 -C 3 alkyl, A is linear or branched C 1 -C 4 alkylene, G is a valence bond or oxygen,
  • (VII.2) at least one organosilicon compound comprising at least one epoxy radical, said compound (VII.2) being preferably 3-glycidoxypropyltrimethoxysilane (GLYMO);
  • the complementary adhesion promoter (VII) is 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.
  • This complementary adhesion promoter (VII) can make it possible to reach the density of Si-bonds claimed by combining its Si-bond potential with that of the adhesion promoter (VI).
  • Crosslinking inhibitors (IX) 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 greater than 250 ° C. Examples that may be mentioned include: ethynyl-1-cyclohexanol 1;
  • alpha-acetylenic alcohols are commercial products.
  • Such an inhibitor (VI) is present at a maximum of 3000 ppm, preferably at 100 to 1000 ppm relative to the total weight of the organopolysiloxanes (I ') and (II).
  • the composition does not comprise a polyorganosiloxane resin.
  • the silicone phase of the composition may comprise at least one polyorganosiloxane resin (X), optionally comprising at least one alkenyl residue in its structure, and this resin has a weight content of alkenyl group (s) inclusive of between 0.1 and 20% by weight and, preferably, between 0.2 and 10% by weight.
  • X polyorganosiloxane resin
  • this resin has a weight content of alkenyl group (s) inclusive 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 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.
  • these resins are alkenylated (vinylated).
  • 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 silicone composition obtained has a Mooney consistency (NF standard
  • T 43005 measuring Mooney Large (1 + 4), using a Mooney viscometer) of between 15 and 75, and preferably between 20 and 45.
  • the present invention also provides an adhesive that can be used for silicone membranes, particularly in the field of textile architecture, and comprising the composition as described above.
  • This glue is particularly intended for gluing silicone parts of textiles, whether or not they are armed.
  • the present invention also relates to a bonding tape, which can be used in particular in the field of two-dimensional silicone complexes, and comprising the adhesive prepared from the composition described above, said adhesive having been laminated.
  • the present invention also relates to a method for bonding a silicone substrate, comprising the implementation of a composition, or an adhesive or a bonding tape as described above.
  • the bonding strip is placed on the junction zone between two silicone complexes to be assembled. Then the application of a pressure and a high temperature causes the crosslinking of the composition and allows the attachment with the silicone contained in each of the two layers of two silicone complexes opposite.
  • the silicone substrate to be bonded is, for example, a silicone membrane with or without a woven, braided, knitted or non-woven fibrous support and, preferably, a woven, knitted or non-woven support made of fibers selected from the group of materials.
  • the composition of the silicone membrane is not essential, but it can be advantageously selected from two-component hot-vulcanizable compounds such as RTV-2 or LSR, it then comprises:
  • At least one polyorganosiloxane having, per molecule, at least two silicon-bonded C2-C6 alkenyl groups (2) at least one polyorganosiloxane having, per molecule, at least two silicon-bonded hydrogen atoms,
  • a ternary adhesion promoter consisting of: (4.1) at least one alkoxylated organosilane containing, per molecule, at least one C3-C6 alkenyl group,
  • M being selected from the group consisting of: Ti, Zr, Ge, Li, Mn, Fe, Al and Mg,
  • lacquers optionally a crosslinking inhibitor and / or other additive (s) used in this type of compositions, (9) and optionally expandable or expandable inorganic hollow microsphere fillers.
  • lacquers which may be applied to the silicone membranes, they may be silicone lacquers, for example those crosslinkable cationically and / or radically, such as those described in the patent application WO 00/59992, or varnish silanes based on essentially unsaturated silane mixtures.
  • Another aspect of the invention relates to the use of a polyorganohydrogensiloxane as adhesion promoter in a silicone elastomer composition, adhesive, and heat-curable, intended in particular for bonding a silicone substrate, characterized in that on the one hand the nature and on the other hand the amount of said polyorganohydrogensiloxane are chosen so that Si-H groups are in excess of the crosslinking reaction of the composition so as to obtain a surface density potential of bonds with the substrate to be bonded. at least one bond per 60 nm 2 , preferably at least one bond per 40 nm 2 .
  • composition and the polyorganohydrogensiloxane are as defined above.
  • the following examples of the preparation of compositions and their application as bonding strips according to the invention will make it possible to better understand the invention and to highlight its advantages.
  • a platinum Karstedt catalyst which brings about 4 ppm of platinum combined with a crosslinking inhibitor, trimethyldodecynol, at a rate of approximately 1000 ppm; 2,5-ditertiobutyl 2,5-hexane peroxide at a level of 0.6%.
  • the concentrations mentioned are relative to the masterbatch used.
  • the mixtures are prepared using a laboratory calender which also straps the catalyzed mixture.
  • composition of the invention has been implemented in the form of laminated bonding strips to assemble two silicone complexes each consisting of: a glass fabric web of weight per unit area of about 250 g / m 2 on one face with less than one adherent silicone coating (Rhodorsil® TCS 7534 marketed by Bluestar Silicone) applied at a rate of about 200 g / m 2 ; this coating layer being suitably crosslinked in accordance with the supplier's recommendations
  • composition according to the invention makes it possible to obtain a high performance silicone elastomer glue, in particular for bonding silicone membranes, both in platinum and peroxidic catalysis.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesive Tapes (AREA)
EP08786623A 2007-08-02 2008-07-30 Composition elastomere silicone adhesive Withdrawn EP2173939A2 (fr)

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FR0705659A FR2919615A1 (fr) 2007-08-02 2007-08-02 Composition elastomere silicone adhesive
PCT/EP2008/059989 WO2009016199A2 (fr) 2007-08-02 2008-07-30 Composition elastomere silicone adhesive

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EP2173939A2 true EP2173939A2 (fr) 2010-04-14

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KR (1) KR20100061799A (enrdf_load_stackoverflow)
CN (1) CN101802296B (enrdf_load_stackoverflow)
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JP5661462B2 (ja) 2015-01-28
FR2919615A1 (fr) 2009-02-06
JP2014196491A (ja) 2014-10-16
WO2009016199A2 (fr) 2009-02-05
US20100282410A1 (en) 2010-11-11
CN101802296A (zh) 2010-08-11
WO2009016199A3 (fr) 2009-11-26
US8535478B2 (en) 2013-09-17
JP2010535260A (ja) 2010-11-18
CN101802296B (zh) 2013-06-19
KR20100061799A (ko) 2010-06-09

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