US20060122323A1 - Aqueous silicone emulsion for coating woven or non-woven fibrous substrates - Google Patents

Aqueous silicone emulsion for coating woven or non-woven fibrous substrates Download PDF

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US20060122323A1
US20060122323A1 US10/518,401 US51840105A US2006122323A1 US 20060122323 A1 US20060122323 A1 US 20060122323A1 US 51840105 A US51840105 A US 51840105A US 2006122323 A1 US2006122323 A1 US 2006122323A1
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emulsion
pos
optionally
weight
catalyzing
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Laurent Dumont
Michel Feder
Francis Layfaysse
Sylvie Robelin
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Elkem Silicones France SAS
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Rhodia Chimie SAS
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Assigned to RHODIA CHIMIE reassignment RHODIA CHIMIE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ROBELIN, SYLVIE, LAFAYSSE, FRANCIS, FEDER, MICHEL, DUMONT, LAURENT
Publication of US20060122323A1 publication Critical patent/US20060122323A1/en
Priority to US12/068,128 priority Critical patent/US7935386B2/en
Assigned to BLUESTAR SILICONES FRANCE. reassignment BLUESTAR SILICONES FRANCE. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RHODIA CHIMIE.
Abandoned legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/40—Organo-silicon compounds
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention relates to an aqueous emulsion of polyorganosiloxane (POS), especially for coating woven (textile) or non-woven substrates, which is intended to produce an elastomer after crosslinking in a thin layer, to a corresponding coating process and to the coated substrates.
  • POS polyorganosiloxane
  • silicone coatings are especially that of binders for improving the mechanical properties of fibrous substrates and notably the tear strength, the fraying resistance, the flexibility or the crumpling ability.
  • Silicone coatings can also contribute towards giving fibrous substrates a degree of impermeability and a water-repellent character.
  • silicone coatings can also provide them with protection against other aggressions and/or give them specific properties for certain applications (e.g. dielectric properties).
  • Applications which may be mentioned in particular are inflatable bags used for protecting vehicle occupants, or airbags, glass braiding (glass fabric sheathing for the thermal and dielectric protection of electric wire), conveyor belts, fire-resistant fabrics or thermal insulators, compensators (leaktight flexible sleeves for piping), clothing, or flexible materials for use in interior or exterior textile architecture (tarpaulins, tents, stalls, marquees, false ceilings, etc.) or solar protection.
  • a first problem relates to the operation involving deposition/impregnation of the non-crosslinked silicone composition on the substrate. It is important that this operation can be carried out easily, rapidly (industrial rate) and, for obvious economic reasons, at reduced deposition rates (e.g. less than 40 microns).
  • a second problem lies in the minimum level of adhesion which the silicone coating must have on the substrate.
  • a third problem results from the ambition to improve the performance characteristics of the silicone elastomer coating from the point of view of its mechanical properties, its protective function and its hydrophobic and impermeabilizing properties, without adversely affecting the flame-retardant qualities of certain textile substrates such as glass fabrics.
  • EP-A-0 535 649 proposes a composition for coating inflatable bags, or airbags, comprising:
  • This emulsion suffers from the following disadvantages: an inadequate 25 compromise in terms of adhesion, reactivity and stability of the emulsions, particularly an inadequate adhesion of the silicone to the substrate, and an incompatibility of the silanes and surfactant used with polyaddition systems based on oils containing ⁇ SiH and on platinum catalyst.
  • European patent application EP-A-0 552 983 describes a 30 composition of the same type obtained from (A) an organopolysiloxane having at least two alkenyl groups [alpha,omega-dimethylvinylsiloxypoly(dimethyl)-(vinylmethyl)siloxane], (B) an organohydrogenopolysiloxane [alpha,omega-tri-methylsiloxypoly(methylhydrogeno)siloxane] having at least three hydrogen atoms, (C) a platinum crosslinking catalyst, (D) a crosslinking inhibitor of the ethynyl-cyclohexanol type, (E) an adhesion promoter of the epoxidized trialkoxysilane or amino-functional silane type (p.
  • A an organopolysiloxane having at least two alkenyl groups [alpha,omega-dimethylvinylsiloxypoly(dimethyl)-(
  • a reinforcing filler such as a colloidal silica, by emulsification in water in the presence of an emulsifier (dodecylbenzenesulfonate and polyvinyl alcohol, PVA).
  • an emulsifier dodecylbenzenesulfonate and polyvinyl alcohol, PVA
  • This emulsion suffers from the following disadvantages: an inadequate compromise between adhesion (to the substrate) and stability (of the emulsion); in particular, the use of dodecylbenzenesulfonate and non-salified amino-functional silane results in a limited stability of polyaddition emulsions.
  • European patent EP-B-0 758 666 relates to aqueous emulsions comprising:
  • This polyaddition silicone solution is preferentially applied in the production of textile coatings (airbag: polyamide substrate).
  • EP-A-1 010 721 relates to the same emulsion as that described in EP-B-0 758 666 except that it has a further additive consisting of carbon black.
  • Patent application FR-A-2 738 830 relates to an aqueous polyorgano-siloxane emulsion for coating textile material. This emulsion is obtained by mixing an emulsion A and an emulsion B.
  • Emulsions A and B are prepared by mixing (without emulsifying) on the one hand components 1 to 6 and on the other hand components 1′, 4′, 7 and 6′, respectively, and then emulsifying the compositions described above by agitating them in the presence of water and polyvinyl alcohol (PVA Rhodoviol® 25/140). Once they have been obtained separately, emulsions A and B are mixed with one another.
  • PVA Rhodoviol® 25/140 polyvinyl alcohol
  • This aqueous silicone emulsion additionally has the following disadvantages: very coarse emulsions are produced, the process is rather inflexible and burdensome because intermediate silicone mixtures have to be produced, and it is difficult to prepare very concentrated emulsions.
  • one of the essential objects of the present invention is to provide a silicone emulsion, crosslinkable by polyaddition, for coating woven or non-woven fibrous substrates, said emulsion possessing rheological properties such that it can easily be deposited on/applied to the fibrous substrate at high speed and at limited deposition rates, for example of less than 40 g/m 2 .
  • Another essential object of the invention is to provide an aqueous silicone emulsion, crosslinkable by polyaddition, for forming protective thin coatings (thin layers) on woven (textile) or non-woven fibrous substrates, the composition of this emulsion being such as to optimize the adhesion of the crosslinked silicone elastomer film to the substrate.
  • Another essential object of the invention is to provide an aqueous silicone emulsion, crosslinkable by polyaddition, for coating woven or non-woven fibrous substrates, the composition of this emulsion being such as to produce a crosslinked silicone elastomer coating capable of giving the substrate excellent mechanical qualities (cohesion, flexibility, fraying resistance, tear strength, crumpling ability).
  • Another essential object of the invention is to provide an aqueous silicone emulsion that crosslinks by polyaddition to give an elastomer coating for a woven or non-woven fibrous substrate, the composition of this emulsion being such as to satisfy the specifications of easy deposition in a limited amount, adhesion to the substrate, and mechanical quality.
  • Another essential object of the invention is to provide an aqueous silicone emulsion, crosslinkable by polyaddition, for forming, on mineral fibrous substrates of low adhesiveness (particularly textile or non-textile glass fiber substrates), silicone coatings that adhere to the fibers but give them anti-adhesion, hydrophobic and impermeable properties and satisfy the specifications of easy deposition in a limited amount, adhesion to substrates, mechanical properties (flexibility/tear strength and fraying resistance) and incombustibility corresponding to a gross calorific value (GCV), measured according to NFP 92510, below 4200 kJ/kg and preferably below 2500 kJ/kg.
  • GCV gross calorific value
  • Another essential object of the invention is to provide an aqueous silicone emulsion that crosslinks by polyaddition, on woven or non-woven fibrous substrates, to give protective, impermeable, flame-retardant, flexible, strong and optionally flame-retardant elastomer coatings, the composition of this emulsion being such that, in the case of glass fiber substrates, the elastomer film is a good binder capable of giving the coated glass substrates stability, cohesion and flexibility, while at the same time minimizing the phenomenon of creasing.
  • Another essential object of the invention is to produce emulsions that are chemically stable (preservation of the -SiH and the reactivity) and physically stable (limited creaming and coalescence during storage of the emulsion) and have good characteristics in terms of reactivity (crosslinking by polyaddition) and adhesion to the substrate, by drying the treated fabric.
  • POS polyorganosiloxane
  • the emulsion is devoid of:
  • the ratio amount by weight of adhesion promoter (C)/surface area developed by the substrate ranges from 0.1I to 10 mg/m 2 and preferably from 25 0.2 to 5 mg/m 2 .
  • “Surface area developed by the substrate” is understood according to the invention as meaning the surface area developed by the fibers that constitute the fabric and are to be covered with the emulsion.
  • the aqueous silicone emulsion according to the invention is of the type that crosslinks by polyaddition at room temperature (EVF or RTV), it being known that this platinum-catalyzed crosslinking can be thermally activated (100-200° C.).
  • This aqueous silicone emulsion according to the invention adheres to numerous woven or non-woven fibrous substrates, for example made of glass fibers or optionally of synthetic textile fibers of the polyester or polyamide type.
  • the emulsion according to the invention makes it possible to obtain glass fabrics coated with thin layers of silicone elastomers that are hydrophobic and have good mechanical properties of flexibility, tear strength and fraying resistance and do not release much heat on combustion: GCV ⁇ 4500 kJ/kg, preferably GCV ⁇ 2500 kJ/kg.
  • One of the essential constituents of the emulsion according to the invention is the special adhesion promoter (C), which is carefully selected so that the adhesion is provided by:
  • the protective hydrocolloid used preferably PVA, is exclusively dedicated to the function of adhesion promoter (C).
  • the surfactant (E) can consist at least in part of at least one protective hydrocolloid, preferably a PVA.
  • the protective colloid preferably PVA
  • the emulsion has to comprise a main emulsifier or surfactant (E).
  • the protective colloid preferably PVA, as adhesion promoter and emulsifier, is present in an amount of 1.5 to 7% of dry PVA, based on the total weight of silicone oils.
  • the protective hydrocolloid is preferably a polyvinyl alcohol (PVA) or a mixture of PVA, preferably PVA grades which, in aqueous solution (at 4% and at 20° C.), have a standard dynamic viscosity ( ⁇ sd ) of between 5 and 40 mPa ⁇ s and preferably of between 10 and 30 mPa ⁇ s, and an ester number greater than or equal to 80, preferably greater than or equal to 100 and especially of between 120 and 200.
  • PVA polyvinyl alcohol
  • ⁇ sd standard dynamic viscosity
  • the PVA is used in the form of an aqueous solution with a standard dynamic viscosity ( ⁇ sd ) of between 5 and 40 mPa ⁇ s and preferably of between 10 and 30 mPa ⁇ s, and an ester number greater than or equal to 80, preferably greater than or equal to 100 and especially of between 120 and 200.
  • ⁇ sd standard dynamic viscosity
  • Polyvinyl alcohols are compounds obtained indirectly from their esters by hydrolysis in an aqueous medium or by alcoholysis in an anhydrous medium.
  • the esters used as starting materials are commonly polyvinyl acetates.
  • lysis of the esters to give the PVA is not complete.
  • Acyl radicals remain in the molecule and their proportion influences the properties of the PVA, especially its solubility.
  • One method of defining PVA is therefore based on an indication of the ester number (EN), which is inversely proportional to the degree of hydrolysis.
  • EN is measured in a manner known per se by neutralizing any acidity in the polyvinyl alcohol, saponifying the acyl groups and titrating the excess alkalinity.
  • the polyvinyl alcohols according to the invention are also characterized by their degree of condensation, which can be evaluated by determining the dynamic viscosity of a standard solution (designated by ⁇ sd in the present disclosure), in the knowledge that this variable increases with the degree of condensation.
  • the viscosity ⁇ sd corresponds to the coefficient of dynamic viscosity of a 4% by weight aqueous solution of PVA, measured at a temperature of 20 ⁇ 5° C. using an Ostwald viscometer.
  • protective hydrocolloids which may also be mentioned are water-dispersible sulfonated polyesters, especially of the sulfonated polyethylene terephthalate type.
  • Water-dispersible sulfonated polyesters are known and commercially available products. They can be prepared by co-condensing an organic diacid (such as a saturated or unsaturated aliphatic diacid, an aromatic diacid, a diacid having several aromatic rings, an arylaliphatic diacid), one of its diesters or its anhydride and a sulfonated organic diacid or one of its diesters with a diol in the presence of a customary polyesterification catalyst such as tetraisopropyl orthotitanate.
  • an organic diacid such as a saturated or unsaturated aliphatic diacid, an aromatic diacid, a diacid having several aromatic rings, an arylaliphatic diacid
  • a customary polyesterification catalyst such as tetraisopropyl orthotitanate.
  • the preferred water-dispersible sulfonated polyesters are those having a number-average molecular weight of between 10,000 and 35,000, an acid number below 5 mg KOH/g and a sulfur content of between 0.8 and 2% by weight and preferably of between 1.2 and 1.8%. Polyesters of this type which can be used in particular are the products marketed by RHODIA under the mark GEROL PS20.
  • the silanes with hydroxyl and salified amino units which can be constituent components of the promoter (C) are obtained from non-salified precursors; examples of these which may be mentioned are monoaminotrihydroxymonosilanes such as NH 2 (CH 2 ) 3 —Si(OH) 3 optionally oligomerized by partial condensation of the SiOH groups.
  • the water-soluble adhesion promoter (C) preferably comprises POS with hydroxyl and salified amino units.
  • the salified amino-POS is a resin having a mean silicon functionality greater than 2, corresponding to x+y ⁇ 2:
  • siloxy units M, D, T and Q of the POS (C) are defined as follows:
  • radicals R are identical or different and correspond to:
  • linear hydroxylated POS resin which can be used as promoter (C) is polymethylsiloxane of which both ends carry a hydroxyl and in which each silicon atom carries a salifiable or salified amino unit.
  • the resins selected more particularly are those of the type T(OH), DT(OH), DQ(OH), DT(OH), MQ(OH), MDT(OH) or MDQ(OH) or mixtures thereof.
  • Each OH group in these resins is carried by a silicon atom belonging to a unit D, T or Q.
  • These resins are products resulting from the condensation (mono-condensation or polycondensation, heterocondensation or homocondensation) of POS monomers, oligomers or polymers carrying condensable groups, preferably of a hydroxyl nature.
  • the promoter (C) carries one or more salifiable or salified amino units that are identical to or different from one another.
  • the amine can be primary, secondary or tertiary. In variants the amine can be included in a ring or in isocyanurate groups or HALS groups (of the piperidine type or another type).
  • HALS groups can be defined as a cyclic hydrocarbon chain (HALS) of the formula in which:
  • the salifiable or salified amino units are advantageously selected so as to be capable of binding to the substrate to which the emulsion is applied, in order to provide adhesion, without adversely affecting the solubility in water that is desirable for the promoter (C).
  • salifiable amino units which may be mentioned in particular are:
  • One of the essential characteristics of the promoter (C) selected according to the invention is to be salified via the amino units as described above, which comprise at least one ⁇ N + .X ⁇ , where X is a counteranion selected from carboxylates and halides, preferably a lactate, an acetate or a chloride.
  • the aqueous continuous phase of the dispersion has a pH such that said promoter (C) (preferably a hydroxylated POS resin) is maintained in ionized form.
  • the pH is chosen, in a manner known per se, according to the pKa of the acid corresponding to the counteranion used.
  • the preferred promoter (C) in the form of a hydroxylated resin is included in the aqueous continuous phase of the dispersion, being solubilized or finely dispersed therein.
  • the invention also covers mixtures of promoters (C) of different natures.
  • the silicone phase of the emulsion according to the invention comprises POS for generating the elastomer by crosslinking/curing at room temperature (23° C.) according to a polyaddition mechanism. It is possible to accelerate the crosslinking by thermal activation at a temperature above room temperature. Elastomers that vulcanize in the cold by polyaddition and elastomers that vulcanize under the action of heat by polyaddition fall within the framework of the invention.
  • sicone phase are to be understood as meaning “non-aqueous phase” in the emulsion.
  • polyorganosiloxanes which are the main constituents of the compositions according to the invention, can be linear, branched or crosslinked and can contain hydrocarbon radicals and/or reactive groups such as hydroxyl groups, hydrolyzable groups, alkenyl groups, hydrogen atoms, etc. It should be pointed out that organopolysiloxane compositions are amply described in the literature and especially in the work by Walter NOLL entitled “Chemistry and Technology of Silicones”, Academic Press, 1968, 2nd edition, pages 386 to 409.
  • the POS which are the main constituents of the compositions according to the invention consist of siloxy units of the general formula R n 9 ⁇ SiO 4 - n 2 ( II ) and/or siloxy units of the formula Z n ⁇ R y 9 ⁇ SiO 4 - x - y 2 ( III )
  • organic radicals R 9 directly bonded to silicon atoms methyl; ethyl; propyl; isopropyl; butyl; isobutyl; n-pentyl; t-butyl; chloromethyl; dichloromethyl; ⁇ -chloroethyl; ⁇ , ⁇ -dichloroethyl; fluoromethyl; difluoromethyl; ⁇ , ⁇ -difluoroethyl; 3,3,3-trifluoropropyl; trifluorocyclopropyl; 4,4,4-trifluorobutyl; 3,3,4,4,5,5-hexafluoropentyl; ⁇ -cyanoethyl; ⁇ -cyanopropyl; phenyl; p-chlorophenyl; m-chloro-phenyl; 3,5-dichlorophenyl; trichlorophenyl; tetrachlorophenyl
  • the organic radicals R 9 bonded to silicon atoms are methyl or phenyl radicals, it optionally being possible for these radicals to be halogenated, or cyanoalkyl radicals.
  • the symbols Z can be hydrogen atoms or vinyl groups.
  • organopolysiloxane compositions that crosslink at room temperature or under the action of heat by means of polyaddition reactions, essentially by the reaction of hydrogenosilyl groups with alkenylsilyl groups, generally in the presence of a metal catalyst preferably based on platinum, said compositions being described e.g. in patents U.S. Pat. Nos. 3,220,972, 3,284,406, 3,436,366, 3,697,473 and 4,340,709.
  • the organopolysiloxanes forming part of these compositions generally consist of pairs based on the one hand on at least one linear, branched or crosslinked polysiloxane consisting of units (III) in which the radical Z is an alkenyl group and x is equal to at least 1, optionally in association with units (II), and on the other hand on at least one linear, branched or crosslinked hydrogenopolysiloxane consisting of units (III) in which the radical Z this time is a hydrogen atom and x is equal to at least 1, optionally in association with units (II).
  • the unsaturated polysiloxane constituent containing units (III) can be an oil having a dynamic viscosity at 25° C. of between 200 and 500,000 mPa ⁇ s.
  • a mixture based on the above-mentioned oil and an unsaturated gum having a viscosity greater than 500,000 mPa ⁇ s and capable of ranging up to 10 6 mPa ⁇ s can also be used, if required, as the unsaturated polysiloxane constituent containing units (III).
  • the emulsions according to the invention also contain at least one non-hydroxylated silicone resin (F).
  • F non-hydroxylated silicone resin
  • These silicone resins are well-known branched POS polymers that are available commercially. In each molecule they have at least two different units selected from those of the formulae R 10 SiO 1/2 (unit M), R 10 2 SiO 2/2 (unit D), R 10 SiO 3/2 (unit T) and SiO 4/2 (unit Q).
  • the radicals R are identical or different and are selected from linear or branched alkyl radicals, vinyl radicals, phenyl radicals and 3,3,3-trifluoropropyl radicals.
  • the alkyl radicals preferably have from 1 to 6 carbon atoms inclusive.
  • Alkyl radicals R which may be mentioned more particularly are methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals.
  • At least some of the radicals R 10 are vinyl radicals (Vi content especially between 0.1 and 2% by weight). These vinyl groups are carried by the units M, D or T. Examples which may be mentioned are vinylated resins MDQ, such as MD Vi Q, or resins MM Vi Q.
  • surfactants (E) other than the protective hydrocolloid (PVA) these can be anionic [except in the case where the emulsion comprises a salified amine as promoter (C)], cationic or non-ionic; in particular, they can be one or more polyethoxylated fatty alcohols.
  • the surfactants (E) are non-ionic.
  • the role of the surfactant will be especially to refine the particle size of the emulsion and optionally to improve its stability.
  • the emulsion according to the invention can also contain other formulating additives (I) such as a condensation catalyst for promoting the condensation of the silanols of the salified aminosilane or amino-POS without inhibiting the platinum catalysis (e.g. titanium or zirconium salts or possibly certain tin salts), a bactericide, one or more mineral or organic pigments and one or more organic thickeners (polyethylene oxide, xanthan gum, hydroxyethyl cellulose, acrylic or cationic polymers, etc.) or mineral thickeners (laponite).
  • a condensation catalyst for promoting the condensation of the silanols of the salified aminosilane or amino-POS without inhibiting the platinum catalysis
  • a bactericide e.g. titanium or zirconium salts or possibly certain tin salts
  • mineral or organic pigments e.g. titanium or zirconium salts or possibly certain tin salts
  • organic thickeners polyethylene oxide, xanthan gum,
  • the emulsion according to the invention comprises a system for maintaining the pH at alkaline values, for example of between 7 and 8.
  • This pH maintenance system can be e.g. sodium bicarbonate.
  • the agent for fixing and maintaining the pH is preferably a buffer system comprising HCO 3 ⁇ /CO 3 2 ⁇ and/or H 2 PO 4 ⁇ /HPO 4 2 ⁇ .
  • a buffer system comprising HCO 3 ⁇ /CO 3 2 ⁇ and/or H 2 PO 4 ⁇ /HPO 4 2 ⁇ .
  • an HCO 3 ⁇ and/or H 2 PO 4 ⁇ salt such as NaHCO 3 and/or Na 2 CO 3 and/or NaH 2 PO 4 and/or Na 2 HPO 4 .
  • any other salt with a different counteranion e.g. K
  • the buffer system used in practice consists of NaHCO 3 , which is incorporated into the emulsion.
  • the emulsion can contain mineral reinforcing or bulking fillers preferably selected from combustion silicas and precipitated silicas. They have a specific surface area, measured by the BET methods, of at least 50 m 2 /g, especially of between 50 and 400 m 2 /g and preferably greater than 70 m 2 /g, a mean primary particle size of less than 0.1 micrometer ( ⁇ m) and an apparent density of less than 200 g/liter.
  • mineral reinforcing or bulking fillers preferably selected from combustion silicas and precipitated silicas. They have a specific surface area, measured by the BET methods, of at least 50 m 2 /g, especially of between 50 and 400 m 2 /g and preferably greater than 70 m 2 /g, a mean primary particle size of less than 0.1 micrometer ( ⁇ m) and an apparent density of less than 200 g/liter.
  • hydrophilic silicas preferably incorporated as such into the (continuous) aqueous phase of the emulsion.
  • these silicas can optionally be treated with one or more organosilicon compounds normally used for this purpose.
  • the silicas can be predispersed in silicone oil.
  • These compounds include methylpolysiloxanes such as hexamethyldisiloxane and octamethylcyclotetrasiloxane, methylpolysilazanes such as hexamethyldisilazane and hexamethylcyclotrisilazane, chlorosilanes such as dimethyldichlorosilane, trimethylchlorosilane, methylvinyldichlorosilane and dimethylvinylchlorosilane, and alkoxysilanes such as dimethyldimethoxysilane, dimethylvinylethoxysilane and trimethylmethoxysilane.
  • This treatment can increase the initial weight of the silicas by up to 20%.
  • siliceous fillers it is also possible to use, in addition to or in place of siliceous fillers, other mineral fillers such as calcium carbonates, ground quartz, calcined clays and diatomaceous earths, optionally in the form of an aqueous dispersion (slurry).
  • other mineral fillers such as calcium carbonates, ground quartz, calcined clays and diatomaceous earths, optionally in the form of an aqueous dispersion (slurry).
  • non-siliceous mineral materials can be used as semireinforcing or bulking mineral fillers or mineral fillers with specific properties.
  • these non-siliceous fillers which can be used by themselves or in a mixture, are carbon black, titanium dioxide, aluminum oxide, hydrated alumina, expanded vermiculite, non-expanded vermiculite, calcium carbonate, zinc oxide, mica, talcum, iron oxide, barium sulfate 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 m 2 /g.
  • composition of the emulsion according to the invention is e.g. as follows:
  • the present invention further relates to a process for the preparation of an aqueous POS emulsion as defined above, characterized in that an emulsion is formed by introducing the constituents (A) to (K) into the same reactor, except for the catalyst (D), which is emulsified separately and added when the impregnating bath is made up.
  • the emulsion is obtained by:
  • the emulsion is produced by mixing pre-emulsions which are each incapable of crosslinking separately because they do not contain all the reactive species and the catalyst ( ⁇ SiVi POS+ ⁇ SiH POS+platinum) necessary for the polyaddition. It is possible, for example, to produce an emulsion containing the ⁇ SiVi, the ⁇ SiH and the inhibitor (part A) and a catalyzing emulsion based on platinum and ⁇ SiVi oil (part B), which will be combined when the coating bath is made up.
  • ingredients (A) and/or (B) and/or (C) in the form of pre-emulsions that may or may not contain the other ingredients (D) to (J).
  • the catalyzing emulsion is added to the other, non-catalyzing silicone pre-emulsions (especially the one based on SiH) when the bath is formulated, prior to application to the fabric.
  • Another advantageous modality of the invention can consist in introducing the adhesion promoter (C), especially the salified aminosilane or amino-POS, only when the coating bath is prepared.
  • Another possibility would be to prepare emulsions A and B or pre-emulsions (i), (ii) and (iii) containing no adhesion promoter, and to make provision for incorporating the latter separately when A and B or (i), (ii) and (iii) are mixed.
  • the present invention further relates to a process for the preparation of a fibrous substrate coated with at least one layer of elastomers obtained by crosslinking the aqueous POS emulsion as defined above.
  • This process comprises the following steps:
  • the deposition step is advantageously a coating operation.
  • the coating step can be carried out especially with a knife, particularly a cylinder knife, an air knife or a belt knife, or by padding, i.e. squeezing between two rolls, or with a sweeping roll, rotating frame or reverse roll, or by transfer or spraying.
  • a knife particularly a cylinder knife, an air knife or a belt knife, or by padding, i.e. squeezing between two rolls, or with a sweeping roll, rotating frame or reverse roll, or by transfer or spraying.
  • the coating of both sides advantageously being carried out by padding after impregnation of the fabric with the emulsion.
  • the fabric After passing between the rolls, the fabric is uniformly coated with a thin layer of emulsion.
  • drying and crosslinking preferably by means of hot air or infrared, especially for 30 s to 5 min, at a crosslinking temperature not exceeding the degradation temperature of the substrate.
  • a knife When only one side is coated, it is preferable to use a knife.
  • the emulsion is deposited continuously on the top side of the fabric and then passes underneath the knife prior to drying and crosslinking as above.
  • coating is carried out by:
  • the layer of elastomer is preferably present in an amount such that the ratio of the dry weight of the coating to the weight of the fibrous substrate is less than 0.2 and preferably between 0.05 and 0.11.
  • the process comprises a previous step in which the two components are mixed.
  • the present invention further relates to any product obtainable by depositing the emulsion as defined above on a fibrous substrate—preferably made of glass fibers—after which the POS contained in the emulsion applied to the substrate are crosslinked to an elastomer.
  • inflatable bags used for protecting vehicle occupants, or airbags, glass braiding (glass fabric sheathing for the thermal and dielectric protection of electric wire), conveyor belts, fire-resistant fabrics or thermal insulators, compensators (leaktight flexible sleeves for piping), clothing, or flexible materials for use in interior or exterior textile architecture (tarpaulins, tents, stalls, marquees, etc.).
  • glass braiding glass fabric sheathing for the thermal and dielectric protection of electric wire
  • conveyor belts fire-resistant fabrics or thermal insulators
  • compensators leaktight flexible sleeves for piping
  • clothing or flexible materials for use in interior or exterior textile architecture (tarpaulins, tents, stalls, marquees, etc.).
  • fibrous substrates to be coated are woven fabrics, nonwovens or knitted fabrics or, more generally, any fibrous substrate comprising fibers, and/or fibers selected from the group of materials comprising glass, silica, metals, ceramic, silicon carbide, carbon, boron, natural fibers such as cotton, wool, hemp or flax, artificial fibers such as viscose or cellulosic fibers, and synthetic fibers such as polyesters, polyamides, polyacrylics, chlorofibers, polyolefins, synthetic rubbers, polyvinyl alcohol, aramides, fluorofibers, phenolics, etc.
  • any fibrous substrate comprising fibers, and/or fibers selected from the group of materials comprising glass, silica, metals, ceramic, silicon carbide, carbon, boron, natural fibers such as cotton, wool, hemp or flax, artificial fibers such as viscose or cellulosic fibers, and synthetic fibers such as polyesters, polyamides, polyacrylics, chlorofiber
  • Preferred examples of fibrous substrates which may be mentioned are glass fabrics.
  • these coated glass fabrics have a good tear strength and fraying resistance. Furthermore, they are flexible and are not subject to creasing. Also, their gross calorific value (GCV) is less than or equal to 2500 kJ/kg.
  • the present invention further relates to the use of an emulsion as defined above, or obtained by the process described above, for coating a fibrous substrate, except for any architectural textile.
  • “Architectural textile” is understood as meaning a woven fabric or nonwoven and, more generally, any fibrous substrate which, after coating, is intended to be used in the construction of:
  • Rhodasurf ROX 35 g of water and the POS (A-1) oil, in which the inhibitor ECH has been dispersed beforehand, are introduced into an IKA laboratory reactor equipped with a scraping anchor and a base (cooled by cold water circulation). After stirring for 15 min at 80 rpm, a concentrated oil/water emulsion is obtained which has the appearance of a viscous gel.
  • the resin (F.1) is then poured in over 85 min, with stirring (80 rpm), the final temperature being about 30° C.
  • the mean particle size of the emulsion is then 0.28 ⁇ m.
  • the mean particle size of the emulsion, characterized on the Coulter LS130, is 0.29 ⁇ m.
  • the emulsion is diluted by gradually adding the rest of the demineralized water (i.e. 310 g), followed by the sorbic acid, and the final emulsion is transferred to a polyethylene flask.
  • demineralized water i.e. 310 g
  • the 10% aqueous solution of polyvinyl alcohol (Rhodoviol 25/140) and the sorbic acid are introduced into an IKA laboratory reactor equipped with a scraping anchor and a base (cooled by cold water circulation).
  • the resin (E.1) is poured in over 170 min, with stirring, the final temperature being about 22° C.
  • the POS (A-1) oil (ViMe 2 SiO-blocked polydimethylsiloxane oil having a viscosity of 60,000 mPa ⁇ s and containing 0.07% of Vi), in which the ethynyl-cyclohexanol (ECH) has been predispersed, is then poured in over 150 min, the final temperature reaching 17° C.
  • the mean particle size of the emulsion, characterized on the Coulter LS130, is 5.9 ⁇ m.
  • the mean particle size drops to 3 ⁇ m.
  • Emulsion B is produced according to the same protocol as emulsion A2 by pouring the POS-1 oil 621V60000 (in which the catalyst (D) has been predispersed) into the 10% aqueous solution of polyvinyl alcohol. The bicarbonate is added at the end to the diluted emulsion.
  • A1 or A2 100 parts of A1 or A2 are mixed with 10 parts of B, optionally together with diluting water to adjust the viscosity and concentration of the bath (so as to regulate the amount of silicone deposited on the fabric), when the coating bath is made up before being applied to the fabric.
  • the pH of the bath is between 7 and 8.
  • the fabric arrives vertically between the rolls where the emulsion is deposited continuously, the fabric being impregnated on both sides as it leaves the rolls. It then passes through an oven for one minute.
  • the installation operates at 10 m/min.
  • the inlet and outlet temperatures of the ovens are set at 120 and 160° C., respectively.
  • the pressure on the squeezing rolls is in the order of 1.5 bar.
  • the fabrics are weighed before and after coating in order to measure the weight deposited.
  • Example 2 is identical to Example 2 except that the pressure on the squeezing rolls is in the order of 1 bar.
  • the fabrics are weighed before and after coating in order to measure the weight deposited.
  • the fabric is immersed in a trough located upstream from the squeezing rolls and arrives at an angle of 20° between the rolls, which are at a squeezing pressure of 1.5 bars. The fabric then passes through an oven for one minute.
  • the installation operates at 10 m/min.
  • the inlet and outlet temperatures of the ovens are set at 120 and 160° C., respectively.
  • the fabrics are weighed before and after coating in order to measure the weight deposited.
  • This fabric is coated by the process of Example 4 with an emulsion of Example 1 (mixture of emulsions A2+B (without additive)).
  • the dry extract of this bath was adjusted to 55.7% and then to 48%.
  • the coated fabric has an attractive appearance.
  • the gross calorific value measured according to NFP92-5 10, is 1900 kJ/kg.
  • the fraying resistance is good, as represented by a combing resistance, measured according to DIN54301, of more than 50 N.
  • This fabric is coated by the process of Example 2 with an emulsion of Example 1 (mixture of emulsions A2+B (without additive)).
  • the dry extract of this bath was adjusted to 55.7% and then to 42%.
  • the coated fabric has an attractive appearance.
  • the gross calorific value measured according to NFP92-5 10, is 2150 kJ/kg.
  • the fraying resistance is good, as represented by a combing resistance, measured according to DIN54301, of more than 50 N.
  • This fabric is coated by the process of Example 3 with an emulsion of Example 1 (mixture of emulsions A2+B (without additive)).
  • the dry extract of this bath was adjusted to 55.7% and then to 42%.
  • the coated fabric has an attractive appearance, particularly on the top side which has received the emulsion.
  • the gross calorific value measured according to NFP92-510, is 1800 kJ/kg.
  • the fraying resistance is good, as represented by a combing resistance, measured according to DIN54301, of more than 50 N.
  • This silane was used after salification, which was effected by neutralization of the aqueous solution by adding a sufficient amount of acetic acid to bring its pH to between 6 and 7.
  • FIG. 1 corresponds to a polyester fabric substrate.
  • FIG. 2 corresponds to a glass fabric substrate.
  • control corresponds to the adhesion results obtained when the fabric is treated with emulsion 1.2 of Example 1 without the incorporation of additional adhesion promoter.
  • salified aminosilanes appreciably improve the adhesion to glass fabric.
  • the salified aminosilane 6.2 also improves the adhesion to polyester fabric.
  • the 180° peel test on a fibrous substrate is a measure of the adhesion of PA emulsions.
  • the procedure for this test is as follows:
  • Strips of ⁇ 12 by 17 cm are cut out of the fibrous substrate.
  • the contours marked out on the fabric are coated with a silicone elastomer that crosslinks rapidly in the cold (CAF). Small amounts of CAF are therefore deposited with a gun and spread along the contours with a spatula. Cutting is easier once the CAF is dry.

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US10/518,401 2002-06-18 2003-06-17 Aqueous silicone emulsion for coating woven or non-woven fibrous substrates Abandoned US20060122323A1 (en)

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FR0207498A FR2840912B1 (fr) 2002-06-18 2002-06-18 Emulsion silicone aqueuse pour le revetement de supports fibreux tisses ou non
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PCT/FR2003/001835 WO2003106758A2 (fr) 2002-06-18 2003-06-17 Emulsion silicone aqueuse pour le revetement de supports fibreux tisses ou non

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EP1513979A2 (fr) 2005-03-16
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ATE536438T1 (de) 2011-12-15
FR2840912A1 (fr) 2003-12-19
JP2005530052A (ja) 2005-10-06
AU2003258809A1 (en) 2003-12-31
CN1671916A (zh) 2005-09-21
US7935386B2 (en) 2011-05-03
EP1513979B1 (fr) 2011-12-07
JP4563173B2 (ja) 2010-10-13
US20080207827A1 (en) 2008-08-28
CN100335712C (zh) 2007-09-05
WO2003106758A3 (fr) 2004-04-08
WO2003106758A2 (fr) 2003-12-24

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