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
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
  • C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/55—Boron-containing compounds
• • 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
  • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • 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
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2962—Silane, silicone or siloxane in coating
• • 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
• • 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
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2525—Coating or impregnation functions biologically [e.g., insect repellent, antiseptic, insecticide, bactericide, etc.]

Definitions

• the general field of the invention is that of polymer coatings or varnishes capable of imparting, in particular, anti-fouling properties to supports, which can in particular be constituted:
• the present invention also relates to the methods of applying the anti-fouling varnish which it relates to, on various supports.
• the subject of the invention is the supports coated with such anti-fouling varnishes and in particular, flexible supports such as textile fabrics coated with a layer of silicone elastomer on which the anti-fouling varnish is applied, such fabrics which may be used for manufacturing:
• the term "architectural textile” means a fabric or nonwoven and more generally any fibrous support intended after coating to the garment: - shelters, mobile structures, textile buildings, partitions, flexible doors, tarpaulins, tents, stands or marquees;
• these flexible supports different from architectural textiles can be, for example, those intended for the manufacture of in particular: - air bags used to protect the occupants of a vehicle, in English "airbag”,
• silicone elastomer coatings on textile substrates already provide numerous advantages to the composites thus formed, namely among others: o flexibility, o mechanical resistance, o thermal resistance, o and longevity.
• this varnish also meets upstream specifications, namely in particular: o it can be easily spread over a silicone layer, o adhere perfectly to this silicone layer , o and more generally be easy and economical to implement on an industrial level.
• PCT application WO-A-00/59992 describes silicone compositions which are useful in particular for the production of varnishes applicable on substrates, the friction coefficient of which is sought to be reduced.
• compositions comprises: at least one polyorganosiloxane A (POS) crosslinkable via functional crosslinking groups (GFR) by cationic and / or radical route:
• POS polyorganosiloxane A
• GFR functional crosslinking groups
• an initiator C chosen from onium borates
• silylated compound D substituted by secondary functional groups - preferably of alkoxy type - carried by silicon atoms and selected from those comprising at least one alkoxy and / or epoxy and / or carboxy unit, and optionally GFRs of the (meth) acrylate and / or vinyl ether and / or epoxide and / or oxethane - preferably epoxide - type, these may for example be the following compounds:
• a filler eg silica
• a filler for example: combustion silicas treated with hexamethyldisilazane or octamethylcyclotetrasiloxane (specific surface up to approximately 300 m 2 / g), smoked silicas, synthetic or natural fibers (polymers) crushed, calcium carbonates, talc, clays, titanium dioxides ...
• compositions are used as anti-fouling varnishes for RTV silicone coatings of fabrics for "air bags", for thermal transfer ribbons or for packaging films.
• Such varnishes can be improved in terms of anti-fouling properties, bondability, or even reduction of the sliding coefficient.
• they require the use of specific silicones which can be crosslinked canonically under UV activation, which leaves room for improvement on the economic level and in terms of the simplification of the means used.
• one of the essential objectives of the present invention is to provide an anti-fouling varnish composition for various silicone supports, in particular for flexible supports (textiles) coated with silicone elastomers or solid supports in silicone elastomer, this composition varnish, having for qualities essential to have a good resistance to soiling and to allow the assembly by gluing of the parts on which it is applied.
• Another essential objective of the present invention is to provide an anti-fouling and "coUable” varnish, which provides the desired low surface slippage, which is perfectly anchored on the support and in particular on the coated elastomer layer, which has a shiny appearance, while remaining economical.
• Another essential objective of the present invention is to provide an anti-fouling varnish which can be easily applied to various types of support.
• Another essential objective of the invention is to provide a crosslinkable anti-fouling varnish, easy to use and economical.
• Another essential objective of the present invention is to provide a varnish composition essentially based on non-silylated species and yet compatible with silicone elastomers and useful in particular for the production of anti-fouling varnishes, this composition having to be of a reasonable cost price and simple to prepare.
• Another objective of the invention is to provide a simple and economical varnishing process for various silicone or silicone supports formed, for example, by woven or nonwoven fibrous substrates and coated with a layer of crosslinked silicone elastomer or by supports massive at least partly constituted by silicone, using an anti-fouling varnish based on silylated species compatible with silicone elastomers.
• Another essential objective of the invention is to provide a composite comprising a support coated with at least one layer of elastomer and covered with a silicone varnish as defined above, for example a canvas (architectural textile) coated with crosslinked silicone elastomer, high resistance to soiling.
• a silicone varnish as defined above, for example a canvas (architectural textile) coated with crosslinked silicone elastomer, high resistance to soiling.
• a cationically polymerizable / crosslinkable varnish having in particular anti-fouling properties, and comprising per 100 parts by weight: -1- at least 80 parts by weight of at least one base compound comprising, per molecule, at least two polymerization / crosslinking groups, at least one of these groups being chosen from the following groups: alkenyl ether, epoxy, oxethane; these two groups being preferably selected from the group of the following associations of groups: epoxy-epoxy, oxetane-hydroxy, oxetane-alkoxysilyl, carboxy-oxetane, oxetane-oxetane, alkenyl ether-hydroxy, epoxy-alkoxy, epoxy-alkoxysilyles,
• A represents an element from groups 15 to 17 such as for example: I, S, Se, P or N,
• R 1 represents a carbocyclic or heterocyclic C6-C 2 Q aryl radical, said heterocyclic radical possibly containing nitrogen or sulfur as heteroelements,
• a phenyl radical substituted by at least one electron-withdrawing group such as for example OCF 3s CF 3 , N0 2 , CN, and / or by at least 2 halogen atoms (especially fluorine), and this when the cationic entity is an onium of an element from groups 15 to 17,
• a phenyl radical substituted by at least one element or an electron-withdrawing group in particular a halogen atom (particularly fluorine), CF 3 , OCF 3 , NO, CN, and this when the cationic entity is an organometallic complex of an element groups 4 to 10,> an aryl radical containing at least two aromatic rings such as for example biphenyl, naphthyl, optionally substituted by at least one element or an electron-withdrawing group, in particular an atom halogen including fluorine in particular, OCF 3 , CF 3 , N0 2 , CN, whatever the cationic entity,
• this initiator preferably being chosen from the group consisting of:
• non-toxic onium salt the cationic structure of which is of formula (III):
• R 3 represents the radical - ⁇ -R 4
• R 4 being a linear or branched alkyl radical comprising from 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms and of anionic structure chosen from the group comprising : Cl “ , Br “ , BF 4 " , PF 6 “ , CF 3 S0 3 ⁇ N (SO 2 CF 3 ) 2 -, C (S0 2 SF 3 ) 2 ; B (C 6 F 5 ) 4 " , B (PhOCF 3 ) 4 “ , SbF 6 “ and / or AsF 6 " .
• POS polyorganosiloxane
• the varnish according to the invention is advantageous in that it makes it possible to greatly increase the resistance to soiling and the ability to stick, while having a low coefficient of sliding and a shiny appearance.
• alkenyl is meant an unsaturated, linear or branched hydrocarbon chain, substituted or not, having at least one olefinic double bond, and more preferably a single double bond.
• the "alkenyl” group has from 2 to 8 carbon atoms, better still from 2 to 6.
• This hydrocarbon chain optionally comprises at least one heteroatom such as O, N, S.
• Preferred examples of "alkenyl” groups are vinyl, allyl and homoallyl groups; vinyl being particularly preferred.
• the basic compounds -1- selected from: o -1.1- those in which the polymerization / crosslinking groups are oxetanes, and preferably from the epoxy monomers of the following formula:
• silicone oligomer and / or polymer consisting of at least one crosslinkable and / or polymerizable silicone oligomer and / or polymer which is liquid at room temperature or hot-melt at temperature below 100 ° C., the silicone oligomer and / or polymer comprising: D at least a pattern of formula (1.2):
• ⁇ R ° represents an alkyl, cycloalkyl, aryl, vinyl, hydrogen, hydroxy or alkoxy radical, preferably a lower C 6 alkyl,
• Z is an organic substituent comprising at least one reactive epoxy, and / or alkenylether and / or oxetane and / or dioxolane and / or carbonate function, D and at least two silicon atoms.
• the reactive functions Z of the silicone polymer or oligomer 1.2 can be very varied. However, particularly advantageous varnishes are obtained when the silicone oligomer or polymer (-1.2-) comprises at least one unit (FS) in which Z represents an organic substituent Zl comprising at least one reactive epoxy and / or dioxolane function, and preferably at least one reactive epoxy function.
• FS unit
• Z represents an organic substituent Zl comprising at least one reactive epoxy and / or dioxolane function, and preferably at least one reactive epoxy function.
• the silicone oligomer or polymer -1.2- with at least one reactive Zl epoxy and or dioxolane function, and preferably at least one reactive Zl epoxy function can:
• the varnish can also comprise other oligomers and / or silicone polymers and different from the oligomer / polymer -1.2- comprising other reactive functions Z2 such as the alkenyl ether, oxetane functions and / or carbonate and optionally Zl reactive functions.
• other reactive functions Z2 such as the alkenyl ether, oxetane functions and / or carbonate and optionally Zl reactive functions.
• reactive functions Z these can be chosen in particular from the following radicals:
• R represents a linear or branched C 6 -C 6 alkyl radical.
• the silicone polymer or oligomer -1.2- consists of at least one silicone of the following average formula:
• the cationic initiator -2- is selected from the group comprising:
• the additive -3- is:
• alkenylated polyorganosiloxane POS
• alkenyl groups each of which comprise at least one (meth) acrylic or (meth) acrylate function, said alkenyl groups being more particularly selected from the groups of general formula below:
• R, R are hydrogenated or hydrocarbon radicals identical or different from each other and preferably represent hydrogen, a linear or branched C 4 -C 4 alkyl or a phenyl optionally substituted by at least one C-- alkyl G,
• R is methyl or hydrogen, the additive -3.1- being more especially still selected from POS (poly) (meth) acrylates;
• POS (poly) (meth) acrylates are polyorganosiloxanes comprising, per molecule, one or more acrylate or methacrylate functionalities.
• esters of acrylic acid and methacrylic acid they also target, according to the invention, the acid forms as such.
• the grafted POS thus obtained is reacted with (meth) acrylic acid and or an (meth) acrylic acid anhydride.
• the reaction is catalyzed by diazabicyclo (2,2,2) octane.
• This grafting of the acrylate or methacrylate function by means of a first epoxy functionalization takes place both on Si-H units located in the chain and on terminal Si-H units.
• French patent application FR-A-2 611 729 discloses a process for preparing a POS with acrylate or methacrylate functionality.
• the starting material used is a POS with ⁇ SiH patterns present in the chain or at the end of the silicone chain. It may be, for example, a linear poly (dimethyl) (methylhydrogen) siloxane ⁇ , ⁇ -trimethylsilyl: MD 110 D H 5 M POS, which is reacted with allylglycedyl ether (AGE).
• the epoxy functionalized POS obtained is placed in the presence of acrylic acid, n-butanol, MIBK, hydroquinone and a catalyst based on chromium triacetate monohydrate.
• the acrylic acid is attached to the ether-epoxy graft by opening the epoxy ring.
• the article "Makromol. Chem., RAPID COMMUN. 7, 703-707 (1986)" discloses the synthesis of POS ⁇ , ⁇ -bis acrylates obtained from POS with motifsSiH terminal units which are reacted with EFA in the presence of chloroplatinic acid. The epoxy-terminated POS thus obtained is reacted with methacrylic acid in the presence of chromium di-isopropyl salicylate. This article corresponds to the French RHONE POULENC patent mentioned above.
• EP-A-0 940 458 and EP-A-0 940 422 describes POSs comprising (meth) acrylate groups, obtained from POSs with Si-H units, which is reacted with a polyhydroxy alkenyl ether of formula:
• the silicone carrying a polyhydroxylated ether graft thus obtained is then subjected to an esterification with (meth) acrylic acid and optionally with a monocarboxylic acid free of double bond.
• This "acrylation" of polyhydroxyalkylsiloxane is catalyzed by triflic acid.
• the starting materials used are ⁇ , ⁇ -dimethylhydrogensiloxy POSs, which are reacted by hydrosilylation on one of the double bonds of (meth) acrylate compounds each comprising at at least two (meth) acryloyl groups, preferably three.
• this hydrosilylation is carried out in the presence of a metal catalyst, preferably based on platinum.
• the POS with SiH motif is preferably a polydimethylsiloxane ⁇ , ⁇ -diethoxyhydrogenosiloxy obtained from a polydimethyl siloxane ⁇ , ⁇ -diol which is condensed with triethoxysilane.
• French patent application FR-A-2 634 769 discloses a diorganopolysiloxane having a thioalkylacrylate function obtained by reacting a vinyl POS, for example a linear ⁇ , ⁇ -vinylated polydimethylsiloxane, with a mercaptoalkanol which reacts with the vinyl functions via thiol groups, so as to produce a polydimethylsiloxane, ⁇ -thioalkylhydroxylé.
• This alcohol is capable of reacting with acrylic acid by esterification.
• POS operates in the presence of a free radical generator of the azobisisobutyronitrile (AIBN) type.
• AIBN azobisisobutyronitrile
• the unpublished French patent application No. 0108896 of 06/29/2001 relates to a polyorganosiloxane (POS) carrying at least one group (A) ester of unsaturated carboxylic acid, preferably (meth) acrylate, characterized in that that it is obtained by reacting at least one POS (I) or (II) carrying at least one ⁇ Si-H motif with at least one unsaturated epoxide (III), then with at least one polyhydroxylated nucleophile (IV) capable of opening the epoxy function (s) involved, and finally with at least one unsaturated carboxylic acid (V), preferably (meth) acrylic acid, which combines with the hydroxyls of the nucleophile (IV) to form the ester groups (A).
• POS acrylates are obtained for example as indicated below
• PCT application WO 01/77240 discloses a composition based on acrylate functionalized POSs, comprising dimethylsiloxy units, trimethylsiloxy terminal units and methyl-acrylate-siloxy units.
• the POSs (poly) (meth) acrylates usable as an additive -3- according to the invention can be those marketed under the names BYK SILCLEAN 3700®, TEGO RC 902 ⁇ ®, TEGO RC 702, PC 900, PC 911, POS acrylics marketed by RHODIA INC and corresponding to those described in WO-A-01/77240.
• epoxidized POSs they comprise at least one epoxy group per molecule, in the chain and / or at the ends of the chain.
• the group (s) epoxides can for example be included in the substituents X of the silicon of the following formula:
• ⁇ E and D which are identical or different radicals chosen from linear or branched C ⁇ -C alkyls, ⁇ z which is equal to 0 or 1,
• ⁇ R 9 ; R 10 , R 11 which are identical or different radicals representing hydrogen or a linear or branched C1-C4 alkyl, hydrogen being more particularly preferred, ⁇ R 9 and R 10 or R 1 can alternately constitute together with the two carbons carrying the epoxy, an alkyl ring having 5 to 7 members.
• the silylated compound -4- is an epoxy alkoxysilane, preferably corresponding to the following general formula:
• R 7 is a linear or branched C t -C alkyl radical
• R 8 is a linear or branched alkyl radical, y is equal to 0, 1, 2 or 3, preferably to 0 or 1 and, more preferably still to 0, X * meets the same definition as that given above for X or corresponds to a group comprising at least one (meth) acrylate functionality.
• the additive -4- is more preferably chosen from the group comprising:
• silylated compounds -4- mention may be made of ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane of the type sold by the company OSI under the registered trademark silane CoatOSil® 1770, 3-glycidyloxypropyl-triethoxysilane of the type of that marketed by DEGUSSA under the registered trademark silane DYNASILAN® GLYEO; 3-glycidyloxypropyl-trimethoxysilane of the type sold by the company DEGUSSA under the registered trademark silane DYNASILAN® GLYMO; or alternatively 3-methacryloxypropyltrimethoxysilane of the type sold by the company DEGUSSA under the registered trademark DYNASILAN® MEMO.
• silylated compound -5- alkenyl and epoxide and / or alkenyl ether and / or oxethane it is preferable to use in accordance with the invention a compound chosen from epoxyfunctional and alkenylfunctional polydiorganosiloxanes comprising at least one unit of formula:
• X ′ comprises at least one group corresponding to the same definition as that given above for the epoxide X radical of formula (V) or for the Z (Ei, E 2 ) radical in formula 1.2, - X "comprises at least one group corresponding to the same definition as that given above for the alkenyl radical of formula (IV) as defined above,
• G has the same meaning as G ', G "above and r has a value between 0 and 3, for example between 1 and 3.
• silylated compounds -5- mention may be made of polydimethylsiloxan ⁇ s functionalized with epoxies and (poly) - (meth) -acrylates or -acrylics. It may for example be a silicone epoxyacrylate resin of the type described in US-B-4,663,185.
• the additive -6- ultrafine charge is preferably selected from mineral fillers having an average particle diameter ⁇ me close to or less than 0.5 ⁇ m, advantageously 0.1 ⁇ m; preferably from: o siliceous fillers belonging to the group of silica powders (colloidal silicas, combustion and precipitation silicas, or their mixtures), o other mineral fillers selected from the group comprising: Ti0 2 and Al 2 O 3 , o and their mixtures.
• At least one thickener -7- chosen from waxes-preferably based on micronized polyamide-.
• the varnish according to the invention can comprise other functional additives -8-. They may be covering products such as, for example, pigments / dyes (8.1), stabilizers (8.2) - in particular with respect to UV-, diluents ⁇ solvents ⁇ (8.3) or agents resistant to acid rain. .
• the preferred varnish composition is of the type of those which can be crosslinked cationically, under activation, in particular UV, and comprising on dry:
• This dynamic viscosity ⁇ at 25 ° C, called “Newtonian”, is measured, in a manner known per se, at a shear speed gradient of 100 s "1 , sufficiently low for the viscosity measured to be independent of the speed gradient.
• the varnish is in the form of a single-component system capable of quickly crosslinking under UV by cation.
• the silicone varnish according to the invention is likely to have outlets in numerous fields of application and in particular in the field of coating: o supports with a woven or non-woven fibrous core, silicone or not (ie coated on at least one of its faces with at least one layer of elastomer), o or else supports constituted by solid silicone parts and / or silicone or not.
• the invention relates to a varnishing process characterized in that the composition as defined above is applied, as anti-fouling varnish, on a support optionally constituted at least in part by silicone, preferably elastomeric silicone.
• this process essentially consists of:
• the varnish is applied to the support according to a deposition rate less than or equal to 35 g / m 2 , preferably between 2 and
• the varnish according to the invention can for example be applied to a support by any suitable coating or transfer means (for example doctor blade, coating cylinder, gravure printing, dynamic screen printing, brush, spraying: spray gun , etc.).
• the crosslinking of the varnish applied to the support to be coated can be activated for example by heating the impregnated or even coated support to a temperature between
• the thermal activation means are of the type known and suitable for this purpose, for example oven or I.R.
• the above-defined varnishing process can relate either to architectural textiles or to supports other than architectural textiles.
• the present invention also relates to the varnished (or composite) support - with the exclusion or not of any architectural textile as defined below - endowed with anti-fouling properties and a low coefficient of slip, capable of being obtained by the process as referred to above.
• This composite is characterized in that it comprises: o a support, preferably flexible, and more preferably still chosen from the group comprising:
• the polymer films in particular polyester, polyamide, polyolefin, polyurethane, polyvinyl chloride or silicone, o optionally a coating integral with at least one of the faces of the support and consisting of at least one layer of silicone elastomer, o at least one layer of varnish based on the composition as defined above.
• the composite capable of being obtained by the process referred to above may comprise: - a solid support optionally made of silicone and / or optionally at least partially coated with silicone, the silicone preferably being a silicone elastomer, and at least one layer of varnish based on the composition as defined above.
• the silicone coating is optional, for example when the support is itself silicone.
• the support for the composite according to the invention comprises at least one material chosen from the group comprising: - glass in mass form or in the form of fibers,
• the flexible supports concerned by the invention can be, among others, architectural textiles.
• non-woven fibrous supports polymer films, optionally a coating integral with at least one of the faces of the support and consisting of at least one layer of silicone elastomer and at least one other (co) polymer, at least one layer of varnish as defined above.
• the support included in this architectural textile comprises at least one material chosen from the group comprising: glass in the form of fibers, ceramics in the form of fibers, - natural or synthetic polymers, in the form of fibers or under form of films, in particular polyester, polyamide, polyurethane, polyvinyl chloride or silicone, cellulosic, lignocellulosic materials without mass or fibrous form, in particular paper, cardboard or the like.
• the present invention aims: o these manufactured articles comprising composite as defined above and different from those included in the constitution of architectural textiles, o as well as manufactured articles comprising architectural textiles based on the composite also defined above.
• the fibrous supports intended to be coated and then varnished in accordance with the invention can be, for example fabrics, nonwovens or knits or more generally any fibrous support comprising fibers chosen from the group of materials comprising: glass, silica, metals, ceramics, silicon carbide, carbon, boron, natural fibers like cotton, wool, hemp, flax, artificial fibers like viscose, or cellulosic fibers, synthetic fibers such as polyesters, polyamides, polyacrylics, chlorofibers, polyolefins, synthetic rubbers, polyvinyl alcohol, aramides, fluorofibers, phenolics, silicones ...
• fibrous supports mention may be made of glass, polyester, polyamide, polyurethane, polyolefin, polyvinyl chloride or silicone fabrics.
• the anti-fouling varnish according to the invention can be applied:
• plastic films e.g. polyester
• thermal transfer ribbons for printers of the same name
• protective protective plastic films e.g. polyester, polyurethane, polyamide, polyolefin (polyethylene or polypropylene), polyvinyl chloride or silicone].
• the present invention also relates to the use of the composition as defined above, as anti-fouling varnish, for example for coating a fibrous support with the exception or not of any architectural textile.
• the present invention also relates to the use, as anti-fouling varnishes, of a composition which can be polymerized / crosslinkable by the cationic route and comprising per 100 parts by weight:
• the massive supports concerned by the invention can be, among others, pieces chosen from the group comprising: - furniture,
• the present invention finally relates to any manufactured article comprising composite as defined above.
• the silicone capable of forming the coating or the bulk part on which the varnish composition according to the invention can be applied may be an elastomer based on polyorganosiloxane (s), crosslinkable or at least partially crosslinked, and preferably chosen from:
• the anti-fouling varnish obtained from the composition, as defined above, is applied to the (or more) layer (s) (upper (s)) of silicone elastomer.
• RTV Room Temperature Vulcanizing
• LSR Low Temperature Rubber
• EVC Hot Vulcanizable Elastomer
• the invention relates more precisely to the supports (for example textiles such as those used for the manufacture of "airbags") coated on one and / or the other of their faces with a layer of silicone elastomer crosslinked RTV, EVC or LSR, itself coated with a coating of anti-fouling silicone varnish as defined above.
• the problem of providing anti-fouling properties is particularly acute with regard to these crosslinked silicone elastomeric coatings since, as has already been indicated above, the latter have the characteristic of having a tacky feel.
• the polyorganosiloxanes, main constituents of the tacky layers of crosslinked elastomers or solid supports / parts to which the varnish according to the invention is capable of being applied, can be linear, branched or crosslinked, and include hydrocarbon radicals and / or reactive groups such as, for example, hydroxyl groups, hydrolyzable groups, alkenyl groups and hydrogen atoms.
• hydrocarbon radicals and / or reactive groups such as, for example, hydroxyl groups, hydrolyzable groups, alkenyl groups and hydrogen atoms.
• varnishable polyorganosiloxanes consist of siloxyl units of general formula:
• the symbols Z ° identical or different, each represent a hydrogen atom, a C2-C5 alkenyl group, a hydroxyl group, a hydrolyzable atom, a hydrolysable group;
• - m an integer equal to 0, 1, 2 or 3;
• - Xi an integer equal to 0, 1, 2 or 3;
• organic radicals R ° directly linked to the silicon atoms methyl groups; ethyl; propyl; isopropyl; butyl; isobutyl; n-pentyl; t-butyl; chloromethyl; dichloromethyl; ⁇ -chloroethyl; ⁇ , ⁇ - dichloroethyl; fluoromethyl; difluoromethyl; ⁇ , ⁇ -difluoroethyl; trifluoro-3,3,3 propyl; trifluoro cyclopropyl; 4,4,4-trifluorobutyl; hexafluoro-3,3,4,4,5,5 pentyl; ⁇ -cyanoethyl; ⁇ -cyanopropyl; phenyl: p-chlorophenyl; m-chlorophenyl; 3,5-dichloro phenyl; trichlorophenyl; tet
• the organic radicals R ° linked to the silicon atoms are methyl, phenyl radicals, these radicals possibly being halogenated or alternatively cyanoalkyl radicals.
• the symbols Z ° may be hydrogen atoms, hydrolysable atoms such as halogen atoms, in particular chlorine atoms, vinyl groups, hydroxyl groups or hydrolysable groups such as for example: amino, amido, aminoxy, oxime, alkoxy, alkenyloxy, acyloxy.
• the polyorganosiloxanes used in these compositions generally consist of couples based on a part of a linear, branched or crosslinked polysiloxane consisting of units (II) in which the remainder Z ° represents a C2-Cg alkenyl group and where xi is at least equal to 1, optionally associated with units (I '), and on the other hand of a linear, branched or crosslinked hydrogenopolysiloxane consisting of units (II ') in which the remainder Z ° then represents a hydrogen atom and where xj e st at least equal to 1, possibly associated with patterns (T).
• the two-component or single-component polyorganosiloxane compositions crosslinking at room temperature (RTV) by polycondensation reactions under the action of moisture, generally in the presence of a metal catalyst, for example a tin compound, are described for example for the monocomponent compositions in patents US-A-3,065,194, 3,542,901, 3,779,986, 4,417,042, and in patent FR-A-2,638,752, and for bicomponent compositions in patents US-A-3 678 002, 3 888 815, 3 933 729 and 4 064 096.
• the polyorganosiloxanes used in these compositions are generally linear, branched or crosslinked polysiloxanes consisting of units (II ′) in which the remainder Z ° is a hydroxyl group or a atom or hydrolysable group and where xi is at least equal to 1, with the possibility of having at least one Z ° residue which is equal to a hydroxyl group or to an atom or to a hydrolyzable group and at least one Z ° residue which is equal to an alkenyl group when xj is equal to 2 or 3, said units (II ') being optionally associated with units (I 1 ).
• Such compositions may also contain a crosslinking agent which is in particular a silane carrying at least three hydrolysable groups such as for example a silicate, an alkyltrialkoxysilane or an aminoalkyltrialkoxysilane.
• RTV polyorganosiloxane compositions which crosslink by polyaddition or polycondensation reactions, advantageously have a viscosity at 25 ° C at most equal to 100,000 mPa.s and, preferably, between 10 and 50,000 mPa.s.
• compositions which crosslink with heat by polyaddition reactions and more precisely of compositions known as EVC polyaddition type, having a viscosity at 25 ° C at least equal to 500,000 mPa.s and, preferably between 1 million mPa.s and 10 million mPa.s and even more.
• compositions curable at high temperature under the action of organic peroxides such as 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, t-butyl perbenzoate, cumyl peroxide, peroxide of di-t-butyl.
• organic peroxides such as 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, t-butyl perbenzoate, cumyl peroxide, peroxide of di-t-butyl.
• the polyorganosiloxane or gum used in such compositions then essentially consists of siloxy units (Y), optionally associated with units (II ') in which the remainder Z ° represents an C2-C8 alkenyl group. and where x is equal to 1.
• EVCs are for example described in the patents US-A-3 142 655, 3 821 140, 3 836 489 and 3 839 266).
• These compositions advantageously have a viscos
• polyorganosiloxane compositions which can be varnished by the silicone varnish composition according to the invention are those, single-component or two-component, crosslinking with heat by polyaddition reactions, called LSR compositions. These compositions meet the definitions given above with respect to the preferred compositions called RTV, except as regards their viscosity which is this time in the range from a value greater than 100,000 mPa.s to 500,000 mPa. s.
• the elastomeric silicone coatings to which the anti-fouling varnish according to the invention can be applied are more especially coatings obtained from RTV cold vulcanizable silicone elastomer compositions, in particular of the bicomponent type (RTV 2), by polyaddition.
• the anti-fouling is measured by applying smoke black to the varnish coating and sweeping off the dirt using absorbent tissue.
• the assembly properties are determined by measuring the adhesion strength of an EVC.
• the principle of the assemblies is presented below.
• the slip coefficients Ks and Kd are determined according to the APL / END / ET / T219 procedure on coated fabric.
• the support sample is a coating of RTV II applied to a 700 dctex polyamide fabric impregnated with RTV 1530 (grammage 45 g / m 2 ) previously treated with Corona.
• This RTV II coating is prepared as follows:
• a heating phase is started during which the mixture is placed under a stream of nitrogen (30m3 / h); the heating continues until reaching approximately 140 ° C., a plateau temperature which is maintained for 2 hours in order to remove the volatile materials from the composition. The suspension is then left to cool.
• part A and part B are formulated in suitable reactors.
• Part A contains:
• Part B contains: 480 g of the suspension
• Parts A and B are mixed in the ratio of 100 to 10 and, after boiling, the test pieces necessary for measuring the mechanical properties and the adhesion properties are prepared.
• Crosslinking on the support in question is carried out by staying for 10 minutes in a ventilated oven maintained at 150 ° C.
• the thickness of the coating is sufficient (approximately 300 ⁇ m) so that the coated surface is smooth and the nature of the fabric used becomes completely screened.
• the varnish formulations are coated with Meyer's bar.
• the varnish layer has a grammage of the order of 15 g / m 2 .
• the polymerization is carried out on an IST UV bench (2 type H lamps with a power of 160 W), with a running speed of 20 m / min.
• the basic formulation of the varnish consists of> -1- of the basic monomer compound CYRACURE® 6105 from the company Dow Chemical:
• PDMS polydimethylsiloxane
• the varnish formulations allowing access to the targeted performances obtain at least 4 in the soiling test, a KD ⁇ 0.8 and allow a level of adhesion> 70 N.
• a complementary test ia was carried out by replacing CYRACURE ® -1- by the polymer S200 -1-, this test is conclusive.

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• Wood Science & Technology (AREA)
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• 2002
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