EP1969063A1 - Method of preventing the appearance of misting when coating flexible media with a crosslinkable liquid silicone composition in a multi-roll device - Google Patents

Method of preventing the appearance of misting when coating flexible media with a crosslinkable liquid silicone composition in a multi-roll device

Info

Publication number
EP1969063A1
EP1969063A1 EP06830433A EP06830433A EP1969063A1 EP 1969063 A1 EP1969063 A1 EP 1969063A1 EP 06830433 A EP06830433 A EP 06830433A EP 06830433 A EP06830433 A EP 06830433A EP 1969063 A1 EP1969063 A1 EP 1969063A1
Authority
EP
European Patent Office
Prior art keywords
coating
carbon atoms
optionally substituted
optionally
misting
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Withdrawn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
EP06830433A
Other languages
German (de)
French (fr)
Inventor
Frédéric MAGD
Tania Ireland
Lucile Gambut-Garel
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 EP1969063A1 publication Critical patent/EP1969063A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • 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
    • C08G77/20—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
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • 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
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
    • D21H23/56—Rolls
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/001—Release paper

Definitions

  • the invention relates to the general field of silicone coating on high-speed cylinders of various flexible supports, such as sheets of paper or of synthetic polymer (polyolefin, polyester, etc.), or even of textile.
  • the invention relates to the coating of flexible materials with liquid compositions containing one or more crosslinkable polyorganosiloxanes by polyaddition, by dehydrogenocondensation, by polycondensation, by cationic or by radical route so as to form a protective film or coating having in particular anti-adhesion and / or hydrophobic properties.
  • the flexible supports can be papers, cardboards, plastic films, or metallic films.
  • the applications of these silicone coated supports are for example: food paper (baking molds, packaging), label / adhesive tape, seal, etc.
  • the coating of these flexible supports with crosslinkable liquid silicones is carried out on coating devices operating continuously, and at very high speed.
  • These devices include coating heads made up of several cylinders including in particular a pressure cylinder and a coating cylinder, which is continuously supplied with crosslinkable liquid silicone composition, by means of a series of cylinders joined to each other.
  • the flexible support strip circulates at high speed between the pressure cylinder and the coating cylinder to be coated on at least one of its faces with a silicone film intended to crosslink by means of crosslinking means arranged downstream of the head d coating.
  • These crosslinking means can be emitters of heat, radiation (eg ultraviolet) or electron beams for example.
  • This phenomenon firstly results in a loss of consumable, and above all a deposit of droplets of coating liquid on the support downstream (for example at the level of the oven), which seriously affects the quality of the coating.
  • roller coating device causes rapid fouling of the roller coating device, resulting in maintenance constraints and premature wear.
  • Another approach for combating the formation of fog in roller coating machines consists in acting on the formulation of the liquid silicone coating composition.
  • the process for the preparation of these star silicone polymers consists in reacting (by hydrosilylation) incompletely a polyorganosiloxane comprising reactive units ⁇ SiH with a long chain olefin in order to obtain a partially substituted polyhydrogenoorganosiloxane which is then reacted by hydrosilylation with a vinylized silicone resin of type MQ and a long chain diolefin. It is clear that such compositions are relatively complex and therefore expensive to obtain. Furthermore, they still need to be improved as regards the fight against the formation of mist in the silicone coating on cylinders, at high speed.
  • European patent EP-O 716 115 describes a process for manufacturing a silicone coating composition at high speed with cylinders, this composition being presented as allowing the reduction of the fog density.
  • a polydimethyl-methylhydrogenosiloxane with trimethylsilyl ends of degree of polymerization equal to 12 is used, as well as 0.01% of a polydimethylsiloxane substituted by perfluoethylbutyl and methylvinyl functions, the ends of which are of the dimethylvinylsiloxyl type.
  • a degree of polymerization equal to 300, as well as polypropylene glycol and optionally a stearic or oleic alcohol.
  • polydimethylsiloxanes functionalized by polyoxypropylene groups are combined with other functionalized polydimethylsiloxanes, e.g. by hexylene units as well as with a hydrosilylation catalyst based on platinum, to form silicone coating compositions making it possible to reduce the formation of mist.
  • the functionalization patterns can be hydrophobic residues such as stearic or oleic acid residues.
  • silicone compositions intended to be coated on flexible supports to form, after crosslinking by the cationic route under UV, a non-stick coating.
  • these compositions include cellulose fibers having an average length of between 15 and 100 ⁇ m and an average thickness of between 5 and 40 ⁇ m.
  • the polyorganosiloxanes used are polyorganosiloxanes functionalized by crosslinking groups of the acryloxy or methacryloxy type, allowing crosslinking by radical route under UV.
  • the cellulose fibers incorporated into the composition make it possible to provide a solution to the technical problem which is to obtain a non-brittle crosslinked non-stick silicone coating.
  • Cellulose fibers are presented as providing improvements with regard to the transfer of the coating silicone film onto the support, the cutting resistance, the mechanical properties (tensile and tear resistance), the fixing of the coating. on paper, the reduction in the absorption of coating liquid within the paper, and incidentally the reduction in the formation of mist.
  • Patent application WO-0198418 describes the use of an antimisting agent which is a branched polyorgosiloxane with a reactive motif ⁇ SiH in a silicone coating composition.
  • This anti-misting agent is obtained according to a process which consists in reacting a large excess of at least one organohydrogensilicon-based compound containing at least three ⁇ SiH groups with at least one compound containing at least two alkenyl groups, in the presence of a catalyst containing a platinum group metal with the condition that the ratio [number of reactive unit ⁇ SiH1: [number of reactive unit ⁇ Si-alkenyli> 4.6: 1.
  • JP-62 64 011 describes a coating liquid containing a film-forming resin and a solvent and which also contains wax particles with a diameter between 1 and 10 ⁇ m, the diameter of the particle the largest being at most equal to 150% of the thickness of the wet coating film applied to the support.
  • a coating liquid would allow an increase in the coating speed of at least 10 to 30 m / min, a priori thanks to a limitation of the formation of mist.
  • the teaching of such a document should be discarded because it does not concern silicone coatings.
  • one of the essential objectives of the invention is to propose an effective method of combating the appearance of mist when coating flexible supports with a liquid silicone composition precursor of crosslinked coatings, this coating being carried out using a cylinder coating device operating at high speed.
  • Another essential objective of the invention is to provide an economical and simple method of combating the appearance of fog when coating flexible supports with a silicone composition intended to crosslink, this coating taking place in a device for high speed roller coating.
  • Another essential objective of the invention is to propose a process for coating flexible supports at high speed on cylinders, flexible materials, by means of crosslinkable silicone compositions in non-stick coatings, in which the formation of mist is reduced.
  • dehydrogenocondensation by polycondensation, by cationic route or by radical route,
  • At least one catalyst or photoinitiator C optionally at least one catalyst or photoinitiator C, the nature of which is chosen according to the type of reaction envisaged for said polyorganosiloxane A,
  • step a) a liquid anti-fog additive E (“antimisting” additive) is added to said liquid silicone composition X, which is:
  • R 1 , R 2 , R 3 , R ' 3 , R 4 , R 5 , R 6 and R 7 identical or different, each represent independently of one another:
  • alkyl radical containing 1 to 20 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl,
  • an aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens and / or alkyls, with
  • At least one polyorganosiloxane G having, per molecule, at least 3 C 2 -C 6 alkenyl groups linked to silicon in the presence:
  • the polyaddition catalyst H is composed of at least one metal belonging to the platinum group, and
  • an anti-misting additive E which is a branched polyorganosiloxane L (or a mixture comprising one or more branched polyorganosiloxanes L) carrying at least one reactive unit ⁇ SiH and only on units M ′, in order to obtain effective control of the formation of fog, which results in a significant improvement of the problem linked to the appearance of said fog in a cylinder coating system operating at high speed. It is also of the merit of the inventors to have prepared this additive via a polyaddition reaction from:
  • a polyorganosiloxane oil F terminated in ⁇ , ⁇ by reactive units ⁇ SiH (thus comprising only two reactive units ⁇ SiH), and
  • a polyorgasiloxane oil G comprising at least three reactive units ⁇ Si-alkenyl, with the condition that the nature and the amounts of components F and G are chosen so that the ratio [number of reactive unit ⁇ Si HI : [number of reactive unit ⁇ Si-alkenyli> 1: 1.
  • a polyorgasiloxane oil comprising at least two reactive units ⁇ Si-alkenyl
  • the conditions defined in the method of preparation of the anti-fog additive E (“antimisting” additive) makes it possible to obtain an additive having anti-fog properties in all remarkable respects. Without wishing to be limited to a scientific theory or to a mechanism, it seems that this property is due to the presence of branched polymer (s) L according to the invention whose viscoelastic properties make it possible to combat the appearance of fog in a cylinder coating system operating at high speed.
  • the anti-fog additive E according to the invention is used in quantities sufficient to reduce the amount of misting during coating. Of course, the skilled person, by routine tests, can easily determine these quantities. For example, it can use the additive according to the invention in quantities of between 0.1 and 15 parts by weight relative to the total weight of the liquid silicone composition X silicone coating precursor (s).
  • the polyorganosiloxane G has:
  • - X is a C 2 -C 6 alkenyl group
  • - Z is a monovalent hydrocarbon group, free from any unfavorable action on the activity of the catalyst and chosen from alkyl groups having from 1 to 8 carbon atoms included, optionally substituted by at least one halogen atom, and also from aryl groups,
  • motifs of medium formula optionally at least part of the other motifs are motifs of medium formula:
  • Polyorganosiloxanes F and G can react with each other according to a known polyaddition mechanism, which leads to crosslinking of the silicone composition. It is also possible to use a polyaddition catalyst H, preferably the polyaddition catalyst H is composed of at least one metal belonging to the platinum group. This catalyst can in particular be chosen from platinum and rhodium compounds.
  • the generally preferred catalyst is platinum.
  • the quantity by weight of the polyaddition catalyst H, calculated by weight of platinum metal is generally between 2 and 400 ppm, preferably between 5 and 300 ppm based on the total weight of the polyorganosiloxanes F and G.
  • polyorganosiloxanes A of the liquid silicone composition X silicone coating precursor (s) can be of the type which crosslink at room temperature or with heat by polyaddition reactions in the presence of a metal catalyst in this case based on platinum.
  • the polyaddition or monocomponent RTV or EVC polyaddition polyorganosiloxane compositions harden or crosslink essentially by reaction of hydrogenosilylated groups on silylated alkenyl groups, generally in the presence of a metal catalyst (preferably platinum). They are described for example in US Patents 3,220,972, 3,284,406, 3,436,366, 3,697,473 and 4,340,709.
  • Polyorganosiloxanes A can also be of the type which crosslink at room temperature by polycondensation reactions under the action of moisture, generally in the presence of a metal catalyst, for example a tin compound (RTV polycondensation) .
  • a metal catalyst for example a tin compound (RTV polycondensation)
  • RTV polycondensation a metal catalyst
  • the compositions using this type of polyorganosiloxane are described for example in US Patents 3,065,194, 3,542,901, 3,779,986, 4,417,042 and in Patent FR-2,638,752 (single-component compositions) and in patents US-3,678,002, 3,888,815, 3,933,729 and 4,064,096 (two-component compositions).
  • the polyorganosiloxanes A which enter into these polycondensation RTV compositions are linear branched or crosslinked polysiloxanes carrying hydroxyl groups or hydrolysable groups, for example alkoxy.
  • Such compositions may also contain a crosslinking agent, which is, in particular, a compound carrying at least 3 hydrolysable groups such as for example a silicate, an alkyltrialkoxysilane or an aminoalkyl trialkoxysilane.
  • the liquid silicone composition X can also comprise one or more polyorganosiloxanes A crosslinkable by cationic or radical route:
  • cationic initiator systems thermal initiators and / or photoinitiators
  • - initiators of the onium borate type or of organometallic complexes organic solvents donating protons (isopropyl alcohol, benzyl alcohol ,. .), and or
  • - as the case may be, in the presence of a radical initiator, via activation by actinic radiation (UV) or by electron beams.
  • UV actinic radiation
  • polyorganosiloxanes are for example epoxysilicones and / or
  • the functional epoxy polyorganosiloxanes can be prepared by hydrosylylation reactions between oils with ⁇ SiH units and epoxy-functional compounds such as vinyl-4-cyclohexenone or allyl-glycidyl ether.
  • the vinyloxyfunctional polyorganosiloxanes can be prepared by hydrosilylation reaction between oils having SiH units and vinyloxyfunctional compounds such as aHylvinylether or allylvinyloxyethoxybenzene.
  • the crosslinking inhibitor D is generally used to give the ready-to-use composition a certain pot life ("pot-life").
  • pot life By playing on the one hand on the nature of the catalytic assembly and on its concentration in the composition (from which it results a given crosslinking speed) and on the other hand on the nature of the retarder and on its concentration, it is possible to 'adjust the pot life.
  • the activity of the catalytic assembly is restored by heating (thermoactivation).
  • the retarder is preferably chosen from alcohols
  • acetylenics ethynylcyclohexanol: ECH
  • / or diallylmaleates and / or triallylisocyanurates and / or dialkylmaleates diethylmaleates and / or dialkylalcinyledicarboxylates
  • I tetramethylvinylcyxlotetrasiloxane being particularly preferred, or alkylated maleates.
  • Acetylenic alcohols are useful retarders according to the invention.
  • phosphinic derivatives for example tris- (2,4-di-tert-butylphenyl) phosphite (sold by the company CIBA under the reference lrgafos-168 ® ) or those described in the international patent application WO2004 / 061003 and in particular the Irgafos ® P-EPQ compound of the formula:
  • Such a retarder is in particular present at a rate of 1-100 molar / metal equivalent of the catalytic system.
  • crosslinking inhibitors I and I 'envisaged for the process according to the invention are, for example, those described for the inhibitor D.
  • I' is tris- (2,4-di-tert-butylphenyl) phosphite ( marketed by the company CIBA under the reference lrgafos-168 ® ).
  • liquid silicone composition X precursor of silicone coating (s) it may be advantageous to use at least one adhesion modulating system K, to allow control of the anti-adhesion properties of the crosslinked silicone coating.
  • the adhesion modulator system K is:
  • diluent and / or solvent J, J ′ and J mention may be made of aliphatic and aromatic solvents, chlorinated solvents, eg: white spirit, ketones such as methyl ethyl ketone and acetone, alcohols such as isopropanol and n-butyl alcohol, saturated, unsaturated or aromatic hydrocarbons, advantageously pentane, hexane, heptane, octane, toluene, xylene, benzene, "naphtha” petroleum fractions; C 7 -C 8 petroleum fractions, halogenated hydrocarbons and their mixtures.
  • chlorinated solvents eg: white spirit, ketones such as methyl ethyl ketone and acetone, alcohols such as isopropanol and n-butyl alcohol, saturated, unsaturated or aromatic hydrocarbons, advantageously pentane, hexane, heptane, oc
  • the liquid silicone composition X silicone coating precursor (s) to which the anti-fog additive E (“antimisting”) is added comprises:
  • the catalyst C1 can be chosen from the compounds defined for the polyaddition catalyst H described above.
  • the polyorganosiloxane A crosslinkable by polyaddition has units of formula (Vl) and optionally at least a portion of the other units are units of medium formula (VII):
  • W is an alkenyl group, preferably vinyl or allyl
  • alkyl radical containing 1 to 20 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl,
  • cycloalkyl radical containing between 5 and 8 cyclic carbon atoms, optionally substituted
  • aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens and / or alkyls.
  • a is 1 or 2, preferably equal to 1
  • - c 0, 1, 2 or 3.
  • polyorganosiloxanes A which can be crosslinked by polyaddition are dimethylpolysiloxanes with dimethylvinylsilyl ends, copolymers
  • crosslinking organosilicon compound B is preferably of the type of those having units of formula (VIII) and optionally at least part of the other units are units of average formula (IX):
  • alkyl radical containing 1 to 20 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl,
  • cycloalkyl radical containing between 5 and 8 cyclic carbon atoms, optionally substituted
  • an aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens and / or alkyls,
  • crosslinking organosilicon compound B examples are, for example:
  • liquid silicone composition X silicone coating precursor (s) can also contain at least one additive which is common in silicone compositions which crosslink by polyaddition, by polycondensation, by cationic route or by radical route.
  • at least one additive which is common in silicone compositions which crosslink by polyaddition, by polycondensation, by cationic route or by radical route.
  • the branched polyorganosiloxane L has as an average crude formula:
  • R alkyl patella of the connected polymer
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 identical or different, each represent independently of one another:
  • alkyl radical containing 1 to 20 carbon atoms, optionally substituted with at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl,
  • the liquid silicone composition X silicone coating precursor (s) to which the anti-fog additive E (“antimisting”) according to the invention is added comprises:
  • Another object of the invention relates to the use of the anti-fog additive E as defined above to reduce the appearance of mist ("misting") when coating flexible supports with a liquid silicone composition X silicone coating precursor as defined in any one of the preceding claims.
  • the last object of the invention relates to a method of coating flexible supports with at least one liquid silicone composition X precursor of silicone coating (s) as defined above, this coating being carried out using a roller coating device, characterized in that the method of combating the appearance of mist ("misting") according to the invention is used.
  • the invention provides an original simple, economical and reliable means of combating the production of mist when coating flexible supports (for example paper, film or polymer film) in coating devices. with cylinder operating at high speed.
  • the practical industrial consequence is that the running speeds can be further increased without the appearance of this phenomenon of fog detrimental to the quality of the coating.
  • the control means proposed by the invention also has the non-negligible advantage of not affecting the appearance qualities, the coverage, the anti-adhesion properties, as well as the mechanical properties (rub-off) of the coating. crosslinked silicone that is sought to be obtained on at least one of the faces of the flexible support.
  • the reduction in misting significantly improves the health and safety conditions for personnel working with industrial silicone coating devices on cylinders operating at high speed.
  • Example 3 Example 3:
  • Branched silicones prepared in part I) were tested as an anti-misting additive. The results observed are collated in the following tables, in quantity of misting measured (mg / m3) or in the form of ratio of “misting” measured with additive and without additive for different speeds of rotation of the rollers.
  • the two pressure / coating rollers have a diameter of 10 cm.
  • the pressure cylinder is covered with rubber and the chrome coating cylinder.
  • the coating cylinder was cut in a dumbbell so that the speed of the two cylinders were synchronous.
  • the pressure cylinder driven by a motor is in constant pressure contact with the coating cylinder.
  • the silicone coating liquid is poured directly into the air gap between the two rollers. The amount of fluid used is 0.25 ml.
  • compositions were then prepared by mixing a silicone polymer A1 (polydimethylsiloxane whose ends are blocked by a dimethylvinylsiloxy group whose viscosity is 220 mPa.s) and the products described above in examples 1 to 3 at a rate of 2 parts by weight of product in 100 parts by weight of polymer.
  • the compositions are homogenized with a keg for the time necessary.
  • the rotary system described above is then used on the rollers on which the preparation in question is spread. The speed of rotation of the rollers is then gradually increased.
  • the density of the fog is measured by placing near the place of contact, between the cylinders, a measuring instrument called a particle counter sold by the company ITS (France).
  • the result of the mist density measurement is expressed in mg of silicone aerosol per m 3 of air at a given measurement speed.
  • the table below brings together the results obtained:
  • the baths are obtained by successively mixing the following products:
  • the proportions of the mixture are calculated so that a ratio is obtained in the final bath between the total number in moles of vinyl groups and the total number in moles of hydrogenosiloxane groups of 1.75, a platinum concentration of 110 ppm and a rate of ethynylcyclohexanol-1 of the order of 0.15% by weight relative to the weight of the formulation. Furthermore, the anti-misting additive according to the invention is added to the silicone polymer of

Abstract

The invention relates to the general field of coating various flexible media, such as sheets of paper or synthetic polymer (polyolefin, polyester, etc.) or else a textile, with a silicone on high-speed rolls. The invention relates to an effective method of preventing the appearance of misting when coating flexible media with a liquid silicone composition that is the precursor of crosslinked coatings, this coating operation being performed using a roll coater operating at high speed.

Description

PROCÉDÉ DE LUTTE CONTRE L'APPARITION DE BROUILLARD LORS DE L'ENDUCTION DE SUPPORTS FLEXIBLES AVEC UNE COMPOSITION SILICONE LIQUIDE RÉTICULABLE,  METHOD FOR CONTROLLING THE APPEARANCE OF FOG DURING THE COATING OF FLEXIBLE SUPPORTS WITH A CROSSLINKABLE LIQUID SILICONE COMPOSITION,
DANS UN DISPOSITIF A CYLINDRES  IN A CYLINDER DEVICE
L'invention se rapporte au domaine général de l'enduction silicone sur cylindres à grande vitesse de supports flexibles divers, tels que les feuilles de papier ou de polymère synthétique (polyoléfine, polyester...), ou bien encore de textile. The invention relates to the general field of silicone coating on high-speed cylinders of various flexible supports, such as sheets of paper or of synthetic polymer (polyolefin, polyester, etc.), or even of textile.
Plus précisément, l'invention concerne l'enduction de matériaux flexibles avec des compositions liquides contenant un ou plusieurs polyorganosiloxanes réticulables par polyaddition, par déshydrogénocondensation, par polycondensation, par voie cationique ou par voie radicalaire de façon à former un film ou revêtement protecteur ayant notamment des propriétés d'anti-adhérence et/ou hydrophobes.  More specifically, the invention relates to the coating of flexible materials with liquid compositions containing one or more crosslinkable polyorganosiloxanes by polyaddition, by dehydrogenocondensation, by polycondensation, by cationic or by radical route so as to form a protective film or coating having in particular anti-adhesion and / or hydrophobic properties.
Les supports flexibles peuvent être des papiers, des cartons, des films plastiques, ou des films métalliques. Les applications de ces supports enduits de silicone sont par exemple : papier alimentaire (moules à pâtisserie, emballage), étiquette/ruban adhésif, joint, etc..  The flexible supports can be papers, cardboards, plastic films, or metallic films. The applications of these silicone coated supports are for example: food paper (baking molds, packaging), label / adhesive tape, seal, etc.
L'enduction de ces supports flexibles avec des silicones liquides réticulables est réalisée sur des dispositifs d'enduction fonctionnant en continu, et à très grande vitesse. Ces dispositifs comportent des têtes d'enduction constituées de plusieurs cylindres dont notamment un cylindre presseur et un cylindre enducteur, lequel est alimenté en continu en composition silicone liquide réticulable, au moyen d'une série de cylindres accolés les uns aux autres. La bande de support flexible circule à grande vitesse entre le cylindre presseur et le cylindre enducteur pour être enduite sur au moins une de ses faces d'un film silicone destiné à réticuler par l'intermédiaire de moyens de réticulation disposés en aval de la tête d'enduction. Ces moyens de réticulation peuvent être des émetteurs de chaleur, de radiations (e. g. ultraviolet) ou de faisceaux d'électrons par exemple.  The coating of these flexible supports with crosslinkable liquid silicones is carried out on coating devices operating continuously, and at very high speed. These devices include coating heads made up of several cylinders including in particular a pressure cylinder and a coating cylinder, which is continuously supplied with crosslinkable liquid silicone composition, by means of a series of cylinders joined to each other. The flexible support strip circulates at high speed between the pressure cylinder and the coating cylinder to be coated on at least one of its faces with a silicone film intended to crosslink by means of crosslinking means arranged downstream of the head d coating. These crosslinking means can be emitters of heat, radiation (eg ultraviolet) or electron beams for example.
Dans la course à la productivité, les fabricants de supports flexibles revêtus de silicone anti-adhérent sont demandeurs de formulations silicone liquides d'enduction, adaptées à des vitesses linéaires de défilement de la bande de supports flexibles de plus en plus élevées. Le facteur économique n'est évidement pas anodin dans cette recherche de nouvelles formulations silicone pour enduction à grande vitesse.  In the race for productivity, the manufacturers of flexible supports coated with non-stick silicone are asking for liquid silicone formulations for coating, adapted to increasingly high linear speeds of movement of the strip of flexible supports. The economic factor is obviously not trivial in this search for new silicone formulations for high speed coating.
Or, on sait que les grandes vitesses sur des machines d'enduction en continu, sont synonymes de problèmes de transfert du film liquide silicone du cylindre enducteur sur la bande de support flexible défilante. Ces problèmes de transfert ("splitting") se traduisent notamment par l'apparition d'un brouillard ou d'un aérosol ("misting", "fogging") dans l'environnement de la tête d'enduction et, plus particulièrement, au niveau des contacts entre les cylindres en rotation et/ou entre le cylindre enducteur et le support flexible à enduire. La densité de ce brouillard ou de cet aérosol augmente lorsque la vitesse linéique de défilement et donc la vitesse de rotation des cylindres augmente. However, it is known that the high speeds on continuous coating machines are synonymous with problems of transfer of the liquid silicone film from the coating cylinder onto the flexible traveling support strip. These transfer problems ("splitting") are reflected in particular by the appearance of a mist or an aerosol ("misting", "fogging") in the environment of the coating head and, more particularly, at the level of the contacts between the rotating cylinders and / or between the coating cylinder and the flexible support to be coated. The density of this fog or this aerosol increases when the linear speed of travel and therefore the speed of rotation of the cylinders increases.
Ce phénomène a pour conséquence tout d'abord une perte de consommable, et surtout un dépôt de gouttelettes de liquide d'enduction sur le support en aval (par exemple au niveau du four), ce qui nuit gravement à la qualité du revêtement.  This phenomenon firstly results in a loss of consumable, and above all a deposit of droplets of coating liquid on the support downstream (for example at the level of the oven), which seriously affects the quality of the coating.
En outre, cette formation indésirable de brouillard a des conséquences néfastes sur le plan de l'hygiène industrielle et de la sécurité des opérateurs, qui sont exposés au voisinage du dispositif d'enduction à cylindres, à une forte teneur en aérosol. Cela peut s'avérer nocif.  In addition, this undesirable formation of mist has harmful consequences in terms of industrial hygiene and the safety of operators, who are exposed in the vicinity of the roller coating device, to a high aerosol content. It can be harmful.
Par ailleurs, le "misting" provoque l'encrassement rapide du dispositif d'enduction à cylindres, d'où des contraintes d'entretien et une usure prématurée.  Furthermore, "misting" causes rapid fouling of the roller coating device, resulting in maintenance constraints and premature wear.
Pour se prémunir des conséquences de ce brouillard, on dispose en général autour de la tête d'enduction, un système d'aspiration permettant de capter ledit brouillard. To guard against the consequences of this mist, there is generally around the coating head, a suction system for capturing said mist.
Par ailleurs, l'homme du métier connaît un certain nombre de réglages de la tête d'enduction pour contrecarrer ce phénomène. On en citera quelques exemples ci-après :  Furthermore, those skilled in the art know a certain number of adjustments to the coating head to counteract this phenomenon. Some examples are given below:
A. baisser la vitesse au détriment de la productivité ;  A. lower speed at the expense of productivity;
B. diminuer le taux de dépôt de silicone au détriment des propriétés du support flexible siliconé que l'on cherche à obtenir (aspect, couverture, anti-adhérence, propriétés mécaniques) ;  B. reduce the rate of deposition of silicone to the detriment of the properties of the flexible silicone support that one seeks to obtain (appearance, coverage, non-sticking, mechanical properties);
C. augmentation de la différence entre la vitesse tangentielle du cylindre enducteur et la vitesse linéaire du papier. Mais au-delà d'un certain différentiel, l'homogénéité de la couche enduite est gravement perturbée. De plus, cela permet de réduire la densité du brouillard sans pour autant l'annihiler suffisamment pour permettre une augmentation significative de la vitesse d'enduction ;  C. increase in the difference between the tangential speed of the coating cylinder and the linear speed of the paper. But beyond a certain differential, the homogeneity of the coated layer is seriously disturbed. In addition, this makes it possible to reduce the density of the mist without destroying it sufficiently to allow a significant increase in the coating speed;
D. augmentation de la pression entre le cylindre enducteur et le cylindre presseur; là encore dans une certaine limite et sans suppression intéressante du phénomène de formation de brouillard.  D. increase in pressure between the coating cylinder and the pressure cylinder; here again within a certain limit and without interesting suppression of the phenomenon of formation of fog.
Une autre approche pour lutter contre la formation de brouillard dans les machines d'enduction à cylindres, consiste à agir sur la formulation de la composition silicone liquide d'enduction. Another approach for combating the formation of fog in roller coating machines consists in acting on the formulation of the liquid silicone coating composition.
Selon cette approche, il est connu de réduire le degré de polymérisation moyen en nombre des polyorganosiloxanes constituant le liquide d'enduction silicone et, par voie de conséquence, de réduire la viscosité du bain d'enduction silicone pour limiter la densité du brouillard.  According to this approach, it is known to reduce the number-average degree of polymerization of the polyorganosiloxanes constituting the silicone coating liquid and, consequently, to reduce the viscosity of the silicone coating bath to limit the density of the mist.
Ces méthodes connues souffrent d'un grave inconvénient qui est de modifier sensiblement les propriétés et, notamment, l'anti-adhérence du support flexible siliconé que l'on cherche à obtenir. A titre d'illustration de cette approche au travers de la formulation silicone, on peut citer la demande de brevet internationale WO 2004/046248 qui décrit l'utilisation de polymères silicone en étoile utilisés en tant qu'additif anti-brouillard pour des applications de revêtement sur des supports flexibles. Le procédé de préparation de ces polymères silicones étoiles consiste à faire réagir (par hydrosilylation) de manière incomplète un polyorganosiloxane comprenant des motifs réactifs≡SiH avec une oléfine à longue chaîne afin d'obtenir un polyhydrogénoorganosiloxane partiellement substituée que l'on fait ensuite réagir par hydrosilylation avec une résine silicone vinylée de type MQ et une dioléfine à longue chaîne. Il est clair que de telles compositions sont relativement complexes et donc coûteuses à obtenir. Par ailleurs, elles restent encore perfectibles en ce qui concerne la lutte contre la formation de brouillard dans l'enduction silicone sur cylindres, à grande vitesse. These known methods suffer from a serious disadvantage which is to modify the properties appreciably and, in particular, the anti-adhesion of the flexible silicone support which it is sought to obtain. As an illustration of this approach through the silicone formulation, mention may be made of international patent application WO 2004/046248 which describes the use of star-shaped silicone polymers used as anti-fog additive for applications of coating on flexible supports. The process for the preparation of these star silicone polymers consists in reacting (by hydrosilylation) incompletely a polyorganosiloxane comprising reactive units≡SiH with a long chain olefin in order to obtain a partially substituted polyhydrogenoorganosiloxane which is then reacted by hydrosilylation with a vinylized silicone resin of type MQ and a long chain diolefin. It is clear that such compositions are relatively complex and therefore expensive to obtain. Furthermore, they still need to be improved as regards the fight against the formation of mist in the silicone coating on cylinders, at high speed.
Le brevet européen EP-O 716 115 décrit un procédé de fabrication d'une composition silicone d'enduction à grande vitesse avec des cylindres, cette composition étant présentée comme permettant la réduction de la densité de brouillard. Selon ce procédé, on met en oeuvre un polydiméthyl-méthylhydrogénosiloxane à extrémités triméthylsilyle de degré de polymérisation égale à 12, ainsi que 0,01 % d'un polydiméthylsiloxane substitué par des fonctions perfluo- éthylbutyle et méthylvinyle, dont les extrémités sont du type diméthylvinylsiloxyle et de degré de polymérisation égale à 300, ainsi que du polypropylèneglycol et éventuellement un alcool stéarique ou oléique. Cela conduit à des polydiméthylsiloxanes fonctionnalisés par des groupements de polyoxy-propylène. Ces polydiméthylsiloxanes fonctionnalisés sont associés avec d'autres polydiméthylsiloxanes fonctionnalisés, e.g. par des motifs héxènyles ainsi qu'avec un catalyseur d'hydrosilylation à base de platine, pour former des compositions silicone d'enduction permettant de réduire la formation de brouillard. Les motifs de fonctionnalisation peuvent être des restes hydrophobes tels que des restes d'acide stéarique ou oléique. European patent EP-O 716 115 describes a process for manufacturing a silicone coating composition at high speed with cylinders, this composition being presented as allowing the reduction of the fog density. According to this process, a polydimethyl-methylhydrogenosiloxane with trimethylsilyl ends of degree of polymerization equal to 12 is used, as well as 0.01% of a polydimethylsiloxane substituted by perfluoethylbutyl and methylvinyl functions, the ends of which are of the dimethylvinylsiloxyl type. and a degree of polymerization equal to 300, as well as polypropylene glycol and optionally a stearic or oleic alcohol. This leads to polydimethylsiloxanes functionalized by polyoxypropylene groups. These functionalized polydimethylsiloxanes are combined with other functionalized polydimethylsiloxanes, e.g. by hexylene units as well as with a hydrosilylation catalyst based on platinum, to form silicone coating compositions making it possible to reduce the formation of mist. The functionalization patterns can be hydrophobic residues such as stearic or oleic acid residues.
Le brevet américain US-4 808 391 concerne des encres et des vernis à base de silicone, et plus précisément un procédé d'application de ces encres/vernis sur un substrat, à l'aide de machine d'enduction à rouleau fonctionnant à grande vitesse. Ce brevet divulgue notamment des compositions comprenant des polydiméthylsiloxanes à extrémités vinylées de viscosité à 25°C comprise entre 15000 et 50000 mPa.s. Ces compositions liquides d'enduction comprennent également un catalyseur à base de platine et un additif rhéologique constitué par de la silice à haute surface spécifique, en particulier de la silice de combustion. American patent US-4 808 391 relates to inks and varnishes based on silicone, and more precisely a process for applying these inks / varnishes to a substrate, using a roller coating machine operating at high speed. speed. This patent notably discloses compositions comprising polydimethylsiloxanes with vinyl ends having a viscosity at 25 ° C. of between 15,000 and 50,000 mPa.s. These liquid coating compositions also comprise a platinum-based catalyst and a rheological additive consisting of silica with a high specific surface, in particular combustion silica.
Le brevet américain US-6 057 033 divulgue des compositions silicones destinées à être enduites sur des supports flexibles pour former après réticulation par voie cationique sous UV à un revêtement anti-adhérent. En plus des polyorganosiloxanes, ces compositions comprennent des fibres de cellulose ayant une longueur moyenne comprise entre 15 et 100 μm et une épaisseur moyenne comprise entre 5 et 40μm. Les polyorganosiloxanes mis en oeuvre sont des polyorganosiloxanes fonctionnalisés par des groupements de réticulation du type acryloxy ou méthacryloxy, permettant la réticulation par voie radicalaire sous UV. American patent US Pat. No. 6,057,033 discloses silicone compositions intended to be coated on flexible supports to form, after crosslinking by the cationic route under UV, a non-stick coating. In addition to polyorganosiloxanes, these compositions include cellulose fibers having an average length of between 15 and 100 μm and an average thickness of between 5 and 40 μm. The polyorganosiloxanes used are polyorganosiloxanes functionalized by crosslinking groups of the acryloxy or methacryloxy type, allowing crosslinking by radical route under UV.
Les fibres de cellulose incorporées dans la composition permettent d'apporter une solution au problème technique qui est d'obtenir un revêtement silicone anti-adhérent réticulé non cassant. Les fibres de cellulose sont présentées comme procurant des améliorations en ce qui concerne le transfert du film de silicone d'enduction sur le support, la résistance au découpage, les propriétés mécaniques (résistance à la tension et à la déchirure), la fixation du revêtement sur le papier, la diminution de l'absorption du liquide d'enduction au sein du papier, et accessoirement la réduction de la formation de brouillard.  The cellulose fibers incorporated into the composition make it possible to provide a solution to the technical problem which is to obtain a non-brittle crosslinked non-stick silicone coating. Cellulose fibers are presented as providing improvements with regard to the transfer of the coating silicone film onto the support, the cutting resistance, the mechanical properties (tensile and tear resistance), the fixing of the coating. on paper, the reduction in the absorption of coating liquid within the paper, and incidentally the reduction in the formation of mist.
Sur ce dernier point, le brevet US 6 057 033 ne fournit aucun élément quantitatif d'appréciation de la réduction de brouillard entraîné par les fibres cellulosiques. Il y a tout lieu de penser que cette réduction demeure tout à fait insuffisante.  On this last point, US Pat. No. 6,057,033 does not provide any quantitative element for assessing the reduction in fog caused by cellulosic fibers. There is every reason to believe that this reduction remains entirely insufficient.
La demande de brevet WO-0198418 décrit l'utilisation d'un agent antimisting qui est un polyorgosiloxane branché à motif réactif ≡SiH dans une composition de revêtement de silicone. Cet agent anti-misting est obtenu selon un procédé qui consiste à mettre en réaction un grand excès, d'au moins un composé à base d'organohydrogénosilicium contenant au moins trois groupes ≡SiH avec au moins un composé contenant au moins deux groupes alcényle, en présence d'un catalyseur contenant un métal du groupe du platine avec la condition selon laquelle le ratio [nombre de motif réactif≡SiH1:[nombre de motif réactif≡Si-alcénylei > 4,6:1. Patent application WO-0198418 describes the use of an antimisting agent which is a branched polyorgosiloxane with a reactive motif ≡SiH in a silicone coating composition. This anti-misting agent is obtained according to a process which consists in reacting a large excess of at least one organohydrogensilicon-based compound containing at least three ≡SiH groups with at least one compound containing at least two alkenyl groups, in the presence of a catalyst containing a platinum group metal with the condition that the ratio [number of reactive unit≡SiH1: [number of reactive unit≡Si-alkenyli> 4.6: 1.
On citera également pour mémoire la demande de brevet japonais JP-62 64 011 qui décrit un liquide d'enduction contenant une résine filmogène et un solvant et qui contient également des particules de cire de diamètre compris entre 1 et 10μm, le diamètre de la particule la plus grosse étant au plus égale à 150% de l'épaisseur du film humide de revêtement appliqué sur le support. Un tel liquide d'enduction permettrait un accroissement de la vitesse de revêtement d'au moins 10 à 30 m/min, a priori grâce à une limitation de la formation de brouillard. L'enseignement d'un tel document est à écarter car il ne concerne pas les revêtements silicone. Mention will also be made for the record of Japanese patent application JP-62 64 011 which describes a coating liquid containing a film-forming resin and a solvent and which also contains wax particles with a diameter between 1 and 10 μm, the diameter of the particle the largest being at most equal to 150% of the thickness of the wet coating film applied to the support. Such a coating liquid would allow an increase in the coating speed of at least 10 to 30 m / min, a priori thanks to a limitation of the formation of mist. The teaching of such a document should be discarded because it does not concern silicone coatings.
Dans un tel état de la technique, l'un des objectifs essentiels de l'invention est de proposer un procédé efficace de lutte contre l'apparition de brouillard lors de l'enduction de supports flexibles avec une composition silicone liquide précurseur de revêtements réticulés, cette enduction s'opérant à l'aide d'un dispositif d'enduction à cylindre fonctionnant à grande vitesse. Un autre objectif essentiel de l'invention est de proposer un procédé économique et simple de lutte contre l'apparition de brouillard lors de l'enduction de supports flexibles avec une composition silicone destinée à réticuler, cette enduction s'opérant dans un dispositif d'enduction à cylindres fonctionnant à grande vitesse. In such a state of the art, one of the essential objectives of the invention is to propose an effective method of combating the appearance of mist when coating flexible supports with a liquid silicone composition precursor of crosslinked coatings, this coating being carried out using a cylinder coating device operating at high speed. Another essential objective of the invention is to provide an economical and simple method of combating the appearance of fog when coating flexible supports with a silicone composition intended to crosslink, this coating taking place in a device for high speed roller coating.
Un autre objectif essentiel de l'invention est de proposer un procédé d'enduction de supports flexibles à grande vitesse sur cylindres, de matériaux flexibles, au moyen de compositions silicone réticulables en revêtements anti-adhérents, dans lequel la formation de brouillard est réduite. Another essential objective of the invention is to propose a process for coating flexible supports at high speed on cylinders, flexible materials, by means of crosslinkable silicone compositions in non-stick coatings, in which the formation of mist is reduced.
Tous ces objectifs, parmi d'autres, sont atteints par la présente invention qui concerne tout d'abord un procédé de lutte contre l'apparition de brouillard ("misting") lors de l'enduction de supports flexibles comprenant les étapes suivantes : All these objectives, among others, are achieved by the present invention which firstly relates to a method of combating the appearance of mist ("misting") during the coating of flexible supports comprising the following steps:
1 ) la préparation d'une composition silicone liquide X précurseur de revêtement(s) silicone comprenant :  1) the preparation of a liquid silicone composition X precursor of silicone coating (s) comprising:
- au moins un polyorganosiloxane A réticulable par polyaddition, par  at least one polyorganosiloxane A crosslinkable by polyaddition, by
déshydrogénocondensation, par polycondensation, par voie cationique ou par voie radicalaire,dehydrogenocondensation, by polycondensation, by cationic route or by radical route,
- éventuellement au moins un composé organosilicique réticulant B, - optionally at least one crosslinking organosilicon compound B,
- éventuellement au moins un catalyseur ou photoamorceur C dont la nature est choisie suivant le type de réaction envisagée pour ledit polyorganosiloxane A,  optionally at least one catalyst or photoinitiator C, the nature of which is chosen according to the type of reaction envisaged for said polyorganosiloxane A,
- éventuellement, au moins un système modulateur d'adhérence K, et  - optionally, at least one adhesion modulator system K, and
- éventuellement au moins un inhibiteur de réticulation D; et  - optionally at least one crosslinking inhibitor D; and
2) l'enduction de ladite composition silicone liquide X sur un support flexible à l'aide d'un dispositif d'enduction à cylindres,  2) coating said liquid silicone composition X on a flexible support using a roller coating device,
ledit procédé étant caractérisé en ce qu'à l'étape a) on ajoute à ladite composition silicone liquide X un additif anti-brouillard E (additif « antimisting »), qui est : said process being characterized in that in step a) a liquid anti-fog additive E (“antimisting” additive) is added to said liquid silicone composition X, which is:
- un polyorganosiloxane branché L (ou un mélange comprenant au moins un  - a branched polyorganosiloxane L (or a mixture comprising at least one
polyorganosiloxane branché L) porteur d'au moins un motif réactif≡SiH et uniquement sur des motifs de formule : branched polyorganosiloxane L) carrying at least one reactive unit≡SiH and only on units of formula:
M'= HR1R2SiOiZ2 (I) ledit additif anti-brouillard E étant obtenu : M '= HR 1 R 2 SiOiZ 2 (I) said anti-fog additive E being obtained:
a) en faisant réagir, de préférence à une température comprise entre 0°C et 200°C: a) by reacting, preferably at a temperature between 0 ° C and 200 ° C:
- au moins un polyorganosiloxane F, porteur de deux motifs réactifs≡SiH par molécule et de formule brute : - at least one polyorganosiloxane F, carrying two reactive units≡SiH per molecule and of crude formula:
M'Ma DaTbQcM' (II) M'M a D a T b Q c M '(II)
dans laquelle : - a, a', b et c sont des nombres > à 0, et de préférence a', b et c =0, in which : - a, a ', b and c are numbers> to 0, and preferably a', b and c = 0,
- M = R'3R3R4SiOi/2; - M = R ' 3 R 3 R 4 SiOi / 2 ;
- M' = HR3R4SiOiZ2; - M '= HR 3 R 4 SiOiZ 2 ;
- D = R5R6SiO2Z2; - D = R 5 R 6 SiO 2 Z 2 ;
- T = R7SiO3Z2; - T = R 7 SiO 3 Z 2 ;
- Q = SiO4Z2; - Q = SiO 4 Z 2 ;
- avec les symboles R1, R2, R3, R'3, R4, R5, R6 et R7, identiques ou différents, représentent chacun indépendamment l'un de l'autre: - with the symbols R 1 , R 2 , R 3 , R ' 3 , R 4 , R 5 , R 6 and R 7 , identical or different, each represent independently of one another:
- un radical alkyle linéaire ou ramifié contenant 1 à 20 atomes de carbone, éventuellement substitué par au moins un halogène, de préférence le fluor, les radicaux alkyles étant de préférence méthyle, éthyle, propyle, octyle et 3,3,3-trifluoropropyle,  a linear or branched alkyl radical containing 1 to 20 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl,
- un radical cycloalkyle contenant entre 5 et 8 atomes de carbone cycliques,  - a cycloalkyl radical containing between 5 and 8 cyclic carbon atoms,
éventuellement substitué,  possibly substituted,
- un radical aryle contenant entre 6 et 12 atomes de carbone éventuellement substitué, et/ou  - an aryl radical containing between 6 and 12 carbon atoms optionally substituted, and / or
- une partie aralkyle ayant une partie alkyle contenant entre 5 et 14 atomes de carbone et une partie aryle contenant entre 6 et 12 atomes de carbone, substituée éventuellement sur la partie aryle par des halogènes et/ou des alkyles, avec  an aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens and / or alkyls, with
- au moins un polyorganosiloxane G présentant, par molécule, au moins 3 groupes alcényles en C2-C6 liés au silicium en présence : at least one polyorganosiloxane G having, per molecule, at least 3 C 2 -C 6 alkenyl groups linked to silicon in the presence:
- d'au moins un catalyseur de polyaddition H, de préférence le catalyseur polyaddition H est composé d'au moins un métal appartenant au groupe du platine, et  at least one polyaddition catalyst H, preferably the polyaddition catalyst H is composed of at least one metal belonging to the platinum group, and
- d'éventuellement au moins un inhibiteur de réticulation I et/ou au moins un solvant J, la nature et les quantités des composants F et G sont déterminées de manière à ce que le ratio : [nombre de motif réactif≡SiH]:[nombre de motif réactif≡Si-alcényle] >1 :1 et de préférence > 2:1 , et  - optionally at least one crosslinking inhibitor I and / or at least one solvent J, the nature and the amounts of the components F and G are determined so that the ratio: [number of reactive unit≡SiH]: [ number of reactive unit≡Si-alkenyl]> 1: 1 and preferably> 2: 1, and
b) en isolant l'additif anti-brouillard E, éventuellement après élimination du catalyseur de polyaddition H et/ou dévolatilisation et/ou addition d'un inhibiteur de réticulation I'. b) by isolating the anti-fog additive E, optionally after elimination of the polyaddition catalyst H and / or devolatilization and / or addition of a crosslinking inhibitor I '.
II est du mérite des inventeurs d'avoir trouvé, de manière tout à fait surprenante et inattendue, qu'il convient d'utiliser un additif anti-misting E, qui est un polyorganosiloxane branché L (ou un mélange comprenant un ou plusieurs polyorganosiloxanes branchés L) porteur d'au moins un motif réactif≡SiH et uniquement sur des motifs M', pour obtenir un contrôle efficace de la formation de brouillard, ce qui se traduit par une amélioration significative du problème lié à l'apparition dudit brouillard dans un système d'enduction à cylindre fonctionnant à grande vitesse. II est aussi du mérite des inventeurs d'avoir préparé cet additif via une réaction de polyaddition à partir : It is to the credit of the inventors to have found, quite surprisingly and unexpectedly, that it is advisable to use an anti-misting additive E, which is a branched polyorganosiloxane L (or a mixture comprising one or more branched polyorganosiloxanes L) carrying at least one reactive unit ≡SiH and only on units M ′, in order to obtain effective control of the formation of fog, which results in a significant improvement of the problem linked to the appearance of said fog in a cylinder coating system operating at high speed. It is also of the merit of the inventors to have prepared this additive via a polyaddition reaction from:
- d'une huile polyorganosiloxane F terminée en α,ω par des motifs réactifs≡SiH (comprenant ainsi seulement deux motifs réactifs≡SiH), et  a polyorganosiloxane oil F terminated in α, ω by reactive units ≡SiH (thus comprising only two reactive units≡SiH), and
- d'une huile polyorgasiloxane G comprenant au moins trois motifs réactifs≡Si-alcényle, avec la condition selon laquelle la nature et les quantités des composants F et G sont choisies de manière à ce que le ratio [nombre de motif réactif ≡Si HI: [nombre de motif réactif ≡Si-alcénylei >1 :1. En effet, il existait un préjugé technique selon la demande de brevet WO-0198418 précité, qui expose qu'un additif anti-misting doit être préparé via une réaction de polyaddition à partir : - a polyorgasiloxane oil G comprising at least three reactive units ≡Si-alkenyl, with the condition that the nature and the amounts of components F and G are chosen so that the ratio [number of reactive unit ≡Si HI : [number of reactive unit ≡Si-alkenyli> 1: 1. Indeed, there was a technical prejudice according to the aforementioned patent application WO-0198418, which states that an anti-misting additive must be prepared via a polyaddition reaction from:
- d'un large excès d'une huile polyorganosiloxane contenant au moins trois groupes≡SiH, et - a large excess of a polyorganosiloxane oil containing at least three ≡SiH groups, and
- d'une huile polyorgasiloxane comprenant au moins deux motifs réactifs≡Si-alcényle, a polyorgasiloxane oil comprising at least two reactive units ≡Si-alkenyl,
avec la condition selon laquelle le ratio [nombre de motif réactif≡SiH]:[nombre de motif réactif≡Si- alcénylei > 4,6:1. with the condition that the ratio [number of reactive unit≡SiH]: [number of reactive unit≡Si- alkenyli> 4.6: 1.
Ainsi le choix judicieux des réactifs F et G selon l'invention pour préparer l'agent anti- misting E selon l'invention permet de s'affranchir de la condition enseignée par la référence WO- 0198418 précitée selon laquelle le ratio : Thus, the judicious choice of reagents F and G according to the invention for preparing the anti-misting agent E according to the invention makes it possible to overcome the condition taught by the reference WO-0198418 mentioned above, according to which the ratio:
[≡SiH]:[≡Si-alcényle] > 4,6:1. [≡SiH]: [≡Si-alkenyl]> 4.6: 1.
Les conditions définis dans le mode de préparation de l'additif anti-brouillard E (additif « antimisting »), permet d'obtenir un additif présentant des propriétés anti-brouillard en tout point remarquable. Sans vouloir se limiter à une théorie scientifique ou à un mécanisme, il semble que cette propriété est due à la présence de(s) polymère(s) branché(s) L selon l'invention dont les propriétés viscoélastiques permettent de lutter contre l'apparition de brouillard dans un système d'enduction à cylindre fonctionnant à grande vitesse. L'additif anti-brouillard E selon l'invention est mis en œuvre dans des quantités suffisantes pour réduire la quantité de misting lors de l'enduction. Bien entendu l'homme de métier, par des essais de routine, peut déterminer sans difficulté ces quantités. Par exemple, il peut mettre en œuvre l'additif selon l'invention dans des quantités comprises entre, 0,1 à 15 parties en poids par rapport au poids total de la composition silicone liquide X précurseur de revêtement(s) silicone. The conditions defined in the method of preparation of the anti-fog additive E (“antimisting” additive) makes it possible to obtain an additive having anti-fog properties in all remarkable respects. Without wishing to be limited to a scientific theory or to a mechanism, it seems that this property is due to the presence of branched polymer (s) L according to the invention whose viscoelastic properties make it possible to combat the appearance of fog in a cylinder coating system operating at high speed. The anti-fog additive E according to the invention is used in quantities sufficient to reduce the amount of misting during coating. Of course, the skilled person, by routine tests, can easily determine these quantities. For example, it can use the additive according to the invention in quantities of between 0.1 and 15 parts by weight relative to the total weight of the liquid silicone composition X silicone coating precursor (s).
Selon un mode de réalisation avantageux du procédé selon l'invention, le polyorganosiloxane G présente :  According to an advantageous embodiment of the process according to the invention, the polyorganosiloxane G has:
a) par molécule, au moins 3 groupes alcényles en C2-C6 liés au silicium, b) des motifs de formule : a) per molecule, at least 3 C 2 -C 6 alkenyl groups linked to silicon, b) reasons for the formula:
dans laquelle :  in which :
- X est un groupe alcényle en C2-C6, - X is a C 2 -C 6 alkenyl group,
- Z est un groupe hydrocarboné monovalent, exempt d'action défavorable sur l'activité du catalyseur et choisi parmi les groupes alkyles ayant de 1 à 8 atomes de carbone inclus, éventuellement substitués par au moins un atome d'halogène, et ainsi que parmi les groupes aryles,  - Z is a monovalent hydrocarbon group, free from any unfavorable action on the activity of the catalyst and chosen from alkyl groups having from 1 to 8 carbon atoms included, optionally substituted by at least one halogen atom, and also from aryl groups,
- d est O, 1 ou 2, et  - d is O, 1 or 2, and
-c) éventuellement au moins une partie des autres motifs sont des motifs de formule moyenne : -c) optionally at least part of the other motifs are motifs of medium formula:
dans laquelle Z a la même signification que ci-dessus et e a une valeur comprise entre in which Z has the same meaning as above and e has a value between
0 et 3. 0 and 3.
Les polyorganosiloxanes F et G peuvent réagir entre eux selon un mécanisme connu de polyaddition, qui mène à la réticulation de la composition silicone. On peut d'ailleurs utiliser un catalyseur de polyaddition H, de préférence le catalyseur polyaddition H est composé d'au moins un métal appartenant au groupe du platine. Ce catalyseur peut notamment être choisi parmi les composés du platine et du rhodium. On peut, en particulier, utiliser les complexes du platine et d'un produit organique décrit dans les brevets US-A-3 159 601 , US-A-3 159 602, US-A-3 220 972 et les brevets européens EP-A-O 057 459, EP-A-O 188 978 et EP-A-O 190 530, les complexes du platine et d'organosiloxanes vinylés décrits dans les brevets US-A-3 419 593, US-A-3 715 334, US-A-3 377 432 et US-A-3 814 730. Le catalyseur généralement préféré est le platine. Dans ce cas, la quantité pondérale du catalyseur de polyaddition H, calculée en poids de platine-métal, est généralement comprise entre 2 et 400 ppm, de préférence entre 5 et 300 ppm basés sur le poids total des polyorganosiloxanes F et G. Polyorganosiloxanes F and G can react with each other according to a known polyaddition mechanism, which leads to crosslinking of the silicone composition. It is also possible to use a polyaddition catalyst H, preferably the polyaddition catalyst H is composed of at least one metal belonging to the platinum group. This catalyst can in particular be chosen from platinum and rhodium compounds. It is possible, in particular, to use the complexes of platinum and of an organic product described in patents US-A-3,159,601, US-A-3,159,602, US-A-3,220,972 and European patents EP- AO 057 459, EP-AO 188 978 and EP-AO 190 530, the platinum and vinyl organosiloxane complexes described in patents US-A-3,419,593, US-A-3,715,334, US-A-3 377,432 and US-A-3,814,730. The generally preferred catalyst is platinum. In this case, the quantity by weight of the polyaddition catalyst H, calculated by weight of platinum metal, is generally between 2 and 400 ppm, preferably between 5 and 300 ppm based on the total weight of the polyorganosiloxanes F and G.
Concernant les polyorganosiloxanes A de la composition silicone liquide X précurseur de revêtement(s) silicone, ils peuvent être du type de ceux qui réticulent à température ambiante ou à la chaleur par des réactions de polyaddition en présence d'un catalyseur métallique en l'occurrence à base de platine. Ce sont des compositions de polyorganosiloxanes réticulables appelées RTV ("Room Température Vulcanising") ou des compositions polyorganosiloxaniques de polyaddition dénommées EVC qui est l'abréviation de "élastomère vulcanisable à chaud". Les compositions polyorganosiloxaniques bicomposantes ou monocomposantes RTV ou EVC de polyaddition, durcissent ou réticulent essentiellement par des réaction de groupements hydrogénosilylés sur des groupements alkényles silylés, en présence généralement d'un catalyseur métallique (de préférence au platine). Elles sont décrites par exemple dans les brevets US-3 220 972, 3 284 406, 3 436 366, 3 697 473 et 4 340 709. Concerning the polyorganosiloxanes A of the liquid silicone composition X silicone coating precursor (s), they can be of the type which crosslink at room temperature or with heat by polyaddition reactions in the presence of a metal catalyst in this case based on platinum. These are crosslinkable polyorganosiloxane compositions called RTV ("Room Temperature Vulcanising") or polyorganosiloxane polyaddition compositions called EVC which is the abbreviation for "hot vulcanizable elastomer". The polyaddition or monocomponent RTV or EVC polyaddition polyorganosiloxane compositions harden or crosslink essentially by reaction of hydrogenosilylated groups on silylated alkenyl groups, generally in the presence of a metal catalyst (preferably platinum). They are described for example in US Patents 3,220,972, 3,284,406, 3,436,366, 3,697,473 and 4,340,709.
Les polyorganosiloxanes A peuvent aussi être du type de ceux qui réticulent à température ambiante par des réactions de polycondensation sous l'action de l'humidité, en présence généralement d'un catalyseur métallique, par exemple un composé de l'étain (RTV polycondensation). Les compositions mettant en œuvre ce type de polyorganosiloxane sont décrites par exemple dans les brevets US-3 065 194, 3 542 901 , 3 779 986, 4 417 042 et dans le brevet FR-2 638 752 (compositions monocomposante) et dans les brevets US-3 678 002, 3 888 815, 3 933 729 et 4 064 096 (compositions bicomposante). Polyorganosiloxanes A can also be of the type which crosslink at room temperature by polycondensation reactions under the action of moisture, generally in the presence of a metal catalyst, for example a tin compound (RTV polycondensation) . The compositions using this type of polyorganosiloxane are described for example in US Patents 3,065,194, 3,542,901, 3,779,986, 4,417,042 and in Patent FR-2,638,752 (single-component compositions) and in patents US-3,678,002, 3,888,815, 3,933,729 and 4,064,096 (two-component compositions).
Les polyorganosiloxanes A qui entrent dans ces compositions RTV polycondensation sont des polysiloxanes linéaires ramifiés ou réticulés porteurs de groupements hydroxyle ou de groupements hydrolysables par exemple alcoxy. De pareilles compositions peuvent contenir en outre un agent de réticulation, qui est, notamment, un composé portant au moins 3 groupements hydrolysables comme par exemple un silicate, un alkyltrialcoxysilane ou un aminoalkyle trialcoxysilane. The polyorganosiloxanes A which enter into these polycondensation RTV compositions are linear branched or crosslinked polysiloxanes carrying hydroxyl groups or hydrolysable groups, for example alkoxy. Such compositions may also contain a crosslinking agent, which is, in particular, a compound carrying at least 3 hydrolysable groups such as for example a silicate, an alkyltrialkoxysilane or an aminoalkyl trialkoxysilane.
La composition silicone liquide X peut également comprendre un ou plusieurs polyorganosiloxanes A réticulables par voie cationique ou radicalaire : The liquid silicone composition X can also comprise one or more polyorganosiloxanes A crosslinkable by cationic or radical route:
- en présence d'une quantité efficace de systèmes amorceurs cationiques (amorceurs thermiques et/ou photoamorceurs) - les amorceurs du type borate d'onium ou de complexes organo- métalliques, les solvants organiques donneurs de protons (alcool isopropylique, alcool benzylique,..), et/ou  - in the presence of an effective quantity of cationic initiator systems (thermal initiators and / or photoinitiators) - initiators of the onium borate type or of organometallic complexes, organic solvents donating protons (isopropyl alcohol, benzyl alcohol ,. .), and or
- selon le cas en présence d'un initiateur radicalaire, par l'intermédiaire d'une activation par rayonnement actinique (UV) ou par faisceaux d'électrons.  - as the case may be, in the presence of a radical initiator, via activation by actinic radiation (UV) or by electron beams.
Ces polyorganosiloxanes sont par exemple des époxysilicones et/ou des These polyorganosiloxanes are for example epoxysilicones and / or
vinyléthersilicones, linéaires ou cycliques. De tels polyorganosiloxanes époxy ou vinyl ethersilicones, linear or cyclic. Such epoxy polyorganosiloxanes or
vinyloxyfonctionnels sont décrits notamment dans les brevets DE-4 009 889, EP-O 396 130, EP- 0 355 381 , EP-O 105 341 , FR-2 1 10 115, FR-2 526 800. Vinyloxyfunctional are described in particular in patents DE-4,009,889, EP-0 396 130, EP-0 355 381, EP-O 105 341, FR-2 1 10 115, FR-2 526 800.
Les polyorganosiloxanes époxy fonctionnels peuvent être préparés par réactions d'hydrosylylation entre des huiles à motifs≡SiH et des composés époxy-fonctionnels tels que le vinyl-4-cyclohexenone ou allyl- glycidyléther. Les polyorganosiloxanes vinyloxyfonctionnels peuvent être préparés par réaction d'hydrosilylation entre des huiles à motifs SiH et des composés vinyloxyfonctionnels tels que l'aHylvinyléther ou l'allyl- vinyloxyéthoxybenzène. The functional epoxy polyorganosiloxanes can be prepared by hydrosylylation reactions between oils with ≡SiH units and epoxy-functional compounds such as vinyl-4-cyclohexenone or allyl-glycidyl ether. The vinyloxyfunctional polyorganosiloxanes can be prepared by hydrosilylation reaction between oils having SiH units and vinyloxyfunctional compounds such as aHylvinylether or allylvinyloxyethoxybenzene.
L'inhibiteur de réticulation D est en général utilisé pour conférer à la composition prête à l'emploi, une certaine durée de vie en pot (« pot-life »). En jouant d'une part sur la nature de l'ensemble catalytique et sur sa concentration dans la composition (dont il découle une vitesse de réticulation donnée) et d'autre part sur la nature du retardateur et sur sa concentration, il est possible d'ajuster la durée de vie en pot. L'activité de l'ensemble catalytique est restituée par chauffage (thermoactivation). Le retardateur est de préférence choisi parmi les alcools The crosslinking inhibitor D is generally used to give the ready-to-use composition a certain pot life ("pot-life"). By playing on the one hand on the nature of the catalytic assembly and on its concentration in the composition (from which it results a given crosslinking speed) and on the other hand on the nature of the retarder and on its concentration, it is possible to 'adjust the pot life. The activity of the catalytic assembly is restored by heating (thermoactivation). The retarder is preferably chosen from alcohols
acétyléniques (éthynylcyclohexanol : ECH) et/ou les diallylmaléates et/ou les triallylisocyanurates et/ou les dialkylmaléates (diéthylmaléates et/ou les dialkylalcinyledicarboxylat.es)  acetylenics (ethynylcyclohexanol: ECH) and / or diallylmaleates and / or triallylisocyanurates and / or dialkylmaleates (diethylmaleates and / or dialkylalcinyledicarboxylates)
(diéthyleacéthylène dicarboxylate) ou bien encore parmi les polyorganosiloxanes,  (diethyleacethylene dicarboxylate) or even among polyorganosiloxanes,
avantageusement cycliques et substitués par au moins un alcényle, le  advantageously cyclic and substituted with at least one alkenyl, the
I tétraméthylvinylcyxlotétrasiloxane étant particulièrement préféré, ou les maléates alkylés.  I tetramethylvinylcyxlotetrasiloxane being particularly preferred, or alkylated maleates.
Les alcools acétyléniques (voir par exemple FR-B-1 528 464 et FR-A-2 372 874) sont des retardateurs utiles selon l'invention. On peut citer à titre d'exemples :  Acetylenic alcohols (see for example FR-B-1,528,464 and FR-A-2,372,874) are useful retarders according to the invention. As examples, we can cite:
. l'éthynyl-1-cyclohexanol 1 ;  . ethynyl-1-cyclohexanol 1;
. le méthyl-3 dodécyne-1 ol-3 ;  . 3-methyl-dodecy-1 ol-3;
. le triméthyl-3,7,1 1 dodécyne-1 ol-3 ;  . trimethyl-3,7,1 1 dodecy-1 ol-3;
. le diphényl-1 ,1 propyne-2 ol-1 ;  . diphenyl-1, 1 propyne-2 ol-1;
. l'éthyl-3 éthyl-6 nonyne-1 ol-3 ;  . 3-ethyl-6-ethyl nonyne-1 ol-3;
. le méthyl-3 pentadécyne-1 ol-3.  . 3-methyl-pentadecyne-1 ol-3.
Ces alcools α-acétyléniques sont des produits du commerce.  These α-acetylenic alcohols are commercial products.
Comme autres exemples de retardateurs utiles selon l'invention on peut citer les dérivés phosphiniques par exemple le tris-(2,4-di-tert- butylphényl) phosphite (commercialisé par la société CIBA sous la référence lrgafos-168®) ou ceux décrits dans la demande de brevet internationale WO2004/061003 et notamment le composé Irgafos® P-EPQ de formule : As other examples of retarders which are useful according to the invention, mention may be made of phosphinic derivatives, for example tris- (2,4-di-tert-butylphenyl) phosphite (sold by the company CIBA under the reference lrgafos-168 ® ) or those described in the international patent application WO2004 / 061003 and in particular the Irgafos ® P-EPQ compound of the formula:
Un tel retardateur est notamment présent à raison de 1-100 équivalent molaire/métal du système catalytique. Such a retarder is in particular present at a rate of 1-100 molar / metal equivalent of the catalytic system.
Les inhibiteurs de réticulation I et I' envisagés pour le procédé selon l'invention sont par exemple, ceux décrits pour l'inhibiteur D. De préférence, I' est le tris-(2,4-di-tert- butylphényl) phosphite (commercialisé par la société CIBA sous la référence lrgafos-168®). The crosslinking inhibitors I and I 'envisaged for the process according to the invention are, for example, those described for the inhibitor D. Preferably, I' is tris- (2,4-di-tert-butylphenyl) phosphite ( marketed by the company CIBA under the reference lrgafos-168 ® ).
Dans la composition silicone liquide X précurseur de revêtement(s) silicone, il peut-être avantageux de mettre en oeuvre au moins un système modulateur d'adhérence K, pour permettre le contrôle des propriétés anti-adhérence du revêtement silicone réticulé. In the liquid silicone composition X precursor of silicone coating (s), it may be advantageous to use at least one adhesion modulating system K, to allow control of the anti-adhesion properties of the crosslinked silicone coating.
A titre d'illustration de système modulateur d'adhérence dans des formulations silicones pour anti-adhérence papier ou ruban adhésif ayant un support polymère, on peut citer la demande de brevet européen EP-A-O 601 938, dont le contenu est intégralement inclus dans le présent exposé.  By way of illustration of an adhesion modulator system in silicone formulations for paper or adhesive non-sticking having a polymer support, mention may be made of European patent application EP-AO 601 938, the content of which is fully included in the this presentation.
Selon une variante, le système modulateur d'adhérence K est : According to a variant, the adhesion modulator system K is:
- dans le cas d'une formulation réticulant par polyaddition : une résine polyorganosiloxane de formule MDV|Q ; MMV|Q ; MMV|DV|Q ; MMV|DDV|Q ; MDHQ ou MMHQ, - in the case of a crosslinking formulation by polyaddition: a polyorganosiloxane resin of formula MD V | Q; MM V | Q; MM V | D V | Q; MM V | DD V | Q; MD H Q or MM H Q,
- dans le cas d'une formulation réticulant par polycondensation : une résine polyorganosiloxane de formule MOHQ, et - in the case of a crosslinking formulation by polycondensation: a polyorganosiloxane resin of formula M OH Q, and
- dans le cas d'une formulation réticulant sous rayonnement : une résine polyorganosiloxane de formule MD'Q ou MM'Q.  - in the case of a crosslinking formulation under radiation: a polyorganosiloxane resin of formula MD'Q or MM'Q.
A titre d'exemples de diluant et/ou de solvant J, J' et J" on peut citer, les solvants aliphatiques, aromatiques, les solvants chlorés, e.g. : white spirit, les cétones telles que la méthyléthylcétone et l'acétone, les alcools tels que l'isopropanol et l'alcool n-butylique, les hydrocarbures saturés, insaturés ou aromatiques, avantageusement le pentane, l'hexane, l'heptane, l'octane, le toluène, le xylène, le benzène, les coupes pétrolières "naphtas"; les coupes pétrolières en C7-C8, les hydrocarbures halogènes et leurs mélanges. As examples of diluent and / or solvent J, J ′ and J ", mention may be made of aliphatic and aromatic solvents, chlorinated solvents, eg: white spirit, ketones such as methyl ethyl ketone and acetone, alcohols such as isopropanol and n-butyl alcohol, saturated, unsaturated or aromatic hydrocarbons, advantageously pentane, hexane, heptane, octane, toluene, xylene, benzene, "naphtha" petroleum fractions; C 7 -C 8 petroleum fractions, halogenated hydrocarbons and their mixtures.
Selon une variante préférée du procédé selon l'invention, la composition silicone liquide X précurseur de revêtement(s) silicone à laquelle on ajoute l'additif anti-brouillard E (« antimisting ») comprend : According to a preferred variant of the process according to the invention, the liquid silicone composition X silicone coating precursor (s) to which the anti-fog additive E (“antimisting”) is added comprises:
- au moins un polyorganosiloxane A réticulable par polyaddition,  at least one polyorganosiloxane A crosslinkable by polyaddition,
- éventuellement au moins un composé organosilicique réticulant B,  - optionally at least one crosslinking organosilicon compound B,
- au moins un catalyseur C1 de la réaction de polyaddition;  - At least one catalyst C1 of the polyaddition reaction;
- éventuellement au moins un système modulateur d'adhérence K, et  - optionally at least one adhesion modulator system K, and
- éventuellement au moins un inhibiteur de réticulation D;  - optionally at least one crosslinking inhibitor D;
Le catalyseur C1 peut-être choisi parmi les composés définis pour le catalyseur de polyaddition H décrit ci-dessus. The catalyst C1 can be chosen from the compounds defined for the polyaddition catalyst H described above.
Selon cette variante préférée, le polyorganosiloxane A réticulable par polyaddition présente des motifs de formule (Vl) et éventuellement au moins une partie des autres motifs sont des motifs de formule moyenne (VII): According to this preferred variant, the polyorganosiloxane A crosslinkable by polyaddition has units of formula (Vl) and optionally at least a portion of the other units are units of medium formula (VII):
WaYb Si0ii2^> (Vl) W a Y b Si0ii2 ^> (Vl)
2  2
Yc SiOiH (VII) Yc SiOiH (VII)
2  2
formules dans lesquelles : formulas in which:
W est un groupe alcényle, de préférence vinyle ou allyle,  W is an alkenyl group, preferably vinyl or allyl,
- les symboles Y, identiques ou différents, représentent :  - the symbols Y, identical or different, represent:
- un radical alkyle linéaire ou ramifié contenant 1 à 20 atomes de carbone, éventuellement substitué par au moins un halogène, de préférence le fluor, les radicaux alkyles étant de préférence méthyle, éthyle, propyle, octyle et 3,3,3- trifluoropropyle,  a linear or branched alkyl radical containing 1 to 20 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl,
- un radical cycloalkyle contenant entre 5 et 8 atomes de carbone cycliques, éventuellement substitué,  - a cycloalkyl radical containing between 5 and 8 cyclic carbon atoms, optionally substituted,
- un radical aryle contenant entre 6 et 12 atomes de carbone éventuellement substitué, et/ou  - an aryl radical containing between 6 and 12 carbon atoms optionally substituted, and / or
- une partie aralkyle ayant une partie alkyle contenant entre 5 et 14 atomes de carbone et une partie aryle contenant entre 6 et 12 atomes de carbone, substituée éventuellement sur la partie aryle par des halogènes et/ou des alkyles. a est 1 ou 2, de préférence égal à 1 , b est 0, 1 ou 2 et a + b = 1 , 2 ou 3, et - c = 0, 1 , 2 ou 3. - An aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens and / or alkyls. a is 1 or 2, preferably equal to 1, b is 0, 1 or 2 and a + b = 1, 2 or 3, and - c = 0, 1, 2 or 3.
Des exemples de polyorganosiloxanes A réticulable par polyaddition sont les diméthylpolysiloxanes à extrémités diméthylvinylsilyle, les copolymères Examples of polyorganosiloxanes A which can be crosslinked by polyaddition are dimethylpolysiloxanes with dimethylvinylsilyl ends, copolymers
méthylvinyldiméthylpolysiloxanes à extrémités triméthylsilyle, les copolymères methylvinyldimethylpolysiloxanes with trimethylsilyl ends, the copolymers
méthylvinyldiméthylpolysiloxanes à extrémités diméthylvinylsilyle. methylvinyldimethylpolysiloxanes with dimethylvinylsilyl ends.
Le composé organosilicique réticulant B est de préférence du type de ceux présentant des motifs de formule (VIII) et éventuellement au moins une partie des autres motifs sont des motifs de formule moyenne (IX): The crosslinking organosilicon compound B is preferably of the type of those having units of formula (VIII) and optionally at least part of the other units are units of average formula (IX):
H Lc Si0(3-c)/2 (VIII) HL c Si0 (3 -c) / 2 (VIII)
Lg Si0(4-g)/2 (IX) L g Si0 ( 4 -g) / 2 (IX)
dans lesquelles : in which :
- les symboles L, identiques ou différents, représentent :  - the symbols L, identical or different, represent:
- un radical alkyle linéaire ou ramifié contenant 1 à 20 atomes de carbone, éventuellement substitué par au moins un halogène, de préférence le fluor, les radicaux alkyles étant de préférence méthyle, éthyle, propyle, octyle et 3,3,3- trifluoropropyle,  a linear or branched alkyl radical containing 1 to 20 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl,
- un radical cycloalkyle contenant entre 5 et 8 atomes de carbone cycliques, éventuellement substitué,  - a cycloalkyl radical containing between 5 and 8 cyclic carbon atoms, optionally substituted,
- un radical aryle contenant entre 6 et 12 atomes de carbone éventuellement substitué, et/ou  - an aryl radical containing between 6 and 12 carbon atoms optionally substituted, and / or
- une partie aralkyle ayant une partie alkyle contenant entre 5 et 14 atomes de carbone et une partie aryle contenant entre 6 et 12 atomes de carbone, substituée éventuellement sur la partie aryle par des halogènes et/ou des alkyles,  an aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens and / or alkyls,
- c = 0, 1 ou 2, et  - c = 0, 1 or 2, and
- g= 0, 1 , 2 ou 3.  - g = 0, 1, 2 or 3.
Des exemples de composé organosilicique réticulant B sont, par exemple, :Examples of crosslinking organosilicon compound B are, for example:
- les polymères diméthylpolysiloxane à extrémités hydrogénodiméthylsilyle, - dimethylpolysiloxane polymers with hydrogenodimethylsilyl ends,
- les polymères poly(diméthylsiloxane) (méthylhydrogénosiloxy) α,ω-diméthylhydrogéno- siloxane,  - poly (dimethylsiloxane) (methylhydrogensiloxy) α, ω-dimethylhydrogenosiloxane polymers,
- MDD' : les copolymères à motifs diméthyl-hydrogénométhylpolysiloxanes (diméthyl) à extrémités triméthylsilyle, - M'DD' : les copolymères à motifs diméthyl-hydrogénométhylpolysiloxanes à extrémités hydrogénodiméthylsilyle, - MDD ': copolymers with dimethyl-hydrogenomethylpolysiloxane (dimethyl) units with trimethylsilyl ends, - M'DD ': copolymers with dimethyl-hydrogenomethylpolysiloxane units with hydrogenodimethylsilyl ends,
- MD' : les hydrogénométhylpolysiloxanes à extrémités triméthylsilyle.  - MD ': hydrogenomethylpolysiloxanes with trimethylsilyl ends.
Outre ces constituants, la composition silicone liquide X précurseur de revêtement(s) silicone peut également contenir au moins un additif courant dans les compositions silicone réticulant par polyaddition, par polycondensation, par voie cationique ou par voie radicalaire. On peut citer par exemple, les pigments,... In addition to these constituents, the liquid silicone composition X silicone coating precursor (s) can also contain at least one additive which is common in silicone compositions which crosslink by polyaddition, by polycondensation, by cationic route or by radical route. We can cite for example, pigments, ...
Selon un autre mode de réalisation avantageux, le polyorganosiloxane branché L a comme formule brute moyenne: According to another advantageous embodiment, the branched polyorganosiloxane L has as an average crude formula:
Mf Dg (Malk)h (Dalk)i Tk Qm (lvV)n (V) M f D g (M alk ) h (D alk ) i T k Q m (lvV) n (V)
avec: with:
- f, g, i, k et m > 0,  - f, g, i, k and m> 0,
- h et m > 0,  - h and m> 0,
- M' = HR8R9SiOiZ2; - M '= HR 8 R 9 SiOiZ 2 ;
- Malk = RR10R11SiOiZ2 - M alk = RR 10 R 11 SiOiZ 2
- Dalk = RR12SiO2Z2 - D alk = RR 12 SiO 2Z2
- D = R13R14SiO2Z2; - D = R 13 R 14 SiO 2 Z 2 ;
- T = R15SiO3Z2; - T = R 15 SiO 3 Z 2 ;
- Q = SiO4Z2; - Q = SiO 4 Z 2 ;
- avec :  - with:
- le symbole R (rotule alkyle du polymère branché) est un groupe alkyle en C2-C6, etthe symbol R (alkyl patella of the connected polymer) is a C 2 -C 6 alkyl group, and
- les symboles R8, R9, R10, R11, R12, R13, R14 et R15, identiques ou différents, représentent chacun indépendamment l'un de l'autre: - the symbols R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 , identical or different, each represent independently of one another:
- un radical alkyle linéaire ou ramifié contenant 1 à 20 atomes de carbone, éventuellement substitué par au moins un halogène, de préférence le fluor, les radicaux alkyles étant de préférence méthyle, éthyle, propyle, octyle et 3,3,3-trifluoropropyle,  a linear or branched alkyl radical containing 1 to 20 carbon atoms, optionally substituted with at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl,
- un radical cycloalkyle contenant entre 5 et 8 atomes de carbone cycliques,  - a cycloalkyl radical containing between 5 and 8 cyclic carbon atoms,
éventuellement substitué,  possibly substituted,
- un radical aryle contenant entre 6 et 12 atomes de carbone éventuellement substitué, et/ou  - an aryl radical containing between 6 and 12 carbon atoms optionally substituted, and / or
- une partie aralkyle ayant une partie alkyle contenant entre 5 et 14 atomes de carbone et une partie aryle contenant entre 6 et 12 atomes de carbone, substituée éventuellement sur la partie aryle par des halogènes et/ou des alkyles. Selon une variante préférée de l'invention, la composition silicone liquide X précurseur de revêtement(s) silicone à laquelle on ajoute l'additif anti-brouillard E (« antimisting ») selon l'invention, comprend : - An aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens and / or alkyls. According to a preferred variant of the invention, the liquid silicone composition X silicone coating precursor (s) to which the anti-fog additive E (“antimisting”) according to the invention is added, comprises:
- au moins un polyorganosiloxane A réticulable par polyaddition,  at least one polyorganosiloxane A crosslinkable by polyaddition,
- au moins un composé organosilicique réticulant B,  - at least one crosslinking organosilicon compound B,
- au moins un catalyseur C1 de la réaction de polyaddition;  - At least one catalyst C1 of the polyaddition reaction;
- éventuellement au moins un système modulateur d'adhérence K, et  - optionally at least one adhesion modulator system K, and
- éventuellement au moins un inhibiteur de réticulation D.  - optionally at least one crosslinking inhibitor D.
Un autre objet de l'invention concerne une utilisation de l'additif anti-brouillard E tel que défini ci-dessus pour réduire l'apparition de brouillard ("misting") lors de l'enduction de supports flexibles avec une composition silicone liquide X précurseur de revêtement(s) silicone telle que définie selon l'une quelconque des revendications précédentes. Another object of the invention relates to the use of the anti-fog additive E as defined above to reduce the appearance of mist ("misting") when coating flexible supports with a liquid silicone composition X silicone coating precursor as defined in any one of the preceding claims.
Le dernier objet de l'invention concerne un procédé d'enduction de supports flexibles avec au moins une composition silicone liquide X précurseur de revêtement(s) silicone telle que définie ci-dessus, cette enduction s'effectuant à l'aide d'un dispositif d'enduction à cylindres, caractérisé en ce que l'on a recours au procédé de lutte contre l'apparition de brouillard ("misting") selon l'invention. The last object of the invention relates to a method of coating flexible supports with at least one liquid silicone composition X precursor of silicone coating (s) as defined above, this coating being carried out using a roller coating device, characterized in that the method of combating the appearance of mist ("misting") according to the invention is used.
II apparaît donc que l'invention propose un moyen original simple, économique et fiable de lutte contre la production de brouillard lors de l'enduction de supports flexibles (par exemple en papier, en film ou en film polymère) dans des dispositifs d'enduction à cylindre fonctionnant à grande vitesse. La conséquence industrielle pratique est que les vitesses de défilement peuvent encore être augmentées sans qu'apparaisse ce phénomène de brouillard nuisible à la qualité de l'enduction. Le moyen de lutte proposé par l'invention a également pour avantage non négligeable de ne pas nuire aux qualités d'aspect, à la couverture, aux propriétés d'anti-adhérence, ainsi qu'aux propriétés mécaniques (rub-off) du revêtement réticulé silicone que l'on cherche à obtenir sur au moins une des faces du support flexible. Par ailleurs, la réduction du misting améliore de façon significative les conditions d'hygiène et de sécurité pour le personnel en poste auprès de dispositifs industriels d'enduction silicone sur cylindres fonctionnant à grande vitesse. Les exemples, qui suivent ont pour vocation d'illustrer des modes de réalisation particuliers de 'invention sans pour autant limiter la portée de l'invention à ces simples modes de réalisations. It therefore appears that the invention provides an original simple, economical and reliable means of combating the production of mist when coating flexible supports (for example paper, film or polymer film) in coating devices. with cylinder operating at high speed. The practical industrial consequence is that the running speeds can be further increased without the appearance of this phenomenon of fog detrimental to the quality of the coating. The control means proposed by the invention also has the non-negligible advantage of not affecting the appearance qualities, the coverage, the anti-adhesion properties, as well as the mechanical properties (rub-off) of the coating. crosslinked silicone that is sought to be obtained on at least one of the faces of the flexible support. In addition, the reduction in misting significantly improves the health and safety conditions for personnel working with industrial silicone coating devices on cylinders operating at high speed. The examples which follow are intended to illustrate particular embodiments of the invention without limiting the scope of the invention to these simple embodiments.
EXEMPLES EXAMPLES
I) Préparation des additifs anti-brouillard E : I) Preparation of anti-fog additives E:
Exemple 1 : Example 1:
Sous atmosphère inerte, on charge 40 g de toluène et 14 mg d'une solution de Pt de Karsted à 10-12% de Pt. Le mélange est chauffé et agité à 85 °C puis 51 g d'une huile  40 g of toluene and 14 mg of a Karsted Pt solution containing 10-12% Pt are charged under an inert atmosphere. The mixture is heated and stirred at 85 ° C. and then 51 g of an oil.
poly(diméthylsiloxane) bloquée à chacune des extrémités des chaînes par un motif (CH3)2HSiOi/2, (contenant 0.2 équivalents de≡SiH pour 100 g) et 49 g d'une huile polyorganosiloxane alcénylée (0.035 équivalents de≡SiVi pour 100g) sont co-coulés en 2 heures sur la solution de catalyseur. Le milieu réactionnel est chauffé pendant 3h supplémentaires à 85 °C. Après « stripping » des volatiles, l'huile silicone branchée obtenue a une viscosité de 2300 mm2/s et contient 0.085 équivalents de≡SiH pour 100g. poly (dimethylsiloxane) blocked at each end of the chains by a motif (CH 3 ) 2 HSiOi / 2 , (containing 0.2 equivalents of ≡SiH per 100 g) and 49 g of an alkenylated polyorganosiloxane oil (0.035 equivalents of ≡SiVi for 100g) are co-poured over 2 hours onto the catalyst solution. The reaction medium is heated for an additional 3 hours at 85 ° C. After “stripping” the volatiles, the branched silicone oil obtained has a viscosity of 2300 mm2 / s and contains 0.085 equivalents of ≡SiH per 100g.
Exemple 2 : Example 2:
Sous atmosphère inerte, on charge 40 g de toluène et 14 mg d'une solution de Pt de Karsted à 10-12% de Pt. Le mélange est chauffé et agité à 85 °C puis 51.6 g d'une huile silicone α,ω-SiH ≡SiH (contenant 0.2 équivalents de≡SiH pour 100g) et 48.4 g d'une huile silicone à motifs≡SiVi pendants et terminaux (0.036 équivalents de≡SiVi pour 100g) sont co-coulés en 2 heures sur la solution de catalyseur. Le milieu réactionnel est chauffé pendant encore 2 h à 85 °C jusqu'à un taux complet de transformation des motifs≡SiVi. Après « stripping » des volatiles, l'huile silicone branchée obtenue a une viscosité de 283 mm2/s et contient 0.081 équivalents de≡SiH pour 100g. 40 g of toluene and 14 mg of a Karsted Pt solution containing 10-12% Pt are charged under an inert atmosphere. The mixture is heated and stirred at 85 ° C. then 51.6 g of a silicone oil α, ω -SiH ≡SiH (containing 0.2 equivalents of ≡SiH per 100g) and 48.4 g of a silicone oil with pendant and terminal ≡SiVi patterns (0.036 equivalents of≡SiVi per 100g) are co-poured into the catalyst solution in 2 hours . The reaction medium is heated for a further 2 hours at 85 ° C. until a complete rate of transformation of the ≡SiVi patterns is achieved. After “stripping” the volatiles, the branched silicone oil obtained has a viscosity of 283 mm 2 / s and contains 0.081 equivalents of ≡SiH per 100g.
Essai comparatif de l'exemple 2 (représentatif de l'art antérieur WO01/98418) Comparative test of Example 2 (representative of the prior art WO01 / 98418)
Sous atmosphère inerte, on charge 40 g de toluène et 14 mg d'une solution de Pt de Karsted à 10-12% de Pt. Le mélange est chauffé et agité à 85 °C puis 50.4 g d'une huile silicone contenant plus de 3 motifs≡SiH par molécule (soit 0.4 équivalents de≡SiH pour 100g) et 48.5 g d'une huile silicone à motifs≡SiVi pendants et terminaux (0.036 équivalents de≡SiVi pour 100g), soit un ratio SiH/SiVi = 11.9 sont co-coulés en 1 heure sur la solution de catalyseur. A la fin de la co-coulée, le milieu a gélifié (réticulé) et n'est plus agitable. Cette composition ne peut donc être utilisée pour l'application visée. Exemple 3 : 40 g of toluene and 14 mg of a Karsted Pt solution containing 10-12% Pt are charged under an inert atmosphere. The mixture is heated and stirred at 85 ° C. and then 50.4 g of a silicone oil containing more than 3 ≡SiH units per molecule (i.e. 0.4 equivalents of ≡SiH per 100g) and 48.5 g of a silicone oil with pendant and terminal ≡SiVi units (0.036 equivalents of≡SiVi per 100g), i.e. a SiH / SiVi ratio = 11.9 are co-poured in 1 hour on the catalyst solution. At the end of the co-pouring, the medium has gelled (crosslinked) and is no longer agitable. This composition cannot therefore be used for the intended application. Example 3:
Sous atmosphère inerte, on charge 40 g de toluène et 14 mg d'une solution de Pt de Karsted à 10-12% de Pt. Le mélange est chauffé et agité à 85 °C puis 95.7 g d'une huile silicone α,ω-SiH (contenant 0.2 équivalents de SiH pour 100g) et 4.3 g d'une huile silicone cyclique à motifs≡SiVi (1.13 équivalents de≡SiVi pour 100g) sont co-coulés en 1.5 heures sur la solution de catalyseur. Le milieu réactionnel est chauffé pendant encore 4 h à 85 °C jusqu'à un taux complet de transformation des motifs≡SiVi. Après « stripping » des volatiles, l'huile silicone branchée obtenue a une viscosité de 103 mm2/s et contient 0.14 équivalents de≡SiH pour 100g. II) Test comme additif anti-misting 40 g of toluene and 14 mg of a Karsted Pt solution containing 10-12% Pt are charged under an inert atmosphere. The mixture is heated and stirred at 85 ° C. and then 95.7 g of a silicone oil α, ω -SiH (containing 0.2 equivalents of SiH per 100g) and 4.3 g of a cyclic silicone oil with ≡SiVi patterns (1.13 equivalents of ≡SiVi per 100g) are co-poured in 1.5 hours onto the catalyst solution. The reaction medium is heated for a further 4 h at 85 ° C. until a complete rate of transformation of the ≡SiVi patterns is achieved. After “stripping” the volatiles, the branched silicone oil obtained has a viscosity of 103 mm 2 / s and contains 0.14 equivalents of ≡SiH per 100g. II) Test as an anti-misting additive
Des silicones branchés préparés dans la partie I) ont été testés en tant qu'additif anti- misting. Les résultats observés sont rassemblés dans les tableaux suivants, en quantité de misting mesuré (mg/m3) ou sous forme de ratio de « misting » mesuré avec additif et sans additif pour différentes vitesses de rotation des rouleaux.  Branched silicones prepared in part I) were tested as an anti-misting additive. The results observed are collated in the following tables, in quantity of misting measured (mg / m3) or in the form of ratio of “misting” measured with additive and without additive for different speeds of rotation of the rollers.
Description du test Description of the test
Pour analyser et quantifier le brouillard produit dans un dispositif d'enduction à cylindres fonctionnant à grande vitesse, on a mis en oeuvre à l'échelle du laboratoire un dispositif (fourni par la société Ermap, Grenoble, France) à 2 rouleaux fonctionnant de manière  To analyze and quantify the fog produced in a roller coating device operating at high speed, a 2-roller device (supplied by the company Ermap, Grenoble, France) was implemented on a laboratory scale.
reproductible et apte à faire défiler une bande de papier à une vitesse linéique de plus de reproducible and able to scroll a strip of paper at a line speed of more than
900m/min. Les deux cylindres presseur/enducteur présentent un diamètre de 10 cm. Le cylindre presseur est recouvert de caoutchouc et le cylindre enducteur de chrome. Le cylindre enducteur a été taillé en haltère de sorte que la vitesse des deux cylindres soient synchrones. Le cylindre presseur entrainable par un moteur, est en contact sous pression constante avec le cylindre enducteur. Le liquide silicone d'enduction est versé directement dans l'entrefer entre les deux rouleaux. La quantité de fluide utilisée est 0,25 ml.  900m / min. The two pressure / coating rollers have a diameter of 10 cm. The pressure cylinder is covered with rubber and the chrome coating cylinder. The coating cylinder was cut in a dumbbell so that the speed of the two cylinders were synchronous. The pressure cylinder driven by a motor is in constant pressure contact with the coating cylinder. The silicone coating liquid is poured directly into the air gap between the two rollers. The amount of fluid used is 0.25 ml.
Différentes compositions ont ensuite été préparés en mélangeant un polymère silicone A1 (polydiméthylsiloxane dont les extrémités sont bloquées par un groupe diméthylvinylsiloxy dont la viscosité est de 220 mPa.s) et les produits décrits ci-dessus dans les exemples 1 à 3 à raison de 2 parties en poids de produit dans 100 parties en poids de polymère. Les compositions sont homogénéisées au roule-fût le temps nécessaire. On utilise ensuite le système rotatif décrit ci- dessus sur les rouleaux sur lesquels est étalée la préparation en question. On augmente ensuite progressivement la vitesse de rotation des rouleaux. Parallèlement, on mesure la densité du brouillard en disposant à proximité du lieu de contact, entre les cylindres, un instrument de mesure appelé compteur de particules commercialisé la société ITS (France). Le résultat de la mesure de densité de brouillard est exprimé en mg d'aérosol silicone par m3 d'air à une vitesse de mesure donnée. Le tableau ci-dessous rassemble les résultats obtenus: Different compositions were then prepared by mixing a silicone polymer A1 (polydimethylsiloxane whose ends are blocked by a dimethylvinylsiloxy group whose viscosity is 220 mPa.s) and the products described above in examples 1 to 3 at a rate of 2 parts by weight of product in 100 parts by weight of polymer. The compositions are homogenized with a keg for the time necessary. The rotary system described above is then used on the rollers on which the preparation in question is spread. The speed of rotation of the rollers is then gradually increased. At the same time, the density of the fog is measured by placing near the place of contact, between the cylinders, a measuring instrument called a particle counter sold by the company ITS (France). The result of the mist density measurement is expressed in mg of silicone aerosol per m 3 of air at a given measurement speed. The table below brings together the results obtained:
Tableau I : Résultats des tests anti-misting en valeur absolue Table I: Results of anti-misting tests in absolute value
On constate donc que l'ajout des produits décrits dans les exemples ci-dessus permet de réduire significativement l'intensité du brouillard produit par les rouleaux en rotation. It can therefore be seen that the addition of the products described in the examples above makes it possible to significantly reduce the intensity of the mist produced by the rotating rollers.
III) Préparation d'un revêtement silicone anti-adhérent sur un support papier III) Preparation of a non-stick silicone coating on a paper support
Les bains sont obtenus en mélangeant successivement les produits suivants:  The baths are obtained by successively mixing the following products:
- un polymère silicone de polydiméthylsiloxane dont les extrémités sont bloquées par un groupe diméthylvinylsiloxy dont la viscosité est de 220 mPa.s,  a silicone polymer of polydimethylsiloxane, the ends of which are blocked by a dimethylvinylsiloxy group, the viscosity of which is 220 mPa.s,
- l'additif selon l'invention (exemples 1 , 2, et 3),  - the additive according to the invention (examples 1, 2, and 3),
- un mélange d'huiles constituées de copolymères de polyhydrogénométhylsiloxane et de polydiméthylsiloxane, les deux types de copolymères étant bloqués par des groupes  - a mixture of oils consisting of polyhydrogenethylsiloxane and polydimethylsiloxane copolymers, the two types of copolymers being blocked by groups
triméthylsiloxane, trimethylsiloxane,
- un catalyseur contenant du Pt (catalyseur de Karsted) et mis en solution dans du  - a catalyst containing Pt (Karsted catalyst) and dissolved in
divinyltétraméthyldisiloxane. divinyltetramethyldisiloxane.
Les proportions du mélange sont calculées de sorte que l'on obtienne dans le bain final un rapport entre le nombre total en moles de groupements vinyles et le nombre total en mole de groupements hydrogénosiloxane de 1.75, une concentration en platine de 110 ppm et un taux d'éthynylcyclohexanol-1 de l'ordre de 0.15% en poids par rapport au poids de la formulation. Par ailleurs, l'additif anti-misting selon l'invention est ajouté au polymère silicone de The proportions of the mixture are calculated so that a ratio is obtained in the final bath between the total number in moles of vinyl groups and the total number in moles of hydrogenosiloxane groups of 1.75, a platinum concentration of 110 ppm and a rate of ethynylcyclohexanol-1 of the order of 0.15% by weight relative to the weight of the formulation. Furthermore, the anti-misting additive according to the invention is added to the silicone polymer of
polydiméthylsiloxane dont les extrémités sont bloquées par un groupe diméthylvinylsiloxy et dont la viscosité est de 220 mPa.s dans une proportion de 2% en poids par rapport au poids total de la formulation. Ces bains sont ensuite utilisés successivement pour enduire un support de papier appelé "glassine" au moyen d'une machine d'enduction dont la tête d'enduction est une tête munie de quatre cylindres humides. En aval de cette tête, une sécherie dans laquelle circule de l'air à 195°C environ est utilisée pour faire durcir l'enduit de silicone en le portant à une température maximale comprise entre 130 et 160°C. Après avoir procédé à l'opération d'enduction en utilisant successivement les bains décrits ci-dessus, on obtient des résultats comparables quand à la réduction du brouillard lors de l'enduction tout en obtenant un revêtement au toucher sec et au caractère anti-adhérent. polydimethylsiloxane whose ends are blocked by a dimethylvinylsiloxy group and whose viscosity is 220 mPa.s in a proportion of 2% by weight relative to the total weight of the formulation. These baths are then used successively to coat a paper support called "glassine" by means of a coating machine, the coating head of which is a head provided with four wet cylinders. Downstream of this head, a dryer in which air circulates at approximately 195 ° C. is used to harden the silicone coating by bringing it to a maximum temperature of between 130 and 160 ° C. After having carried out the coating operation successively using the baths described above, comparable results are obtained when the reduction of the mist during coating while obtaining a coating with a dry feel and non-stick character .

Claims

REVENDICATIONS
1 - Procédé de lutte contre l'apparition de brouillard ("misting") lors de l'enduction de supports flexibles comprenant les étapes suivantes : 1 - Method for combating the appearance of mist ("misting") when coating flexible supports, comprising the following steps:
1 ) la préparation d'une composition silicone liquide X précurseur de revêtement(s) silicone comprenant :  1) the preparation of a liquid silicone composition X precursor of silicone coating (s) comprising:
- au moins un polyorganosiloxane A réticulable par polyaddition, par  at least one polyorganosiloxane A crosslinkable by polyaddition, by
déshydrogénocondensation, par polycondensation, par voie cationique ou par voie radicalaire, - éventuellement au moins un composé organosilicique réticulant B, dehydrogenocondensation, by polycondensation, cationically or radically, - optionally at least one crosslinking organosilicon compound B,
- éventuellement au moins un catalyseur ou photoamorceur C dont la nature est choisie suivant le type de réaction envisagée pour ledit polyorganosiloxane A,  optionally at least one catalyst or photoinitiator C, the nature of which is chosen according to the type of reaction envisaged for said polyorganosiloxane A,
- éventuellement, au moins un système modulateur d'adhérence K, et  - optionally, at least one adhesion modulator system K, and
- éventuellement au moins un inhibiteur de réticulation D; et  - optionally at least one crosslinking inhibitor D; and
2) l'enduction de ladite composition silicone liquide X sur un support flexible à l'aide d'un dispositif d'enduction à cylindres, 2) coating said liquid silicone composition X on a flexible support using a roller coating device,
ledit procédé étant caractérisé en ce qu'à l'étape a) on ajoute à ladite composition silicone liquide X un additif anti-brouillard E (additif « antimisting »), qui est : said process being characterized in that in step a) a liquid anti-fog additive E (“antimisting” additive) is added to said liquid silicone composition X, which is:
- un polyorganosiloxane branché L (ou un mélange comprenant au moins un  - a branched polyorganosiloxane L (or a mixture comprising at least one
polyorganosiloxane branché L) porteur d'au moins un motif réactif≡SiH et uniquement sur des motifs de formule : branched polyorganosiloxane L) carrying at least one reactive unit≡SiH and only on units of formula:
M' = H R1R2 SiOiZ2 (I) ledit additif anti-brouillard E étant obtenu : M '= HR 1 R 2 SiOiZ 2 (I) said anti-fog additive E being obtained:
a) en faisant réagir, de préférence à une température comprise entre 0°C et 200°C: a) by reacting, preferably at a temperature between 0 ° C and 200 ° C:
- au moins un polyorganosiloxane F, porteur de deux motifs réactifs≡SiH par molécule et de formule brute :  - at least one polyorganosiloxane F, carrying two reactive units≡SiH per molecule and of crude formula:
M'Ma DaTbQcM' (II) M'M a D a T b Q c M '(II)
dans laquelle :  in which :
- a, a', b et c sont des nombres > à 0, et de préférence a', b et c =0,  - a, a ', b and c are numbers> to 0, and preferably a', b and c = 0,
- M = R'3R3R4SiOi/2; - M = R ' 3 R 3 R 4 SiOi / 2 ;
- M' = HR3R4SiOiZ2; - M '= HR 3 R 4 SiOiZ 2 ;
- D = R5R6SiO2Z2; - D = R 5 R 6 SiO 2Z2 ;
- T = R7SiO3Z2; - T = R 7 SiO 3 Z 2 ;
- Q = SiO4Z2; - Q = SiO 4 Z 2 ;
- avec les symboles R1, R2, R3, R'3, R4, R5, R6 et R7, identiques ou différents, représentent chacun indépendamment l'un de l'autre: - un radical alkyle linéaire ou ramifié contenant 1 à 20 atomes de carbone, éventuellement substitué par au moins un halogène, de préférence le fluor, les radicaux alkyles étant de préférence méthyle, éthyle, propyle, octyle et 3,3,3-trifluoropropyle, - with the symbols R 1 , R 2 , R 3 , R ' 3 , R 4 , R 5 , R 6 and R 7 , identical or different, each represent independently of one another: a linear or branched alkyl radical containing 1 to 20 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl,
- un radical cycloalkyle contenant entre 5 et 8 atomes de carbone cycliques,  - a cycloalkyl radical containing between 5 and 8 cyclic carbon atoms,
éventuellement substitué,  possibly substituted,
- un radical aryle contenant entre 6 et 12 atomes de carbone éventuellement substitué, et/ou  - an aryl radical containing between 6 and 12 carbon atoms optionally substituted, and / or
- une partie aralkyle ayant une partie alkyle contenant entre 5 et 14 atomes de carbone et une partie aryle contenant entre 6 et 12 atomes de carbone, substituée éventuellement sur la partie aryle par des halogènes et/ou des alkyles, avec  an aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens and / or alkyls, with
- au moins un polyorganosiloxane G présentant, par molécule, au moins 3 groupes alcényles en at least one polyorganosiloxane G having, per molecule, at least 3 alkenyl groups in
C2-C6 liés au silicium en présence : C 2 -C 6 linked to silicon in the presence:
- d'au moins un catalyseur de polyaddition H, de préférence le catalyseur polyaddition H est composé d'au moins un métal appartenant au groupe du platine, et  at least one polyaddition catalyst H, preferably the polyaddition catalyst H is composed of at least one metal belonging to the platinum group, and
- d'éventuellement au moins un inhibiteur de réticulation I et/ou au moins un solvant J, la nature et les quantités des composants F et G sont déterminées de manière à ce que le ratio : - optionally at least one crosslinking inhibitor I and / or at least one solvent J, the nature and the amounts of the components F and G are determined so that the ratio:
[nombre de motif réactif≡SiH]:[nombre de motif réactif≡Si-alcényle] >1 :1 et de préférence > 2:1 , et [number of reactive unit≡SiH]: [number of reactive unit≡Si-alkenyl]> 1: 1 and preferably> 2: 1, and
b) en isolant l'additif anti-brouillard E, éventuellement après élimination du catalyseur de polyaddition H et/ou dévolatilisation et/ou addition d'un inhibiteur de réticulation I'. b) by isolating the anti-fog additive E, optionally after elimination of the polyaddition catalyst H and / or devolatilization and / or addition of a crosslinking inhibitor I '.
2 - Procédé de lutte contre l'apparition de brouillard ("misting") lors de l'enduction de supports flexibles selon la revendication 1 caractérisée en ce que le polyorganosiloxane G présente : 2 - Method for combating the appearance of mist ("misting") during the coating of flexible supports according to claim 1 characterized in that the polyorganosiloxane G has:
a) par molécule, au moins 3 groupes alcényles en C2-C6 liés au silicium, a) per molecule, at least 3 C 2 -C 6 alkenyl groups linked to silicon,
b) des motifs de formule : b) reasons for the formula:
X Zd SiO(^y2 (III) XZ d SiO (^ y 2 (III)
dans laquelle :  in which :
- X est un groupe alcényle en C2-C6, - X is a C 2 -C 6 alkenyl group,
- Z est un groupe hydrocarboné monovalent, exempt d'action défavorable sur l'activité du catalyseur et choisi parmi les groupes alkyles ayant de 1 à 8 atomes de carbone inclus, éventuellement substitués par au moins un atome d'halogène, et ainsi que parmi les groupes aryles,  - Z is a monovalent hydrocarbon group, free from any unfavorable action on the activity of the catalyst and chosen from alkyl groups having from 1 to 8 carbon atoms included, optionally substituted by at least one halogen atom, and also from aryl groups,
- d est 0, 1 ou 2, et  - d is 0, 1 or 2, and
-c) éventuellement au moins une partie des autres motifs sont des motifs de formule moyenne : -c) optionally at least part of the other motifs are motifs of medium formula:
dans laquelle Z a la même signification que ci-dessus et e a une valeur comprise entre 0 et 3,  where Z has the same meaning as above and e has a value between 0 and 3,
3 - Procédé de lutte contre l'apparition de brouillard ("misting") lors de l'enduction de supports flexibles selon la revendication 1 caractérisé en ce que ledit polyorganosiloxane branché L a comme formule brute moyenne: 3 - Method for combating the appearance of mist ("misting") during the coating of flexible supports according to claim 1 characterized in that said branched polyorganosiloxane L has as an average crude formula:
Mf Dg (Malk)h (Dalk)i Tk Qm (IW)n (V) M f D g (M alk ) h (D alk ) i T k Q m (IW) n (V)
avec: with:
- f, g, i, k et m > 0,  - f, g, i, k and m> 0,
- h et m > 0,  - h and m> 0,
- M' = HR8R9SiOiZ2; - M '= HR 8 R 9 SiOiZ 2 ;
- Malk = RR10R11SiOiZ2 - M alk = RR 10 R 11 SiOiZ 2
- Dalk = RR12SiO2Z2 - D alk = RR 12 SiO 2Z2
- D = R13R14SiO2Z2; - D = R 13 R 14 SiO 2 Z 2 ;
- T = R15SiO3Z2; - T = R 15 SiO 3 Z 2 ;
- Q = SiO4Z2; - Q = SiO 4 Z 2 ;
- avec :  - with:
- le symbole R (rotule alkyle du polymère branché) est un groupe alkyle en C2-C6, etthe symbol R (alkyl patella of the connected polymer) is a C 2 -C 6 alkyl group, and
- les symboles R8, R9, R10, R11, R12, R13, R14 et R15, identiques ou différents, représentent chacun indépendamment l'un de l'autre: - the symbols R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 , identical or different, each represent independently of one another:
- un radical alkyle linéaire ou ramifié contenant 1 à 20 atomes de carbone, éventuellement substitué par au moins un halogène, de préférence le fluor, les radicaux alkyles étant de préférence méthyle, éthyle, propyle, octyle et 3,3,3-trifluoropropyle,  a linear or branched alkyl radical containing 1 to 20 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl,
- un radical cycloalkyle contenant entre 5 et 8 atomes de carbone cycliques,  - a cycloalkyl radical containing between 5 and 8 cyclic carbon atoms,
éventuellement substitué,  possibly substituted,
- un radical aryle contenant entre 6 et 12 atomes de carbone éventuellement substitué, et/ou  - an aryl radical containing between 6 and 12 carbon atoms optionally substituted, and / or
- une partie aralkyle ayant une partie alkyle contenant entre 5 et 14 atomes de carbone et une partie aryle contenant entre 6 et 12 atomes de carbone, substituée éventuellement sur la partie aryle par des halogènes et/ou des alkyles,  an aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens and / or alkyls,
4 - Procédé de lutte contre l'apparition de brouillard ("misting") lors de l'enduction de supports flexibles selon l'une quelconque des revendications précédentes dans lequel ladite composition silicone liquide X précurseur de revêtement(s) silicone à laquelle on ajoute l'additif anti-brouillard E (« antimisting ») tel que défini selon l'une des revendications précédentes, comprend : 4 - Process for combating the appearance of mist ("misting") during the coating of flexible supports according to any one of the preceding claims, in which said composition liquid silicone X silicone coating precursor to which the anti-fog additive E (“antimisting”) as defined in one of the preceding claims is added, comprises:
- au moins un polyorganosiloxane A réticulable par polyaddition,  at least one polyorganosiloxane A crosslinkable by polyaddition,
- au moins un composé organosilicique réticulant B,  - at least one crosslinking organosilicon compound B,
- au moins un catalyseur C1 de la réaction de polyaddition;  - At least one catalyst C1 of the polyaddition reaction;
- éventuellement au moins un système modulateur d'adhérence K, et  - optionally at least one adhesion modulator system K, and
- éventuellement au moins un inhibiteur de réticulation D.  - optionally at least one crosslinking inhibitor D.
5 - Procédé de lutte contre l'apparition de brouillard ("misting") lors de l'enduction de supports flexibles selon l'une quelconque des revendications précédentes caractérisé en ce que le polyorganosiloxane A réticulable par polyaddition présente des motifs de formule (Vl) et éventuellement au moins une partie des autres motifs sont des motifs de formule moyenne (VII): 5 - Method for combating the appearance of mist ("misting") during the coating of flexible supports according to any one of the preceding claims, characterized in that the polyorganosiloxane A crosslinkable by polyaddition has units of formula (VI) and optionally at least some of the other units are units of average formula (VII):
WaYb Si0ii2^> (Vl) W a Y b Si0ii2 ^> (Vl)
2  2
Yc SiOiH (VII) Yc SiOiH (VII)
2  2
formules dans lesquelles : formulas in which:
- W est un groupe alcényle, de préférence vinyle ou allyle,  W is an alkenyl group, preferably vinyl or allyl,
- les symboles Y, identiques ou différents, représentent :  - the symbols Y, identical or different, represent:
- un radical alkyle linéaire ou ramifié contenant 1 à 20 atomes de carbone, éventuellement substitué par au moins un halogène, de préférence le fluor, les radicaux alkyles étant de préférence méthyle, éthyle, propyle, octyle et 3,3,3- trifluoropropyle,  a linear or branched alkyl radical containing 1 to 20 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl,
- un radical cycloalkyle contenant entre 5 et 8 atomes de carbone cycliques, éventuellement substitué,  - a cycloalkyl radical containing between 5 and 8 cyclic carbon atoms, optionally substituted,
- un radical aryle contenant entre 6 et 12 atomes de carbone éventuellement substitué, et/ou  - an aryl radical containing between 6 and 12 carbon atoms optionally substituted, and / or
- une partie aralkyle ayant une partie alkyle contenant entre 5 et 14 atomes de carbone et une partie aryle contenant entre 6 et 12 atomes de carbone, substituée éventuellement sur la partie aryle par des halogènes et/ou des alkyles.  - An aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens and / or alkyls.
a est 1 ou 2, de préférence égal à 1 , b est 0, 1 ou 2 et a + b = 1 , 2 ou 3, et a is 1 or 2, preferably equal to 1, b is 0, 1 or 2 and a + b = 1, 2 or 3, and
- c = 0, 1 , 2 ou 3. - c = 0, 1, 2 or 3.
6 - Procédé de lutte contre l'apparition de brouillard ("misting") lors de l'enduction de supports flexibles selon la revendication 9 caractérisé en ce que le composé organosilicique réticulant B présente des motifs de formule (VIII) et éventuellement au moins une partie des autres motifs sont des motifs de formule moyenne (IX): 6 - Method for combating the appearance of mist ("misting") during the coating of flexible supports according to claim 9 characterized in that the crosslinking organosilicon compound B has units of formula (VIII) and optionally at least part of the other units are units of average formula (IX):
H Lc Si0(3-c)/2 (VIII) HL c Si0 (3 -c) / 2 (VIII)
Lg Si0(4-g)/2 (IX) L g Si0 ( 4 -g) / 2 (IX)
dans lesquelles : in which :
- les symboles L, identiques ou différents, représentent :  - the symbols L, identical or different, represent:
- un radical alkyle linéaire ou ramifié contenant 1 à 20 atomes de carbone, éventuellement substitué par au moins un halogène, de préférence le fluor, les radicaux alkyles étant de préférence méthyle, éthyle, propyle, octyle et 3,3,3- trifluoropropyle,  a linear or branched alkyl radical containing 1 to 20 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl,
- un radical cycloalkyle contenant entre 5 et 8 atomes de carbone cycliques, éventuellement substitué,  - a cycloalkyl radical containing between 5 and 8 cyclic carbon atoms, optionally substituted,
- un radical aryle contenant entre 6 et 12 atomes de carbone éventuellement substitué, et/ou  - an aryl radical containing between 6 and 12 carbon atoms optionally substituted, and / or
- une partie aralkyle ayant une partie alkyle contenant entre 5 et 14 atomes de carbone et une partie aryle contenant entre 6 et 12 atomes de carbone, substituée éventuellement sur la partie aryle par des halogènes et/ou des alkyles,  an aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and 12 carbon atoms, optionally substituted on the aryl part by halogens and / or alkyls,
- c = 0, 1 ou 2, et  - c = 0, 1 or 2, and
- g= 0, 1 , 2 ou 3.  - g = 0, 1, 2 or 3.
7 - Utilisation de l'additif anti-brouillard E tel que défini selon l'une quelconque des revendications précédentes pour réduire l'apparition de brouillard ("misting") lors de l'enduction de supports flexibles avec une composition silicone liquide X précurseur de revêtement(s) silicone telle que définie selon l'une quelconque des revendications précédentes. 7 - Use of the anti-fog additive E as defined according to any one of the preceding claims to reduce the appearance of mist ("misting") when coating flexible supports with a liquid silicone composition X precursor of silicone coating (s) as defined in any one of the preceding claims.
8 - Procédé d'enduction de supports flexibles avec au moins une composition silicone liquide X précurseur de revêtement(s) silicone telle que définie selon l'une quelconque des revendications précédentes, cette enduction s'effectuant à l'aide d'un dispositif d'enduction à cylindres, caractérisé en ce que l'on a recours au procédé de lutte contre l'apparition de brouillard ("misting") selon l'une quelconque des revendications 1 à 6. 8 - Method for coating flexible supports with at least one liquid silicone composition X silicone coating precursor (s) as defined in any one of the preceding claims, this coating being carried out using a device d coating with cylinders, characterized in that use is made of the method of combating the appearance of mist ("misting") according to any one of claims 1 to 6.
EP06830433A 2005-12-09 2006-12-07 Method of preventing the appearance of misting when coating flexible media with a crosslinkable liquid silicone composition in a multi-roll device Withdrawn EP1969063A1 (en)

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FR0512508A FR2894589B1 (en) 2005-12-09 2005-12-09 METHOD FOR FIGHTING FOG APPEARANCE DURING THE COATING OF FLEXIBLE CARRIERS WITH A CROSSLINKABLE LIQUID SILICONE COMPOSITION IN A CYLINDERS DEVICE
PCT/EP2006/069408 WO2007065921A1 (en) 2005-12-09 2006-12-07 Method of preventing the appearance of misting when coating flexible media with a crosslinkable liquid silicone composition in a multi-roll device

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KR101137755B1 (en) * 2007-06-21 2012-07-10 블루스타 실리콘즈 프랑스 에스에이에스 Process for combating the appearance of haze during the coating of flexible supports with a crosslinkable liquid silicone composition, in a roll device
CN101955750B (en) * 2010-10-20 2012-07-04 梁承忠 Automotive glass antifogging agent and preparation method thereof
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FR3052784A1 (en) * 2016-06-21 2017-12-22 Bluestar Silicones France METHOD FOR FIGHTING THE FOG IN A CYLINDERS DEVICE WHEN COATING FLEXIBLE CARRIERS WITH A CROSS-LINKABLE LIQUID SILICONE COMPOSITION
RU2716278C1 (en) 2017-02-08 2020-03-11 ЭЛКЕМ СИЛИКОНС ЮЭсЭй КОРП. Storage battery unit with improved thermal control
JP7430727B2 (en) * 2018-12-20 2024-02-13 エルケム・シリコーンズ・フランス・エスアエス Method for prevention of mist formation in roll-containing equipment during coating of flexible substrates with crosslinkable liquid silicone compositions

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US5625023A (en) * 1994-12-09 1997-04-29 Dow Corning Corporation Aerosol suppressant compositions for silicone coatings
US6489407B1 (en) * 2000-06-22 2002-12-03 Dow Corning Corporation Silicone coatings containing silicone mist suppressant compositions
DE10210014A1 (en) * 2002-03-07 2003-09-25 Wacker Chemie Gmbh Siloxane copolymers containing Si-bonded hydrogen atoms as antimisting additives for silicone coating compositions

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