EP2723816A1 - Hydrosilylation reaction inhibitors, and use thereof for preparing stable curable silicone compositions - Google Patents

Hydrosilylation reaction inhibitors, and use thereof for preparing stable curable silicone compositions

Info

Publication number
EP2723816A1
EP2723816A1 EP12735925.5A EP12735925A EP2723816A1 EP 2723816 A1 EP2723816 A1 EP 2723816A1 EP 12735925 A EP12735925 A EP 12735925A EP 2723816 A1 EP2723816 A1 EP 2723816A1
Authority
EP
European Patent Office
Prior art keywords
silicone composition
ppm
inhibitor
platinum
methyl
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Withdrawn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
EP12735925.5A
Other languages
German (de)
French (fr)
Inventor
Sébastien MARROT
Yassine Maadadi
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 EP2723816A1 publication Critical patent/EP2723816A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/12—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing sulfur and oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention relates to the use of inhibiting compounds, in particular inhibiting compounds suitable for inhibiting the curing of a silicon elastomer precursor silicone composition obtained by a hydrosilylation reaction.
  • Curing inhibitors are compounds that slow curing at ambient temperatures, but do not delay curing at higher temperatures. These curing inhibitors are sufficiently volatile to be removed from the coating compositions.
  • acetylenic compounds such as acetylenic alcohols having a boiling point of less than 250 ° C., especially 2-methyl-3-butyne-2-ol and ethynylcyclohexanol, as hydrosilylation inhibitors in curable silicone compositions based on an organosilicon polymer bearing olefinically unsaturated substituents (vinylic in particular), an organohydrogensiloxane polymer and a platinum or platinum-type catalyst.
  • the presence of these acetylenic compounds inhibits the platinum catalyst by preventing it from catalyzing the curing reaction at room temperature, but not at elevated temperature.
  • curable silicone compositions which contain this type of inhibitor can be cured by increasing the temperature of the composition to a temperature above the boiling point or sublimation of the inhibitor, thus evaporating the inhibitor, or part of the inhibitor, and allowing the catalyst to catalyze the hydrosilylation reaction and thereby cure the silicone composition.
  • compositions can be transported in one package instead of two. They can also be used to prolong the processing time or the pot life, in comparison with compositions that do not contain the acetylenic compound.
  • These compositions can be deposited on substrates such as paper, for example by coating and thermally cured at a temperature of the order of 80 to 250 ° C., in particular between 100 and 220 ° C. See, for example, the FR-A- patents. 1,528,464 and FR-A-2,372,874.
  • compositions have the drawback, for the preparation of anti-adhesive coatings, of being unable to crosslink on the support at a temperature below 80 ° C. and of having insufficient stability during coating on a machine, the gelling of the coating bath. already showing up after an hour. This is because these inhibitors are sublimable.
  • This major disadvantage requires the use of significant amounts, which results in a strong inhibition of platinum activity and consequently a slower rate of crosslinking which requires reducing coating rates.
  • US Pat. No. 5,496,906 describes an acid pretreatment of a filler used in a silicone composition in order to eliminate the nitrosamine derivatives during the formation of the elastomer after crosslinking.
  • This filler is incorporated in a vinyl silicone oil and is treated by heating at a temperature between 70 and 80 ° C for one hour in the presence of a vinyltriethoxysilane, water and an acid.
  • the mixture undergoes a "stripping" step at 140 ° C and under vacuum to remove all by-products of the reaction (see Example 1, column 6).
  • One of the essential objectives of the present invention is to provide a novel inhibitor not having the disadvantages mentioned above.
  • Another essential objective of the present invention is to provide a silicone composition X with a low platinum content, that is to say having less than 50 ppm by weight of platinum. relative to the total weight of the composition and capable of hardening by a polyaddition reaction which:
  • the main object of the invention consists of a silicone composition X
  • At least one organopolysiloxane A comprising, by molecule, at least two alkenyl radicals bonded to silicon atoms
  • organohydrogenpolysiloxane B having, per molecule, at least two hydrogen atoms bonded to silicon atoms
  • At least one catalyst C which is a platinum compound and even more preferably a Karsted platinum, the amount by weight of platinum of catalyst C relative to the total weight of silicone composition X is less than 50 ppm and preferably between 1 and 40 ppm and even more preferably between 5 and 25 ppm,
  • At least one inhibitor D1 which is an acetylenic alcohol and preferably a cc-acetylenic alcohol, and
  • At least one acid D2 having in aqueous solution and at 25 ° C at least one pKa ⁇ -0.9, preferably ⁇ -1, 0 and even more preferably within the following range -12.0 ⁇ pKa ⁇ -1, 0,
  • constituents D1 and D2 being initially present in said silicone composition X in amounts sufficient to:
  • Examples of the acid D2 which are useful according to the invention are, for example, chosen from the group consisting of the following acids:
  • H 2 Cr0 - H 2 Cr0 4, Hl, HMn0 4l HN0 3, HRe0 4, H 2 S0 4, CF3SO 3 H, CH 3 SO 3 H, HCl, HBr, hci0 4, H 2 S0 4, HN0 3, H 2 Cr0, HCIO3 and H1.
  • the acid D 2 is chosen from the group consisting of CF 3 SO 3 H and CH 3 SO 3 H and, in an even more advantageous mode, the acid D 2 is the methanesulfonic acid of formula CH 3 S0 3 H.
  • the molar ratio [D1 inhibitor] / [D2 acid] is between
  • the ratio by weight [inhibitor D1] / [catalyst C] is between 30 and 2000 and the molar ratio [acid D2] / [catalyst C] is between 1 and 200.
  • Acetylenic alcohols D1 useful according to the invention may be chosen from the group consisting of the following compounds:
  • Catalyst C which is a catalyst for the hydrosilylation reaction is also well known.
  • Platinum or complexes of platinum and an organic product described in US Pat. Nos. 3,159,601 and 3,220,972 and European patents EP-A-0 057 459 can be used in particular.
  • EP-A-0 188 978 and EP-A-0 190 530 the complexes of platinum and vinyl organosiloxanes described in US-A-3,419,593, US-A-3,715,334 and US Pat. 3,814,730.
  • the proportions of the organopolysiloxane A and of the organohydrogenpolysiloxane B are such that the molar ratio of the silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane B on the silicon-bonded alkenyl radicals in the organopolysiloxane A is between 0.4 and 10.
  • the organopolysiloxane A according to the invention has:
  • T is an alkenyl group
  • Z is a monovalent hydrocarbon group, which has no adverse effect on the activity of the catalyst and is selected from the group consisting of alkyl groups having from 1 to 8 carbon atoms inclusive, optionally substituted with at least one halogen atom, and aryl groups, and
  • a is equal to 1 or 2
  • b is equal to 0, 1 or 2 and the sum a + b is between 1 and 3
  • the organopolysiloxane A has a viscosity of at least 100 mPas and preferably less than 200,000 mPas. .
  • the organohydrogenpolysiloxane B according to the invention has: at least two, and preferably at least three, siloxyl units of formula (B.1):
  • L is a monovalent hydrocarbon group, which has no adverse effect on the activity of the catalyst and is selected from the group consisting of alkyls having 1 to 8 carbon atoms inclusive, optionally substituted with at least one halogen atom, and the aryls,
  • H is a hydrogen atom
  • d is 1 or 2
  • e is 0, 1 or 2
  • the sum d + e is 1, 2 or 3
  • L has the same meaning as above and g is 0, 1, 2 or 3.
  • the dynamic viscosity of the organohydrogenpolysiloxane B is at least 10 mPa.s and preferably it is between 20 and 1000 mPa.s.
  • the proportions of the siloxyl units (A.1) and (B.1) are such that the molar ratio of the silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane B to the silicon-bonded alkenyl radicals in the organopolysiloxane A is between 0.4 and 10.
  • the silicone composition X according to the invention may comprise one or more conventional additives in the field of silicone release coatings for solid support, for example paper. It may be for example an anti-misting additive such as silica particles, or branched polyorganosiloxanes, etc.
  • the silicone composition X according to the invention may also comprise an adhesion modulator system as well as additives that are customary in this type of application, such as: bactericides, anti-freeze agents, wetting agents, anti-blocking agents - foams, fillers, synthetic latexes or dyes.
  • an adhesion modulator system as well as additives that are customary in this type of application, such as: bactericides, anti-freeze agents, wetting agents, anti-blocking agents - foams, fillers, synthetic latexes or dyes.
  • the present invention relates to a silicone elastomer Y obtained by crosslinking or curing the silicone composition X according to the invention and as described above, said crosslinking or curing being carried out at a temperature between 70 ° C and 200 ° C.
  • the present invention also relates to the use of the silicone composition X according to the invention as a coating base for the production of crosslinked elastomeric anti-adhesive and water-repellent coatings on a solid support, preferably a flexible solid support such as a paper, a cardboard, a cellulose sheet, a metal sheet or a plastic film.
  • a solid support preferably a flexible solid support such as a paper, a cardboard, a cellulose sheet, a metal sheet or a plastic film.
  • Another subject of the invention consists of a solid support at least partly coated with the silicone composition X according to the invention and as described above, and crosslinked or cured by heating to a temperature of between 70.degree. ° C and 200 ° C or Y silicone elastomer according to the invention and as described above.
  • the invention also relates to an inhibitor D of the hydrosilylation reaction which is obtainable by mixing:
  • At least one inhibitor D1 according to the invention and as described above which is an acetylenic alcohol and preferably an ⁇ -acetylenic alcohol, and
  • Another subject of the invention consists in the use of the inhibitor D of the hydrosilylation reaction according to the invention and as described above in curable or crosslinkable silicone compositions comprising:
  • At least one organopolysiloxane A comprising, by molecule, at least two alkenyl radicals bonded to silicon atoms
  • At least one catalyst C which is a platinum compound and even more preferably a Karsted platinum and the amount by weight of platinum of the catalyst C relative to the total weight of the silicone composition X is less than 50 ppm and preferably between 1 and 40 ppm and even more preferably between 5 and 25 ppm.
  • the present invention finally relates to a method for rendering soft material sheets non-adherent to surfaces to which they adhere normally, characterized in that it consists in applying a quantity of the composition silicone X according to the invention and as described above, between 0.1 and 5 g per m 2 of surface to be coated and then crosslink the composition by heating at a temperature between 70 ° C and 200 ° C.
  • the silicone composition X according to the invention can be applied using devices used on industrial paper coating machines such as a five-roll coating head, air knife or equalizer systems.
  • the passage time in these furnaces is a function of the temperature; this is usually from 5 to 15 seconds at a temperature of 100 ° C and from 1.5 to 3 seconds at a temperature of 180 ° C.
  • the silicone composition X can be deposited on any flexible material or substrate such as papers of various types (supercalendré, coated, glassine), cardboard, cellulose sheets, metal sheets, plastic films (polyester, polyethylene, polypropylene, etc.). ) ...
  • the amounts of deposited compositions are generally of the order of 0.1 to 5 g per m 2 of surface to be treated, which corresponds to the deposition of layers of the order of 0.1 to 5 pm.
  • the materials or supports thus coated may subsequently be brought into contact with any pressure sensitive rubber, acrylic or other adhesive materials.
  • the adhesive material is then easily detachable from said support or material. All the viscosities referred to herein correspond to a dynamic viscosity quantity which is measured, in a manner known per se, at 25.degree.
  • the polyorganosiloxane oils will be conventionally described using the usual notation in which the letters M, D, T and Q are used to designate various siloxyl units.
  • the silicon atom of a siloxyl unit is engaged in one (M), two (D), three (T) or four (Q) covalent bonds with as many oxygen atoms.
  • M silicon atom
  • D two
  • T three
  • Q four
  • an oxygen atom is shared between two silicon atoms, it is counted for 1 ⁇ 2 and it will not be mentioned in an abbreviated form.
  • the oxygen atom belongs to an alkoxyl or hydroxyl group bonded to a silicon atom, this chemical function will be indicated in parentheses in the abbreviated formula.
  • Silicon bonded hydrocarbon groups via a C-Si bond are not mentioned and most often correspond to an alkyl group, for example a methyl group.
  • a hydrocarbon group has a particular function, it is indicated by exponent. For example, short forms:
  • - M V represents a unit in which the silicon atom is bonded to an oxygen atom and one of the C-Si bond-forming hydrocarbon groups is a vinyl group, i.e. a dialkylvinylsiloxyl unit, and
  • M ' represents a unit in which the silicon atom is bonded to a hydrogen atom, to an atom and to two methyl groups.
  • the pKa values are those measured in aqueous solution and at 25 ° C.
  • Oils polymethylhydrosiloxanes (B.2) mixture: 18% by weight of an oil having the average formula I4 i Mi D2iMo 4, 6- + 82% of an oil polymethylhydrogenosiloxanes MD structure '40 M.
  • the inhibitor ECH (D1.I1) is previously added to the vinylated polydimethylsiloxane oil (A.1). After homogenization of the mixture, the polymethylhydrogen siloxane oil (B.1) is then introduced, then a fixed quantity of 500 ppm (relative to the total weight of the composition) of the acid to be tested and finally a variable amount of the catalyst (C ).
  • the inhibitor ECH (D1.I1) is previously added to the vinylated polydimethylsiloxane oil (A.1). After homogenization of the mixture, the polymethylhydrogensiloxane oil (B.1) is then introduced, followed by the acid to be tested, and finally the amount of catalyst (C) is fixed at 10 ppm platinum relative to the total weight of the composition.
  • the formulations are recorded in the following Table 3:
  • a sample for each composition is taken and analyzed in DSC ("Differential Scanning Calorimetry", METLER type device). The analysis is carried out in aluminum capsule and using a temperature ramp of 25 to 250 ° C. with a gradient of 10 ° C./min. This technique makes it possible to measure for each composition, the temperature peak start (starting the crosslinking reaction) or "T ° C onset”, the peak peak temperature ("T ° C peak”) and the peak end temperature (“T ° C endset”).
  • Thermal profiles, the characteristic data of the exothermic peaks are shown in the following Table 4.
  • composition (I-3) with 500 ppm of methanesulfonic acid, the crosslinking reaction starts at 109.3 ° C] than for the comparative examples that are the compositions:

Abstract

The present invention relates to the use of inhibitor compounds, in particular inhibitor compounds suitable for inhibiting the curing of a silicone composition that is a precursor of a silicone elastomer produced by a hydrosilylation reaction.

Description

INHIBITEURS DE REACTION D'HYDROSILYLATION, ET LEUR APPLICATION POUR LA PREPARATION DE COMPOSITIONS SILICONES DURCISSABLES STABLES.  HYDROSILYLATION REACTION INHIBITORS AND THEIR APPLICATION FOR THE PREPARATION OF STABLE CURABLE SILICONE COMPOSITIONS.
La présente invention concerne l'utilisation de composés inhibiteurs, en particulier de composés inhibiteurs appropriés pour inhiber le durcissement d'une composition silicone précurseur d'élastomère silicone obtenu par une réaction d'hydrosilylation. The present invention relates to the use of inhibiting compounds, in particular inhibiting compounds suitable for inhibiting the curing of a silicon elastomer precursor silicone composition obtained by a hydrosilylation reaction.
Lorsqu'il est nécessaire d'accroître la durée de vie en pot des compositions d'organopolysiloxane durcissables par addition, ou de fournir une composition When it is necessary to increase the pot life of the addition-curable organopolysiloxane compositions, or to provide a composition
d'organopolysiloxane durcissable par addition à un seul composant, il est d'usage d'incorporer un inhibiteur de durcissement. Les inhibiteurs de durcissement sont des composés qui ralentissent le durcissement aux températures ambiantes, mais qui ne retardent pas le durcissement aux températures plus élevées. Ces inhibiteurs de durcissement sont suffisamment volatils pour être chassés des compositions de revêtement. It is customary to incorporate a hardening inhibitor with a one-component addition curable organopolysiloxane. Curing inhibitors are compounds that slow curing at ambient temperatures, but do not delay curing at higher temperatures. These curing inhibitors are sufficiently volatile to be removed from the coating compositions.
Il est connu, voir par exemple le brevet U.S. N° 3 445 420, d'utiliser des composés acétyléniques tels que les alcools acétyléniques de point d'ébullition inférieur à 250°C, notamment le 2-méthyl 3-butyne 2-ol et l'éthynylcyclohexanol, comme inhibiteurs d'hydrosilylation dans des compositions silicones durcissables à base d'un polymère organosilicique portant des substituants à insaturation oléfinique (vinylique notamment), d'un polymère organohydrogénosiloxane et d'un catalyseur du type platine ou composé du platine. La présence de ces composés acétyléniques inhibe le catalyseur au platine en l'empêchant de catalyser la réaction de durcissement à la température ambiante, mais non à température élevée. En effet, les compositions silicones durcissables qui contiennent ce type d'inhibiteur peuvent être durcies en augmentant la température de la composition à une température supérieure au point d'ébullition ou de sublimation de l'inhibiteur, en évaporant ainsi l'inhibiteur, ou une partie de l'inhibiteur, et en permettant au catalyseur de catalyser la réaction d'hydrosilylation et par conséquent de durcir la composition silicone. It is known, see for example US Pat. No. 3,445,420, to use acetylenic compounds such as acetylenic alcohols having a boiling point of less than 250 ° C., especially 2-methyl-3-butyne-2-ol and ethynylcyclohexanol, as hydrosilylation inhibitors in curable silicone compositions based on an organosilicon polymer bearing olefinically unsaturated substituents (vinylic in particular), an organohydrogensiloxane polymer and a platinum or platinum-type catalyst. The presence of these acetylenic compounds inhibits the platinum catalyst by preventing it from catalyzing the curing reaction at room temperature, but not at elevated temperature. Indeed, curable silicone compositions which contain this type of inhibitor can be cured by increasing the temperature of the composition to a temperature above the boiling point or sublimation of the inhibitor, thus evaporating the inhibitor, or part of the inhibitor, and allowing the catalyst to catalyze the hydrosilylation reaction and thereby cure the silicone composition.
L'utilité de ces composés inhibiteurs est reconnue et permet de transporter les compositions sous un seul emballage au lieu de deux. Ils peuvent aussi servir à prolonger le temps de mise en œuvre ou la durée de vie en pot, en comparaison de compositions ne contenant pas le composé acétylénique. Ces compositions peuvent être déposées sur des supports tels que le papier, par enduction par exemple et durcies thermiquement à une température de l'ordre de 80 à 250°C, notamment entre 100 et 220°C voir par exemple les brevets FR-A-1 528 464 et FR-A-2 372 874. The utility of these inhibiting compounds is recognized and allows the compositions to be transported in one package instead of two. They can also be used to prolong the processing time or the pot life, in comparison with compositions that do not contain the acetylenic compound. These compositions can be deposited on substrates such as paper, for example by coating and thermally cured at a temperature of the order of 80 to 250 ° C., in particular between 100 and 220 ° C. See, for example, the FR-A- patents. 1,528,464 and FR-A-2,372,874.
Ces compositions présentent l'inconvénient, pour la préparation de revêtements antiadhérents, de ne pouvoir réticuler sur le support à une température inférieure à 80°C et de présenter une stabilité insuffisante en cours d'enduction sur machine, la gélification du bain d'enduction se manifestant déjà au bout d'une heure. Cela est du au fait que ces inhibiteurs sont sublimables. Cet inconvénient majeur exige de les utiliser en quantité importante, ce qui se traduit par une forte inhibition de l'activité du platine et par voie de conséquence à un ralentissement de la vitesse de réticulation ce qui oblige à réduire les cadences d'enduction. II est à noter que la référence US-5,496,906 décrit un pré-traitement acide d'une charge utilisée dans une composition silicone afin d'éliminer les dérivés de type nitrosamine lors de la formation de l'élastomère après réticulation. Cette charge est incorporée dans une huile silicone vinylée et est traitée par chauffage à une température comprise entre 70 et 80°C pendant une heure en présence d'un vinyltriéthoxysilane, d'eau et d'un acide. Lorsque le traitement chimique est terminé, le mélange subit une étape de « stripping » à 140°C et sous vide afin d'éliminer tous les sous-produits de la réaction (voir exemple 1 , colonne 6). These compositions have the drawback, for the preparation of anti-adhesive coatings, of being unable to crosslink on the support at a temperature below 80 ° C. and of having insufficient stability during coating on a machine, the gelling of the coating bath. already showing up after an hour. This is because these inhibitors are sublimable. This major disadvantage requires the use of significant amounts, which results in a strong inhibition of platinum activity and consequently a slower rate of crosslinking which requires reducing coating rates. It should be noted that the reference US Pat. No. 5,496,906 describes an acid pretreatment of a filler used in a silicone composition in order to eliminate the nitrosamine derivatives during the formation of the elastomer after crosslinking. This filler is incorporated in a vinyl silicone oil and is treated by heating at a temperature between 70 and 80 ° C for one hour in the presence of a vinyltriethoxysilane, water and an acid. When the chemical treatment is complete, the mixture undergoes a "stripping" step at 140 ° C and under vacuum to remove all by-products of the reaction (see Example 1, column 6).
La référence US-2007/0167563 décrit à l'exemple comparatif C1 l'utilisation d'un acide trifluorométhane sulphonique comme catalyseur dans la préparation d'un polysiloxane vinylé comprenant des motifs siloxyles Q et à partir d'un The reference US-2007/0167563 describes in Comparative Example C1 the use of a trifluoromethanesulfonic acid as catalyst in the preparation of a vinyl polysiloxane comprising siloxyl units Q and from a
tétra(diméthylvinylsiloxy)silane. L'homme du métier comprendra qu'à la lecture de l'exemple 1 , la fin de la réaction est suivie d'une étape de neutralisation afin d'éviter la présence de cet acide. tetra (dimethylvinylsiloxy) silane. Those skilled in the art will understand that upon reading of Example 1, the end of the reaction is followed by a neutralization step to avoid the presence of this acid.
Force est donc de constater que les propositions techniques antérieures n'apportent pas de solutions satisfaisantes au problème exposé ci-dessus. It must therefore be noted that the previous technical proposals do not provide satisfactory solutions to the problem set out above.
L'un des objectifs essentiels de la présente invention est de fournir un nouvel inhibiteur ne présentant pas les inconvénients cités ci-dessus. One of the essential objectives of the present invention is to provide a novel inhibitor not having the disadvantages mentioned above.
Un autre objectif essentiel de la présente invention est de fournir une composition silicone X à bas taux de platine, c'est-à-dire ayant moins de 50 ppm en poids de platine par rapport au poids total de la composition et susceptible de durcir par une réaction de polyaddition qui: Another essential objective of the present invention is to provide a silicone composition X with a low platinum content, that is to say having less than 50 ppm by weight of platinum. relative to the total weight of the composition and capable of hardening by a polyaddition reaction which:
- est stable pendant plusieurs heures pour permettre par exemple les opérations d'enduction sur machine ;  is stable for several hours to allow, for example, machine coating operations;
- réticule rapidement sur support à une température de durcissement inférieure à - reticle quickly on support at a curing temperature below
120°C, et 120 ° C, and
- présente une grande stabilité de bain à 25°C et 40°C.  - exhibits high bath stability at 25 ° C and 40 ° C.
Ainsi l'objet principal de l'invention consiste en une composition silicone X Thus the main object of the invention consists of a silicone composition X
susceptible de durcir par une réaction de polyaddition comprenant: capable of hardening by a polyaddition reaction comprising:
(1) au moins un organopolysiloxane A comportant par molécule au moins deux radicaux alcényles liés à des atomes de silicium,  (1) at least one organopolysiloxane A comprising, by molecule, at least two alkenyl radicals bonded to silicon atoms,
(2) au moins un organohydrogénopolysiloxane B comportant par molécule au moins deux atomes d'hydrogène liés à des atomes de silicium,  (2) at least one organohydrogenpolysiloxane B having, per molecule, at least two hydrogen atoms bonded to silicon atoms,
(3) au moins un catalyseur C qui est un composé du platine et encore plus préférentiellement un platine de Karsted, dont la quantité en poids de platine du catalyseur C par rapport au poids total de la composition silicone X est inférieure à 50 ppm et de préférence comprise entre 1 et 40 ppm et encore plus préférentiellement comprise entre 5 et 25 ppm,  (3) at least one catalyst C which is a platinum compound and even more preferably a Karsted platinum, the amount by weight of platinum of catalyst C relative to the total weight of silicone composition X is less than 50 ppm and preferably between 1 and 40 ppm and even more preferably between 5 and 25 ppm,
(4) au moins un inhibiteur D qui est susceptible d'être obtenu par mélange, éventuellement in situ:  (4) at least one inhibitor D that can be obtained by mixing, optionally in situ:
- d'au moins un inhibiteur D1 qui est un alcool acétylénique et de préférence un alcool cc-acétylénique, et  at least one inhibitor D1 which is an acetylenic alcohol and preferably a cc-acetylenic alcohol, and
- d'au moins un acide D2 présentant en solution aqueuse et à 25 °C au moins un pKa < -0,9, de préférence≤-1 ,0 et encore plus préférentiellement compris dans l'interval suivant -12,0 < pKa < -1 ,0,  at least one acid D2 having in aqueous solution and at 25 ° C at least one pKa <-0.9, preferably≤-1, 0 and even more preferably within the following range -12.0 <pKa <-1, 0,
lesdits constituants D1 et D2 étant initialement présents dans ladite composition silicone X dans des quantités suffisantes pour:  said constituents D1 and D2 being initially present in said silicone composition X in amounts sufficient to:
- maintenir l'inhibition du catalyseur C de manière à éviter la formation d'un gel ou d'un élastomère lorsque ladite composition silicone X est stockée à température ambiante, et  maintain the inhibition of catalyst C so as to avoid the formation of a gel or an elastomer when said silicone composition X is stored at room temperature, and
- permettre la dégradation partielle ou complète dudit alcool acétylénique D1 par réaction chimique entre l'inhibiteur D1 et l'acide D2 lorsque la composition silicone X est durcie par chauffage à une température comprise entre 70 °C et 200°C.  allowing partial or complete degradation of said acetylenic alcohol D1 by chemical reaction between the inhibitor D1 and the acid D2 when the silicone composition X is cured by heating at a temperature of between 70 ° C. and 200 ° C.
La demanderesse a trouvé de façon tout-à-fait inattendue, ce qui fait précisément l'objet de la présente invention, que dans des compositions silicones susceptibles de durcir par une réaction de polyaddition contenant un bas taux de platine, c'est-à-dire ayant des quantités en poids de platine inférieures à 50 ppm par rapport au poids total de la composition, l'emploi d'un inhibiteur D qui est obtenu par mélange, éventuellement in situ, d'un inhibiteur d'hydrosilylation D1 qui est un alcool acétylénique et d'un acide fort D2 présentant en solution aqueuse et à 25 °C au moins un pKa < -0,9, permet d'obtenir des compositions: The Applicant has found quite unexpectedly, which is the subject of the present invention, only in silicone compositions capable of hardening by a polyaddition reaction containing a low level of platinum, that is to say -say with quantities by weight of platinum less than 50 ppm relative to the total weight of the composition, the use of an inhibitor D which is obtained by mixing, optionally in situ, a hydrosilylation inhibitor D1 which is an alcohol acetylenic acid and a strong acid D2 having in aqueous solution and at 25 ° C at least one pKa <-0.9, provides compositions:
. qui sont stables pendant plusieurs heures lors des opérations d'enduction sur machine,  . which are stable for several hours during machine coating operations,
. qui réticulent rapidement sur support à une température de durcissement inférieure à 120°C, et  . which rapidly cross-link at a cure temperature of less than 120 ° C, and
. qui présentent une bonne stabilité de bain à 25°C et 40°C.  . which have good bath stability at 25 ° C and 40 ° C.
Il est à remarquer que ces résultats sont obtenus avec des quantités en poids de catalyseur au platine faibles, c'est-à-dire inférieure à 50 ppm en poids de platine par rapport au poids total de la composition. It should be noted that these results are obtained with quantities by weight of platinum catalyst low, that is to say less than 50 ppm by weight of platinum relative to the total weight of the composition.
Des exemples d'acide D2 utiles selon l'invention sont par exemple choisis parmi le groupe constitué par les acides suivants: Examples of the acid D2 which are useful according to the invention are, for example, chosen from the group consisting of the following acids:
- H2Cr04, Hl, HMn04l HN03, HRe04, H2S04, CF3SO3H, CH3SO3H, HCI, HBr, HCI04, H2S04, HN03, H2Cr0 , HCIO3 et Hl. - H 2 Cr0 4, Hl, HMn0 4l HN0 3, HRe0 4, H 2 S0 4, CF3SO 3 H, CH 3 SO 3 H, HCl, HBr, hci0 4, H 2 S0 4, HN0 3, H 2 Cr0, HCIO3 and H1.
Selon un autre mode de réalisation préféré, l'acide D2 est choisi parmi le groupe constitué par CF3S03H et CH3S03H et selon un mode encore plus avantageux l'acide D2 est l'acide méthane sulfonique de formule CH3S03H. D'une manière préférée, le ratio molaire [inhibiteur D1]/[acide D2] est compris entreAccording to another preferred embodiment, the acid D 2 is chosen from the group consisting of CF 3 SO 3 H and CH 3 SO 3 H and, in an even more advantageous mode, the acid D 2 is the methanesulfonic acid of formula CH 3 S0 3 H. In a preferred manner, the molar ratio [D1 inhibitor] / [D2 acid] is between
0,1 et 10, de préférence entre 0,5 et 5. 0.1 and 10, preferably between 0.5 and 5.
Il est avantageux que le ratio en poids [inhibiteur D1]/[catalyseur C] soit compris entre 30 et 2000 et le ratio molaire [acide D2]/[catalyseur C] soit compris entre 1 et 200. It is advantageous that the ratio by weight [inhibitor D1] / [catalyst C] is between 30 and 2000 and the molar ratio [acid D2] / [catalyst C] is between 1 and 200.
Des alcools acétyléniques D1 utiles selon l'invention peuvent être choisis parmi le groupe constitué par les composés suivants: Acetylenic alcohols D1 useful according to the invention may be chosen from the group consisting of the following compounds:
- le 1-éthynyl-1-cyclohexanol, le 2-méthyl-3-butyn-2-ol, le 3,7,11-triméthyl-1-dodécyne- 3-ol, le 3,5-diméthyl-1-hexyn-3-ol, le 1-éthynyl-1-cyclopentanol, le 3-méthyl-1- dodécyne-3-ol ; le 1 ,1-diphényl-2-propyne-1-ol; le 3,6-diéthyl-1-nonyne-3-ol; le 3- méthyl-1-pentadécyne-3-ol , le 2,5-diméthyl-3-hexyne-2,5-diol, le 2,7-diméthyl-3-5- octadiyne-2,7-diol, le 3-méthyl-1-pentyn-3-ol, le 2,4,7, 9-tétraméthyl-5-décyne-4,7-diol, le 1 ,4-bis(1'-hydroxycyclohexyl)-1 ,3-butadiyne, le 1-(1-butynyl)cyclopentanol, le 2,5- diméthyl-5-hexèn-3-yn-2-ol, le 5-diméthylamino-2-méthyl-3-pentyn-2-ol, le 3,6- diméthyl-6-heptèn-4-yn-3-ol, le 3-méthyl-1-octyn-3-ol, le 3,4,4-triméthyl-1-pentyn-3-ol, le 3-isobutyl-5-méthyl-1-hexyn-3-ol, le 2,5,8-triméthyl-1-nonèn-3-yn-5-ol, le 1-(1- propynyl)cyclohexanol, le 3,4-diméthyl-1-pentyn-3,4-diol, le 2,3,6,7-tétraméthyl-4- octyn-3,6-diol et le 4-éthyl-1-octyn-3-ol. 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 3,7,11-trimethyl-1-dodecyn-3-ol, 3,5-dimethyl-1-hexyn 3-ol, 1-ethynyl-1-cyclopentanol, 3-methyl-1-dodecyn-3-ol; 1,1-diphenyl-2-propyn-1-ol; 3,6-diethyl-1-nonyne-3-ol; 3-methyl-1-pentadecyne-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,7-dimethyl-3-5-octadyne-2,7-diol, 3-methyl-1-pentyn-3-ol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 1,4-bis (1'-hydroxycyclohexyl) -1,3- butadiyne, 1- (1-butynyl) cyclopentanol, 2,5- 5-dimethyl-hexen-3-yn-2-ol, 5-dimethylamino-2-methyl-3-pentyn-2-ol, 3,6-dimethyl-6-hepten-4-yn-3-ol, 3-methyl-1-octyn-3-ol, 3,4,4-trimethyl-1-pentyn-3-ol, 3-isobutyl-5-methyl-1-hexyn-3-ol, 2, 5,8-trimethyl-1-nonen-3-yn-5-ol, 1- (1-propynyl) cyclohexanol, 3,4-dimethyl-1-pentyn-3,4-diol, 2,3, 6,7-tetramethyl-4-octyn-3,6-diol and 4-ethyl-1-octyn-3-ol.
Le catalyseur C qui est un catalyseur de la réaction d'hydrosilylation est également bien connu. On peut, en particulier, utiliser le platine ou les complexes du platine et d'un produit organique décrit dans les brevets US-A-3 159 601 , US-A-3 220 972 et les brevets européens EP-A-0 057 459, EP-A-0 188 978 et EP-A-0 190 530, les complexes du platine et d'organosiloxanes vinylés décrits dans les brevets US-A-3 419 593, US-A-3 715 334 et US-A-3 814 730. Catalyst C which is a catalyst for the hydrosilylation reaction is also well known. Platinum or complexes of platinum and an organic product described in US Pat. Nos. 3,159,601 and 3,220,972 and European patents EP-A-0 057 459 can be used in particular. , EP-A-0 188 978 and EP-A-0 190 530, the complexes of platinum and vinyl organosiloxanes described in US-A-3,419,593, US-A-3,715,334 and US Pat. 3,814,730.
Selon une variante de l'invention, les proportions de l'organopolysiloxane A et de l'organohydrogénopolysiloxane B sont telles que le rapport molaire des atomes d'hydrogène liés au silicium dans l'organohydrogénopolysiloxane B sur les radicaux alcényles liés au silicium dans l'organopolysiloxane A est compris entre 0,4 et 10. According to a variant of the invention, the proportions of the organopolysiloxane A and of the organohydrogenpolysiloxane B are such that the molar ratio of the silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane B on the silicon-bonded alkenyl radicals in the organopolysiloxane A is between 0.4 and 10.
Avantageusement, l'organopolysiloxane A selon l'invention présente:  Advantageously, the organopolysiloxane A according to the invention has:
- au moins deux motifs siloxyles de formule (A.1):  at least two siloxyl units of formula (A.1):
Ta Zb SiO4-(a+b)/2 (A.1) T a Z b SiO 4- (a + b) / 2 (A.1)
dans laquelle :  in which :
- T est un groupe alcényle,  T is an alkenyl group,
- Z est un groupe hydrocarboné monovalent, exempt d'action défavorable sur l'activité du catalyseur et choisi parmi le groupe constitué par les groupes alkyles ayant de 1 à 8 atomes de carbone inclus, éventuellement substitués par au moins un atome d'halogène, et les groupes aryles, et  Z is a monovalent hydrocarbon group, which has no adverse effect on the activity of the catalyst and is selected from the group consisting of alkyl groups having from 1 to 8 carbon atoms inclusive, optionally substituted with at least one halogen atom, and aryl groups, and
- a est égal à 1 ou 2, b est égale à 0, 1 ou 2 et la somme a + b est comprise entre 1 et 3, et  a is equal to 1 or 2, b is equal to 0, 1 or 2 and the sum a + b is between 1 and 3, and
- éventuellement au moins une partie des autres motifs siloxyles sont des motifs de formule (A.2):  optionally at least a part of the other siloxyl units are units of formula (A.2):
Zc SiO4-c 2 (A.2) Z c SiO 4-c 2 (A.2)
dans laquelle:  in which:
- Z a la même signification que ci-dessus et c est égal à 0, 1 , 2 ou 3. En général, l'organopolysiloxane A a une viscosité au moins égale à 100 mPa.s et de préférence inférieure à 200.000 mPa.s.  Z has the same meaning as above and c is 0, 1, 2 or 3. In general, the organopolysiloxane A has a viscosity of at least 100 mPas and preferably less than 200,000 mPas. .
Avantageusement, l'organohydrogénopolysiloxane B selon l'invention présente: - au moins deux, et de préférence au moins trois, motifs siloxyles de formule (B.1): Advantageously, the organohydrogenpolysiloxane B according to the invention has: at least two, and preferably at least three, siloxyl units of formula (B.1):
Hd Le Si04-(d+e)/2 (B.1) H d L e Si0 4- (d + e) / 2 (B.1)
dans laquelle:  in which:
- L est un groupe hydrocarboné monovalent, exempt d'action défavorable sur l'activité du catalyseur et choisi parmi le groupe constitué par les alkyles ayant de 1 à 8 atomes de carbone inclus, éventuellement substitués par au moins un atome d'halogène, et les aryles,  L is a monovalent hydrocarbon group, which has no adverse effect on the activity of the catalyst and is selected from the group consisting of alkyls having 1 to 8 carbon atoms inclusive, optionally substituted with at least one halogen atom, and the aryls,
- H est un atome d'hydrogène, et  H is a hydrogen atom, and
- d est égal à 1 ou 2, e est égal à 0, 1 ou 2, la somme d + e est égale à 1 , 2 ou 3, et  d is 1 or 2, e is 0, 1 or 2, the sum d + e is 1, 2 or 3, and
- éventuellement, au moins une partie des autres motifs siloxyles sont des motifs de formule (B.2): optionally, at least a part of the other siloxyl units are units of formula (B.2):
dans laquelle:  in which:
- L a la même signification que ci-dessus et g est égal à 0, 1 , 2 ou 3.  L has the same meaning as above and g is 0, 1, 2 or 3.
En général, la viscosité dynamique de l'organohydrogénopolysiloxane B est au moins égale à 10 mPa.s et, de préférence elle est comprise entre 20 et 1000 mPa.s. Avantageusement, les proportions des motifs siloxyles (A.1) et (B.1) sont telles que le rapport molaire des atomes d'hydrogène liés au silicium dans l'organohydrogénopolysiloxane B sur les radicaux alcényles liés au silicium dans , l'organopolysiloxane A est compris entre 0,4 et 10. Selon une variante de l'invention, la composition silicone X selon l'invention peut comprendre un ou plusieurs additifs classiques dans le domaine des revêtements anti- adhérents silicones pour support solide, par exemple en papier. Il peut s'agir par exemple d'un additif anti-brouillard ("anti-misting") tels que des particules de silice, ou des polyorganosiloxanes branchés,... In general, the dynamic viscosity of the organohydrogenpolysiloxane B is at least 10 mPa.s and preferably it is between 20 and 1000 mPa.s. Advantageously, the proportions of the siloxyl units (A.1) and (B.1) are such that the molar ratio of the silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane B to the silicon-bonded alkenyl radicals in the organopolysiloxane A is between 0.4 and 10. According to one variant of the invention, the silicone composition X according to the invention may comprise one or more conventional additives in the field of silicone release coatings for solid support, for example paper. It may be for example an anti-misting additive such as silica particles, or branched polyorganosiloxanes, etc.
Selon une variante, la composition silicone X selon l'invention peut aussi comprendre un système modulateur d'adhérence ainsi que des additifs usuels dans ce type d'application tels que: des bactéricides, des agents antigels, des agents de mouillage, des agents anti-mousses, des charges, des latex synthétiques ou des colorants. According to one variant, the silicone composition X according to the invention may also comprise an adhesion modulator system as well as additives that are customary in this type of application, such as: bactericides, anti-freeze agents, wetting agents, anti-blocking agents - foams, fillers, synthetic latexes or dyes.
Selon un autre de ses aspects, la présente invention concerne un élastomère silicone Y obtenu par réticulation ou durcissement de la composition silicone X selon l'invention et telle que décrite ci-dessus, ladite réticulation ou durcissement s'effectuant à une température comprise entre 70 °C et 200°C. According to another of its aspects, the present invention relates to a silicone elastomer Y obtained by crosslinking or curing the silicone composition X according to the invention and as described above, said crosslinking or curing being carried out at a temperature between 70 ° C and 200 ° C.
La présente invention concerne également l'utilisation de la composition silicone X selon l'invention comme base d'enduction pour la réalisation de revêtements élastomère réticulés antiadhérents et hydrofuges sur un support solide, de préférence un support solide souple tel qu'un papier, un carton, une feuille de cellulose, une feuille en métal ou un film de matière plastique. Un autre objet de l'invention consiste en un support solide au moins en partie revêtu à l'aide de la composition silicone X selon l'invention et telle que décrite ci-dessus, et réticulé ou durcit par chauffage à une température comprise entre 70°C et 200°C ou de l'élastomère silicone Y selon l'invention et tel que décrit ci-dessus. L'invention concerne aussi un inhibiteur D de la réaction d'hydrosilylation qui est susceptible d'être obtenu par mélange: The present invention also relates to the use of the silicone composition X according to the invention as a coating base for the production of crosslinked elastomeric anti-adhesive and water-repellent coatings on a solid support, preferably a flexible solid support such as a paper, a cardboard, a cellulose sheet, a metal sheet or a plastic film. Another subject of the invention consists of a solid support at least partly coated with the silicone composition X according to the invention and as described above, and crosslinked or cured by heating to a temperature of between 70.degree. ° C and 200 ° C or Y silicone elastomer according to the invention and as described above. The invention also relates to an inhibitor D of the hydrosilylation reaction which is obtainable by mixing:
- d'au moins un inhibiteur D1 selon l'invention et tel que décrit ci-dessus qui est un alcool acétylénique et de préférence un alcool α-acétylénique, et  at least one inhibitor D1 according to the invention and as described above which is an acetylenic alcohol and preferably an α-acetylenic alcohol, and
- d'au moins un acide D2 présentant en solution aqueuse et à 25 °C au moins un pKa < -0,9, de préférence <-1 ,0 et encore plus préférentiellement compris dans l'intervalle suivant -12,0 < pKa < -1 ,0.  at least one D2 acid having in aqueous solution and at 25 ° C at least one pKa <-0.9, preferably <-1.0, and even more preferably within the range -12.0 <pKa <-1, 0.
Un autre objet de l'invention consiste en l'utilisation de l'inhibiteur D de la réaction d'hydrosilylation selon l'invention et tel que décrit ci-dessus dans des compostions silicones durcissable ou réticulable comprenant : Another subject of the invention consists in the use of the inhibitor D of the hydrosilylation reaction according to the invention and as described above in curable or crosslinkable silicone compositions comprising:
(1) au moins un organopolysiloxane A comportant par molécule au moins deux radicaux alcényles liés à des atomes de silicium,  (1) at least one organopolysiloxane A comprising, by molecule, at least two alkenyl radicals bonded to silicon atoms,
(2) au moins un organohydrogénopolysiloxane B comportant par molécule au moins deux atomes d'hydrogène liés à des atomes de silicium, et  (2) at least one organohydrogenpolysiloxane B having per molecule at least two hydrogen atoms bonded to silicon atoms, and
(3) au moins un catalyseur C qui est un composé du platine et encore plus préférentiellement un platine de Karsted et la quantité en poids de platine du catalyseur C par rapport au poids total de la composition silicone X est inférieure à 50 ppm et de préférence comprise entre 1 et 40 ppm et encore plus préférentiellement comprise entre 5 et 25 ppm.  (3) at least one catalyst C which is a platinum compound and even more preferably a Karsted platinum and the amount by weight of platinum of the catalyst C relative to the total weight of the silicone composition X is less than 50 ppm and preferably between 1 and 40 ppm and even more preferably between 5 and 25 ppm.
La présente invention concerne enfin un procédé permettant de rendre des feuilles en matériau souples non adhérentes à des surfaces auxquelles elles adhèrent normalement, caractérisé en ce qu'il consiste à appliquer une quantité de la composition silicone X selon l'invention et telle que décrite ci-dessus, entre 0,1 et 5 g par m2 de surface à enduire puis à réticuler la composition par chauffage à une température comprise entre 70°C et 200°C. La composition silicone X selon l'invention peut être appliquée à l'aide de dispositifs utilisés sur les machines industrielles d'enduction du papier tels qu'une tête d'enduction à cinq rouleaux, des systèmes à lames d'air ou à barre égalisatrice, sur des supports ou matériaux souples, puis durcie par circulation dans des fours-tunnels chauffés à 70- 200°C; le temps de passage dans ces fours est fonction de la température; celui-ci est généralement de 5 à 15 secondes à une température de 100°C et de 1 ,5 à 3 secondes à une température de 180°C. The present invention finally relates to a method for rendering soft material sheets non-adherent to surfaces to which they adhere normally, characterized in that it consists in applying a quantity of the composition silicone X according to the invention and as described above, between 0.1 and 5 g per m 2 of surface to be coated and then crosslink the composition by heating at a temperature between 70 ° C and 200 ° C. The silicone composition X according to the invention can be applied using devices used on industrial paper coating machines such as a five-roll coating head, air knife or equalizer systems. , on flexible substrates or materials, then cured by circulation in tunnel kilns heated to 70-200 ° C; the passage time in these furnaces is a function of the temperature; this is usually from 5 to 15 seconds at a temperature of 100 ° C and from 1.5 to 3 seconds at a temperature of 180 ° C.
La composition silicone X peut être déposée sur tout matériau ou substrat souple tel que papiers de types divers (supercalendré, couché, glassine), cartons, feuilles de cellulose, feuilles en métal, films de matière plastique (polyester, polyéthylène, polypropylène...) ... The silicone composition X can be deposited on any flexible material or substrate such as papers of various types (supercalendré, coated, glassine), cardboard, cellulose sheets, metal sheets, plastic films (polyester, polyethylene, polypropylene, etc.). ) ...
Les quantités de compositions déposées sont en général de l'ordre de 0,1 à 5 g par m2 de surface à traiter, ce qui correspond au dépôt de couches de l'ordre de 0,1 à 5 pm. The amounts of deposited compositions are generally of the order of 0.1 to 5 g per m 2 of surface to be treated, which corresponds to the deposition of layers of the order of 0.1 to 5 pm.
Les matériaux ou supports ainsi enduits peuvent ultérieurement être mis en contact avec des matières adhésives quelconques caoutchoucs, acryliques ou autres, sensibles à la pression. La matière adhésive est alors aisément détachable dudit support ou matériau. Toutes les viscosités dont il est question dans le présent mémoire correspondent à une grandeur de viscosité dynamique qui est mesurée, de manière connue en soi, à 25°C. The materials or supports thus coated may subsequently be brought into contact with any pressure sensitive rubber, acrylic or other adhesive materials. The adhesive material is then easily detachable from said support or material. All the viscosities referred to herein correspond to a dynamic viscosity quantity which is measured, in a manner known per se, at 25.degree.
Dans la suite de la présente demande, on décrira de façon conventionnelle les huiles polyorganosiloxanes à l'aide de la notation usuelle dans laquelle on utilise les lettres M, D, T et Q pour désigner divers motifs siloxyle. Dans cette notation, l'atome de silicium d'un motif siloxyle est engagé dans une (M), deux (D), trois (T) ou quatre (Q) liaisons covalentes avec autant d'atomes d'oxygène. Lorsqu'un atome d'oxygène est partagé entre deux atomes de silicium, il est comptabilisé pour ½ et il ne sera pas mentionné dans une formule abrégée. Par contre, si l'atome d'oxygène appartient à un groupe alcoxyle ou hydroxyle lié à un atome de silicium, cette fonction chimique sera indiquée entre parenthèses dans la formule abrégée. Par défaut, on considère que les liaisons restantes de l'atome de silicium sont engagées avec un atome de carbone. Généralement, les groupes hydrocarbonés liés au silicium par une liaison C— Si ne sont pas mentionnés et correspondent le plus souvent à un groupe alkyle, par exemple un groupe méthyle. Lorsqu'un groupe hydrocarboné possède une fonction particulière, il est indiqué en exposant. Par exemple, les formules abrégées: In the rest of the present application, the polyorganosiloxane oils will be conventionally described using the usual notation in which the letters M, D, T and Q are used to designate various siloxyl units. In this notation, the silicon atom of a siloxyl unit is engaged in one (M), two (D), three (T) or four (Q) covalent bonds with as many oxygen atoms. When an oxygen atom is shared between two silicon atoms, it is counted for ½ and it will not be mentioned in an abbreviated form. On the other hand, if the oxygen atom belongs to an alkoxyl or hydroxyl group bonded to a silicon atom, this chemical function will be indicated in parentheses in the abbreviated formula. By default, it is considered that the remaining bonds of the silicon atom are engaged with a carbon atom. Generally, Silicon bonded hydrocarbon groups via a C-Si bond are not mentioned and most often correspond to an alkyl group, for example a methyl group. When a hydrocarbon group has a particular function, it is indicated by exponent. For example, short forms:
- MV| représente un motif dans lequel l'atome de silicium est lié à un atome d'oxygène et dont l'un des groupes hydrocarbonés formant une liaison C— Si est un groupe vinyle, c'est-à-dire un motif dialkylvinylsiloxyle, et - M V | represents a unit in which the silicon atom is bonded to an oxygen atom and one of the C-Si bond-forming hydrocarbon groups is a vinyl group, i.e. a dialkylvinylsiloxyl unit, and
- M' représente un motif dans lequel l'atome de silicium est lié à un atome d'hydrogène, à un atome et à deux groupements méthyles.  M 'represents a unit in which the silicon atom is bonded to a hydrogen atom, to an atom and to two methyl groups.
A titre d'ouvrage de référence, on peut citer : NOLL " Chemistry and technology of silicones ", chapitre 1.1 , page 1-9, Académie Press, 1968 - 2ème édition. As a reference work, mention may be made of: NOLL "Chemistry and Technology of Silicones", Chapter 1.1, page 1-9, Académie Press, 1968 - 2nd edition.
Les exemples non-limitatifs qui suivent permettront de mieux comprendre l'invention et d'en saisir tous ses avantages et variantes de réalisation. The following non-limiting examples will make it possible to better understand the invention and to grasp all its advantages and variants.
EXEMPLES EXAMPLES
Produits utilisés  Products used
Les valeurs de pKa sont celles mesurées en solution aqueuse et à 25°C. The pKa values are those measured in aqueous solution and at 25 ° C.
- Huile polydiméthylsiloxane vinylée bout de chaîne (A.2): de formule moyenne - End-chain vinylated polydimethylsiloxane oil (A.2): of medium formula
MviD110DviMvi. M vi D 110 D vi M vi .
- Huiles polyméthylhydrogénosiloxanes (B.2): mélange: 18% en poids d'une huile de formule moyenne Mii4D'i4D2iMo,6-+ 82% d'une huile polyméthylhydrogénosiloxanes de structure MD'40M. - Oils polymethylhydrosiloxanes (B.2): mixture: 18% by weight of an oil having the average formula I4 i Mi D2iMo 4, 6- + 82% of an oil polymethylhydrogenosiloxanes MD structure '40 M.
- Catalyseur (C) : Pt Karstedt contenant 2800 ppm de Pt.  Catalyst (C): Pt Karstedt containing 2800 ppm Pt.
- lnhibiteur:(D1.M) : 1-éthynyl-1-cyclohexanol (ECH)  inhibitor: (D1.M): 1-ethynyl-1-cyclohexanol (ECH)
- Acide comparatif  - Comparative acid
- acide heptanoïque (D2.C1): CH3(CH2)5COOH, (pK1=: 4,89). heptanoic acid (D 2 Cl): CH 3 (CH 2 ) 5 COOH, (pK 1 = 4.89).
- acide orthophosphorique (D2.C2): (H3P04) (pK1= 2,15). orthophosphoric acid (D2.C2): (H 3 PO 4 ) (pK 1 = 2.15).
- Acides selon l'invention::  - Acids according to the invention ::
- acide méthanesulfonique (D2.I1): (pK1 = -1 ,9). Exemple 1 : methanesulfonic acid (D2.I1): (pK1 = -1, 9). Example 1
L'inhibiteur ECH (D1.I1) est préalablement ajouté à l'huile polydiméthylsiloxane vinylée (A.1). Après homogénéisation du mélange, on introduit alors l'huile polyméthylhydrogéno siloxane (B.1) puis la quantité d'acide à tester et enfin le catalyseur (C). On mesure le temps nécessaire à la réticulation à température ambiante (25°C) et à 40°C = la durée de vie de bain à 25°C et à 40°C. Les résultats sont consignés dans le Tableau 1 suivant. The inhibitor ECH (D1.I1) is previously added to the vinylated polydimethylsiloxane oil (A.1). After homogenization of the mixture, the polymethylhydrogen siloxane oil (B.1) is then introduced, then the amount of acid to be tested and finally the catalyst (C). The time required for the crosslinking is measured at room temperature (25 ° C.) and at 40 ° C. = the bath life at 25 ° C. and at 40 ° C. The results are reported in the following Table 1.
Tableau 1 Table 1
Ratio molaire [H/Vinyle]  Ratio molar [H / Vinyl]
On remarque que lorsque la quantité de catalyseur en platine est de 50 ppm par rapport au poids total de la composition la présence de quantités variables d'acide méthanesulfonique (D2.I1) ne permet pas d'obtenir une durée de vie de bain satisfaisante, surtout à 40°C. Exemple 2: Note that when the amount of platinum catalyst is 50 ppm relative to the total weight of the composition, the presence of varying amounts of methanesulfonic acid (D2.I1) does not provide a satisfactory bath life, especially at 40 ° C. Example 2
L'inhibiteur ECH (D1.I1) est préalablement ajouté à l'huile polydiméthylsiloxane vinylée (A.1). Après homogénéisation du mélange, on introduit alors l'huile polyméthylhydrogéno siloxane (B.1) puis une quantité fixe de 500 ppm (par rapport au poids total de la composition) de l'acide à tester et enfin une quantité variable du catalyseur (C). On mesure le temps nécessaire à la réticulation à température ambiante (25°C) et à 40°C = la durée de vie de bain à 25°C et à 40°C. Les résultats sont consignés dans le Tableau 2 suivant. The inhibitor ECH (D1.I1) is previously added to the vinylated polydimethylsiloxane oil (A.1). After homogenization of the mixture, the polymethylhydrogen siloxane oil (B.1) is then introduced, then a fixed quantity of 500 ppm (relative to the total weight of the composition) of the acid to be tested and finally a variable amount of the catalyst (C ). The time required for the crosslinking is measured at room temperature (25 ° C.) and at 40 ° C. = the bath life at 25 ° C. and at 40 ° C. The results are reported in the following Table 2.
Tableau 2 Table 2
On remarque que les essais selon l'invention (quantité en poids de platine inférieure à 50 ppm par rapport au poids total de la composition), permettent d'obtenir de très bonnes durées de vie du bain à 25°C qui sont de l'ordre de 24h au lieu de 3h. A 40°C l'amélioration des compositions selon l'invention est de l'ordre de 400% à 650%. Exemple 3: It should be noted that the tests according to the invention (amount by weight of platinum less than 50 ppm relative to the total weight of the composition) make it possible to obtain very good service life of the bath at 25.degree. order of 24h instead of 3h. At 40 ° C the improvement of the compositions according to the invention is of the order of 400% to 650%. Example 3
L'inhibiteur ECH (D1.I1) est préalablement ajouté à l'huile polydiméthylsiloxane vinylée (A.1). Après homogénéisation du mélange, on introduit alors l'huile polyméthylhydrogéno siloxane (B.1) puis l'acide à tester et enfin la quantité de catalyseur (C) est fixée à 10 ppm de platine par rapport au poids total de la composition. Les formulations sont consignées dans le Tableau 3 suivant :  The inhibitor ECH (D1.I1) is previously added to the vinylated polydimethylsiloxane oil (A.1). After homogenization of the mixture, the polymethylhydrogensiloxane oil (B.1) is then introduced, followed by the acid to be tested, and finally the amount of catalyst (C) is fixed at 10 ppm platinum relative to the total weight of the composition. The formulations are recorded in the following Table 3:
Tableau 3 Table 3
Un échantillon pour chaque composition est prélevé et analysé en DSC (« Differential Scanning Calorimetry », appareil de type METLER). L'analyse est effectuée en capsule aluminium et en utilisant une rampe de température de 25 à 250°C avec un gradient de 10°C/min. Cette technique permet de mesurer pour chaque composition, la température de début de pic (démarrage de la réaction de réticulation) ou « T°C onset », la température de sommet de pic (« T°C pic ») et la température de fin de pic (« T°C endset »). Les profils thermiques, les données caractéristiques des pics exothermiques ("PC onset, "PC pic et "PC endset) sont représentés dans le Tableau 4 suivant. A sample for each composition is taken and analyzed in DSC ("Differential Scanning Calorimetry", METLER type device). The analysis is carried out in aluminum capsule and using a temperature ramp of 25 to 250 ° C. with a gradient of 10 ° C./min. This technique makes it possible to measure for each composition, the temperature peak start (starting the crosslinking reaction) or "T ° C onset", the peak peak temperature ("T ° C peak") and the peak end temperature ("T ° C endset"). Thermal profiles, the characteristic data of the exothermic peaks ( "PC onset," peak PC and "PC endset) are shown in the following Table 4.
Tableau 4 : Résultats par analyse DSC Table 4: Results by DSC Analysis
On constate que lorsque les compositions contiennent un faible poids en platine (10 ppm par rapport au poids total de la composition), la levée d'inhibition est bien plus rapide dans le cas de l'invention [composition (I-3) = avec 500 ppm d'acide méthanesulfonique, la réaction de réticulation démarre à 109,3°C] que pour les exemples comparatifs que sont les compositions : It is found that when the compositions contain a low platinum weight (10 ppm relative to the total weight of the composition), the inhibition uprising is much faster in the case of the invention [composition (I-3) = with 500 ppm of methanesulfonic acid, the crosslinking reaction starts at 109.3 ° C] than for the comparative examples that are the compositions:
- (C-5) = sans acide avec 10 ppm de platine, la réaction de réticulation démarre à 126,3°C ,  - (C-5) = without acid with 10 ppm platinum, the crosslinking reaction starts at 126.3 ° C,
- (C-6) = avec 500 ppm d'acide orthophosphorique+ 10 ppm de platine, la réaction de réticulation démarre à 119,8°C, et  (C-6) = with 500 ppm orthophosphoric acid + 10 ppm platinum, the crosslinking reaction starts at 119.8 ° C, and
- (C-7) = avec 500 ppm d'acide heptanoïque+ 10 ppm de platine, la réaction de réticulation démarre à 126,2 °C.  - (C-7) = with 500 ppm of heptanoic acid + 10 ppm of platinum, the crosslinking reaction starts at 126.2 ° C.

Claims

REVENDICATIONS - Composition silicone X susceptible de durcir par une réaction de polyaddition comprenant: CLAIMS - Silicone composition X capable of hardening by a polyaddition reaction comprising:
(1) au moins un organopolysiloxane A comportant par molécule au moins deux radicaux alcényles liés à des atomes de silicium, (1) at least one organopolysiloxane A comprising per molecule at least two alkenyl radicals linked to silicon atoms,
(2) au moins un organohydrogénopolysiloxane B comportant par molécule au moins deux atomes d'hydrogène liés à des atomes de silicium, (2) at least one organohydrogenopolysiloxane B comprising per molecule at least two hydrogen atoms linked to silicon atoms,
(3) au moins un catalyseur C qui est un composé du platine et encore plus préférentiellement un platine de Karsted dont la quantité en poids de platine du catalyseur C par rapport au poids total de la composition silicone X est inférieure à 50 ppm et de préférence comprise entre 1 et 40 ppm et encore plus préférentiellement comprise entre 5 et 25 ppm, (3) at least one catalyst C which is a platinum compound and even more preferably a Karsted platinum whose quantity by weight of platinum of catalyst C relative to the total weight of the silicone composition X is less than 50 ppm and preferably between 1 and 40 ppm and even more preferably between 5 and 25 ppm,
(4) au moins un inhibiteur D qui est susceptible d'être obtenu par mélange, éventuellement in situ: (4) at least one inhibitor D which can be obtained by mixing, possibly in situ:
- d'au moins un inhibiteur D1 qui est un alcool acétylénique et de préférence un alcool α-acétylénique, et - at least one D1 inhibitor which is an acetylenic alcohol and preferably an α-acetylenic alcohol, and
- d'au moins un acide D2 présentant en solution aqueuse et à 25 °C au moins un pKa < -0,9, de préférence≤-1 ,0 et encore plus préférentiellement compris dans l'interval suivant -12,0 < pKa ≤-1 ,0, - at least one acid D2 having in aqueous solution and at 25 °C at least a pKa < -0.9, preferably ≤-1.0 and even more preferably included in the following interval -12.0 < pKa ≤-1.0,
lesdits constituants D1 et D2 étant initialement présents dans ladite composition silicone X dans des quantités suffisantes pour: said constituents D1 and D2 being initially present in said silicone composition
- maintenir l'inhibition du catalyseur C de manière à éviter la formation d'un gel ou d'un élastomère lorsque ladite composition silicone X est stockée à température ambiante, et - maintain the inhibition of catalyst C so as to avoid the formation of a gel or an elastomer when said silicone composition X is stored at room temperature, and
- permettre la dégradation partielle ou complète dudit alcool acétylénique D1 par réaction chimique entre l'inhibiteur D1 et l'acide D2 lorsque la composition silicone X est durcie par chauffage à une température comprise entre 70 °C et 200°C. - allow the partial or complete degradation of said acetylenic alcohol D1 by chemical reaction between the inhibitor D1 and the acid D2 when the silicone composition X is hardened by heating to a temperature between 70°C and 200°C.
Composition silicone X selon la revendication 1 dans laquelle le ratio molaire [inhibiteur D1]/[acide D2] est compris entre 0,1 et 10, de préférence entre 0,5 et 5. Silicone composition
Composition silicone X selon la revendication 1 dans laquelle le ratio en poids [inhibiteur D1]/[catalyseur C] est compris entre 30 et 2000 et le ratio molaire [acide D2]/[catalyseur C] est compris entre 1 et 200. 4 - Composition silicone X selon l'une quelconque des revendications précédentes dans laquelle l'alcool acétylénique D1 est choisi parmi le groupe constitué par les composés suivants: Silicone composition 4 - Silicone composition X according to any one of the preceding claims in which the acetylenic alcohol D1 is chosen from the group consisting of the following compounds:
- le 1-éthynyl-1-cyclohexanol, le 2-méthyl-3-butyn-2-ol, le 3,7,1 1-triméthyl-1- dodécyne-3-ol, le 3,5-diméthyl-1-hexyn-3-ol, le 1-éthyny -cyclopentanol, le 3- méthyl-1-dodécyne-3-ol ; le 1 ,1-diphényl-2-propyne-1-ol; le 3,6-diéthyl-1-nonyne- 3-ol; le 3-méthyl-1-pentadécyne-3-ol , le 2,5-diméthyl-3-hexyne-2,5-diol, le 2,7- diméthyl-3-5-octadiyne-2,7-diol, le 3-méthyl-1-pentyn-3-ol, le 2,4,7,9-tétraméthyl- 5-décyne-4,7-diol, le 1 ,4-bis(1 '-hydroxycyclohexyl)-1 ,3-butadiyne, le 1-(1- butynyl)cyclopentanol, le 2,5-diméthyl-5-hexèn-3-yn-2-ol, le 5-diméthylamino-2- méthyl-3-pentyn-2-ol, le 3,6-diméthyl-6-heptèn-4-yn-3-ol, le 3-méthyl-1-octyn-3-ol, le 3,4,4-triméthyl-1-pentyn-3-ol, le 3-isobutyl-5-méthyl-1-hexyn-3-ol, le 2,5,8- triméthyl-1-nonèn-3-yn-5-ol, le 1-(1-propynyl)cyclohexanol, le 3,4-diméthyl-1- pentyn-3,4-diol, le 2,3,6,7-tétraméthyl-4-octyn-3,6-diol et le 4-éthyl-1-octyn-3-ol. - 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 3,7,1 1-trimethyl-1-dodecyn-3-ol, 3,5-dimethyl-1- hexyn-3-ol, 1-ethyny-cyclopentanol, 3-methyl-1-dodecyn-3-ol; 1,1-diphenyl-2-propyn-1-ol; 3,6-diethyl-1-nonyne-3-ol; 3-methyl-1-pentadecyn-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,7-dimethyl-3-5-octadiyne-2,7-diol, 3-methyl-1-pentyn-3-ol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 1,4-bis(1'-hydroxycyclohexyl)-1,3- butadiyne, 1-(1-butynyl)cyclopentanol, 2,5-dimethyl-5-hexen-3-yn-2-ol, 5-dimethylamino-2-methyl-3-pentyn-2-ol, 3 ,6-dimethyl-6-hepten-4-yn-3-ol, 3-methyl-1-octyn-3-ol, 3,4,4-trimethyl-1-pentyn-3-ol, 3- isobutyl-5-methyl-1-hexyn-3-ol, 2,5,8-trimethyl-1-nonen-3-yn-5-ol, 1-(1-propynyl)cyclohexanol, 3,4- dimethyl-1-pentyn-3,4-diol, 2,3,6,7-tetramethyl-4-octyn-3,6-diol and 4-ethyl-1-octyn-3-ol.
5 - Composition silicone X selon la revendication 1 dans laquelle l'acide D2 est l'acide méthane sulfonique de formule CH3S03H. 6 - Composition silicone X selon l'une quelconque des revendications précédentes caractérisée en ce que les proportions de l'organopolysiloxane A et de l'organohydrogénopolysiloxane B sont telles que le rapport molaire des atomes d'hydrogène liés au silicium dans l'organohydrogénopolysiloxane B sur les radicaux alcényles liés au silicium dans l'organopolysiloxane A est compris entre 0,4 et 10. 5 - Silicone composition X according to claim 1 in which the acid D2 is methane sulfonic acid of formula CH 3 S0 3 H. 6 - Silicone composition organopolysiloxane A and organohydrogenopolysiloxane B are such that the molar ratio of the hydrogen atoms linked to silicon in the organohydrogenopolysiloxane B to the alkenyl radicals linked to silicon in the organopolysiloxane A is between 0.4 and 10.
7 - Elastomère silicone Y obtenu par réticulation ou durcissement de la composition silicone X telle que décrite selon l'une quelconque des revendications 1 à 6, ladite réticulation ou durcissement s'effectuant à une température comprise entre 70 °C et 200°C. 7 - Silicone elastomer Y obtained by crosslinking or hardening of the silicone composition
8 - Utilisation de la composition silicone X telle que décrite selon l'une quelconque des revendications 1 à 6 comme base d'enduction pour la réalisation de revêtements élastomères réticulés antiadhérents et hydrofuges sur un support solide, de préférence un support solide souple tel qu'un papier, un carton, une feuille de cellulose, une feuille en métal ou un film de matière plastique. 9 - Support solide au moins en partie revêtu à l'aide de la composition silicone X telle que décrite selon l'une quelconque des revendications 1 à 6 et réticulé ou durcit par chauffage à une température comprise entre 70 °C et 200°C. 10 - Inhibiteur D de la réaction d'hydrosilylation qui est susceptible d'être obtenu par mélange: 8 - Use of the silicone composition paper, cardboard, cellulose sheet, metal sheet or plastic film. 9 - Solid support at least partly coated using the silicone composition 10 - Inhibitor D of the hydrosilylation reaction which can be obtained by mixing:
- d'au moins un inhibiteur D1 qui est un alcool acétylénique et de préférence un alcool a-acétylénique, et - at least one D1 inhibitor which is an acetylenic alcohol and preferably an a-acetylenic alcohol, and
- d'au moins un acide D2 présentant en solution aqueuse et à 25 °C au moins un pKa < -0,9, de préférence≤-1 ,0 et encore plus préférentiellement compris dans l'intervalle suivant -12,0≤ pKa ≤-1 ,0. - at least one D2 acid having in aqueous solution and at 25 °C at least a pKa < -0.9, preferably ≤-1.0 and even more preferably included in the following interval -12.0≤ pKa ≤-1.0.
11 - Utilisation de l'inhibiteur D de la réaction d'hydrosilylation tel que décrit selon la revendication 10 dans des compostions silicones durcissable ou réticulable comprenant : 11 - Use of the inhibitor D of the hydrosilylation reaction as described according to claim 10 in curable or crosslinkable silicone compositions comprising:
(1) au moins un organopolysiloxane A comportant par molécule au moins deux radicaux alcényles liés à des atomes de silicium, (1) at least one organopolysiloxane A comprising per molecule at least two alkenyl radicals linked to silicon atoms,
(2) au moins un organohydrogénopolysiloxane B comportant par molécule au moins deux atomes d'hydrogène liés à des atomes de silicium, et (2) at least one organohydrogenopolysiloxane B comprising per molecule at least two hydrogen atoms linked to silicon atoms, and
(3) au moins un catalyseur C qui est un composé du platine et encore plus préférentiellement un platine de Karsted et la quantité en poids de platine du catalyseur C par rapport au poids total de la composition silicone X est inférieure à 50 ppm et de préférence comprise entre 1 et 40 ppm et encore plus préférentiellement comprise entre 5 et 25 ppm. 12 - Procédé permettant de rendre des feuilles en matériau souples non adhérentes à des surfaces auxquelles elles adhèrent normalement, caractérisé en ce qu'il consiste à appliquer une quantité de la composition silicone X telle que définie selon l'une quelconque des revendications 1 à 6 comprise entre 0,1 et 5 g par m2 de surface à enduire puis à réticuler la composition par chauffage à une température comprise entre 70°C et 200°C. (3) at least one catalyst C which is a platinum compound and even more preferably a Karsted platinum and the quantity by weight of platinum of the catalyst C relative to the total weight of the silicone composition X is less than 50 ppm and preferably between 1 and 40 ppm and even more preferably between 5 and 25 ppm. 12 - Process for making sheets of flexible material non-adherent to surfaces to which they normally adhere, characterized in that it consists of applying a quantity of the silicone composition X as defined according to any one of claims 1 to 6 between 0.1 and 5 g per m 2 of surface to be coated then crosslinking the composition by heating at a temperature between 70°C and 200°C.
EP12735925.5A 2011-06-21 2012-06-19 Hydrosilylation reaction inhibitors, and use thereof for preparing stable curable silicone compositions Withdrawn EP2723816A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1101918 2011-06-21
PCT/FR2012/000249 WO2012175825A1 (en) 2011-06-21 2012-06-19 Hydrosilylation reaction inhibitors, and use thereof for preparing stable curable silicone compositions

Publications (1)

Publication Number Publication Date
EP2723816A1 true EP2723816A1 (en) 2014-04-30

Family

ID=46516794

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12735925.5A Withdrawn EP2723816A1 (en) 2011-06-21 2012-06-19 Hydrosilylation reaction inhibitors, and use thereof for preparing stable curable silicone compositions

Country Status (6)

Country Link
US (1) US9120935B2 (en)
EP (1) EP2723816A1 (en)
JP (1) JP5945593B2 (en)
KR (1) KR101564857B1 (en)
CN (1) CN103717678B (en)
WO (1) WO2012175825A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3015508B1 (en) 2013-12-20 2016-02-05 Bluestar Silicones France NEW PHOTOACTIVABLE HYDROSILYLATION INHIBITION SYSTEM
US10723891B2 (en) 2016-04-25 2020-07-28 Dow Silicones Corporation Aqueous coating composition
JP2018053229A (en) * 2016-09-21 2018-04-05 住友化学株式会社 Silicone resin composition, method for producing silicone resin composition, and cured product
TW201829672A (en) * 2017-02-10 2018-08-16 美商道康寧公司 Curable composition and coated substrate
TW201835260A (en) 2017-03-16 2018-10-01 美商陶氏有機矽公司 Silicone release coating compositions
KR102316253B1 (en) * 2017-03-30 2021-10-21 엘켐 실리콘즈 프랑스 에스에이에스 Method of making waterproof and non-tacky coatings on substrates
EP3645491B1 (en) * 2017-10-19 2021-09-15 Dow Silicones Corporation Polyorganosiloxane compositions containing a 2-substituted-1-alkynyl-1-cyclohexanol useful as a hydrosilylation reaction inhibitor
JP2023501754A (en) * 2019-11-19 2023-01-18 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン THERMAL INTERFACE MATERIALS AND APPLICATION METHOD
WO2023032781A1 (en) 2021-08-30 2023-03-09 日産化学株式会社 Thermosetting composition

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3220972A (en) 1962-07-02 1965-11-30 Gen Electric Organosilicon process using a chloroplatinic acid reaction product as the catalyst
US3159601A (en) 1962-07-02 1964-12-01 Gen Electric Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes
NL131800C (en) 1965-05-17
FR1528464A (en) 1966-06-23 1968-06-07 Dow Corning One-part curable organopolysiloxane compositions
NL129346C (en) 1966-06-23
US3814730A (en) 1970-08-06 1974-06-04 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
US3715334A (en) 1970-11-27 1973-02-06 Gen Electric Platinum-vinylsiloxanes
DE2654893A1 (en) 1976-12-03 1978-06-15 Wacker Chemie Gmbh PROCESS FOR PRODUCING STICKY FABRIC REPELLENT COATING
US4394317A (en) 1981-02-02 1983-07-19 Sws Silicones Corporation Platinum-styrene complexes which promote hydrosilation reactions
FR2575085B1 (en) 1984-12-20 1987-02-20 Rhone Poulenc Spec Chim PLATINUM-TRIENE COMPLEX AS HYDROSILYLATION REACTION CATALYST AND PREPARATION METHOD THEREOF
FR2575086B1 (en) 1984-12-20 1987-02-20 Rhone Poulenc Spec Chim PLATINUM-ALCENYLCYCLOHEXENE COMPLEX AS HYDROSILYLATION REACTION CATALYST AND PROCESS FOR PREPARING THE SAME
DE3927359A1 (en) * 1989-08-18 1991-02-21 Wacker Chemie Gmbh METHOD FOR PRODUCING ORGANO (POLY) SILOXANES WITH SI-BONDED CONJUGATED DIENYL GROUPS
JPH0657144A (en) * 1992-07-14 1994-03-01 Shin Etsu Chem Co Ltd Releasable silicone emulsion composition
US5496906A (en) * 1994-08-31 1996-03-05 General Electric Company Production of nitrosamine-free silicone articles
JP4646363B2 (en) * 2000-06-29 2011-03-09 東レ・ダウコーニング株式会社 Silicone rubber composition
GB0316162D0 (en) * 2003-07-10 2003-08-13 Dow Corning Silicone release coating compositions
KR20110136901A (en) * 2004-02-24 2011-12-21 상꾜 가부시키가이샤 Amino alcohol compound
US7611998B2 (en) * 2004-06-16 2009-11-03 Bluestar Silicones France Sas Enhanced elastomer coated, protective barrier fabric and process for producing same
DE102004035860A1 (en) * 2004-07-23 2006-02-16 Basf Ag Process for the preparation of 2-alkyne-1-acetals
DE102004050128A1 (en) * 2004-10-14 2006-04-20 Wacker Chemie Ag Silicone rubber composition with improved durability
ME01967B (en) * 2005-01-14 2012-08-31 Schering Corp Exo- and diastereo-selective syntheses of himbacine analogs
JP2007131750A (en) * 2005-11-11 2007-05-31 Shin Etsu Chem Co Ltd Addition curing type organopolysiloxane composition and method for promoting curing thereof
FR2894590B1 (en) 2005-12-09 2008-03-14 Rhodia Recherches & Tech METHOD FOR FIGHTING FOG APPEARANCE DURING THE COATING OF FLEXIBLE CARRIERS WITH A CROSSLINKABLE LIQUID SILICONE COMPOSITION IN A CYLINDERS DEVICE
FR2901800B1 (en) * 2006-05-31 2008-08-29 Rhodia Recherches & Tech CROSS-LINKABLE SILICONE COMPOSITION FOR THE PRODUCTION OF ANTI-ADHERENT COATINGS FOR POLYMERIC FILMS
JP2009091403A (en) * 2007-10-04 2009-04-30 Shin Etsu Chem Co Ltd Addition-curable type silicone rubber composition and method for curing the same
KR100987951B1 (en) 2008-11-24 2010-10-18 에스에스씨피 주식회사 Silicone rubber composition for preparing silicone blanket

Also Published As

Publication number Publication date
JP2014523938A (en) 2014-09-18
CN103717678A (en) 2014-04-09
WO2012175825A1 (en) 2012-12-27
JP5945593B2 (en) 2016-07-05
KR101564857B1 (en) 2015-10-30
US9120935B2 (en) 2015-09-01
US20140329099A1 (en) 2014-11-06
KR20140039056A (en) 2014-03-31
CN103717678B (en) 2015-11-25

Similar Documents

Publication Publication Date Title
WO2012175825A1 (en) Hydrosilylation reaction inhibitors, and use thereof for preparing stable curable silicone compositions
EP2516569B1 (en) Hydrosilylation reaction inhibitors, and use thereof in a coating method
CA2122409C (en) Long-chain alpha-acetylen alcohol as hydrosilylation inhibitors, and their application for the preparation of stable, hardenable silicons compositions
EP3353252B1 (en) Crosslinkable silicone composition for the production of non-stick coatings for flexible substrates and an attachment-promoting additive contained in this composition
EP2443178B1 (en) Silicone composition suitable for cross-linking by dehydrocondensation in the presence of a non-metal catalyst
EP2563870B1 (en) Cross-linkable silicone composition for the production of non-stick coatings for flexible substrates and an attachment-promoting additive contained in said composition
EP2024438B1 (en) Crosslinkable silicon composition for producing non-stick coatings for polymer films
EP2032654B1 (en) Silicone composite that can be reticulated for producing anti-adhesive coatings for flexible supports and additive to promote adhesion contained in this composite
WO2003054059A1 (en) Crosslinking agent for crosslinkable silicone composition with low platinum content based on hydrogenated silicone oil comprising si-h units in chain end and in the chain
EP3083855B1 (en) New inhibiting system for photoactivable hydrosilylation
WO2012085364A1 (en) Hydrosilylation reaction inhibitors and use thereof for preparing stable curable silicone compositions
WO2007068657A1 (en) Method for controlling onset of fog when coating flexible supports with a liquid silicone composition, in a cylinder-type device
EP0146422A1 (en) Ketone inhibitor for platinum catalysts, and polysiloxane compositions containing such an inhibitor
EP2608813B1 (en) Article adhesive to the skin
CA2447104A1 (en) Release regulating silicone system and use thereof for preparing curable release compositions
EP1448674B1 (en) Crosslinking agent for a low-temperature crosslinkable silicone composition based on a hydrogenated silicone oil comprising si-h units at the chain end and in the chain
FR2608617A1 (en) COMPOSITION CONTAINING A DIALKYL ACETYLENEDICARBOXYLATE AS AN INHIBITOR FOR FORMING BY EXPOSURE TO ULTRAVIOLET LIGHT A NON-STICK COATING OF SILICONE AND A METHOD OF USING THE SAME TO PRODUCE ANTIADHESIVE SURFACES
CA2127177A1 (en) Silicone polymers with olefinic groups, their preparation process and curable compositions containing them

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140120

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20161011

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20170222