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
  • 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
  • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • 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.
• the hydrosilylation reactions are widely used in the silicone industry to not only access functionalised silanes or siloxanes but also for the preparation of silicone networks obtained by crosslinking between polymethylhydrogenosiloxane and polymethylvinylsiloxane oils. These reactions are generally carried out by organometallic platinum catalysis and especially Karstedt platinum, which is appreciated for its high reactivity and its solubility in a silicone medium. In these conditions, the hydrosilylation reactions have rapid kinetics at room temperature and only a few tens of ppm (part per million) of catalyst are required to complete a reaction in a few minutes. Silicone compositions that can be crosslinked by hydrosilylation reactions are therefore used to form water-repellent or non-adhering coatings or films on paper or polymer film supports.
• 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. 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.
• ethynylcyclohexanol (ECH)
• 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.
• the hardenable silicone compositions which contain this type of inhibitor can be cured by increasing the temperature of the composition to a temperature above the boiling or sublimation point 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.
• ECH ethynylcyclohexanol
• silicone polyaddition compositions employing true ⁇ -acetylenic alcohols such as ECH are conditioned, prior to their use, in the form of "multi-component", that is to say that the constituents of the composition are placed in separate parts (or
• organohydrogenosiloxane polymer of the catalyst for reasons of safety.
• Part 1 (l) comprising at least polyméthylvinyîstloxanes and the inhibitor of the hydrosilylation reaction which provides stability and implementation formulations,
• part 4 (IV) formulations comprising additives providing intrinsic properties to the desired applications. It is known that when using these compositions packaged in the form of the mufti-component, the parts (I) and the catalyst part (III) should not be directly mixed. It is for this reason that the current practice consists in premixing the parts (I) and (II) comprising the polymethylvinylsiloxanes and the hydrogenosiloxane polymers before introducing the catalyzing part (III) thus avoiding the phenomenon of precipitation of the catalyst and coloring of the composition.
• ⁇ - ⁇ '-acetylenic diols do not exhibit these problems. They can be brought into contact with the platinum catalyst without leading to the precipitation phenomenon described above. This has the advantage of reducing the number of components for the polyaddition system. However, they are insoluble inhibitors in silicone medium leading to opaque formulations. This explains their limited use especially for paper non-stick application where transparency is an essential criterion.
• compositions comprising ⁇ - ⁇ '-acetylenic diols such as for example the compound 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD)
• TMDD 2,4,7,9-tetramethyl-5-decyne-4,7-diol
• ECH true ⁇ -acetylenic alcohol
• One of the essential objectives of the present invention is to provide a silicone composition X capable of hardening by a polyaddition reaction which:
• the main object of the invention consists of a crosslinkable and / or curable composition X by polyaddition reactions in the form of a multi-component system S comprising at least two distinct parts A and B intended to be mixed. to form a composition X 'in which:
• Part A includes:
• At least one polyorganosiloxane V comprising, per molecule, at least two alkenyl radicals bonded to silicon atoms,
• At least one catalyst E composed of at least one metal belonging to the platinum group and preferably a Karstedt platinum
• At least one inhibitor D1 which is an ⁇ - ⁇ '-acetylenic diol
• At least one organic acid or a mineral acid D2 with the proviso that the mineral acid does not contain platinum such as chloroplatinic acid, and
• Part B includes:
• At least one polyorganosiloxane H having, per molecule, at least two hydrogen atoms bonded to an identical or different silicon atom.
• composition X according to the invention is such that:
• Part A includes:
• At least one polyorganosiloxane V comprising, per molecule, at least two alkenyl radicals bonded to silicon atoms,
• At least one catalyst E composed of at least one metal belonging to the platinum group and preferably a platinum of arstedt
• At least one inhibitor D1 which is an ⁇ - ⁇ '-acetylenic diol
• Part B includes:
• At least one polyorganosiloxane H having, per molecule, at least two hydrogen atoms bonded to an identical or different silicon atom,
• the composition comprises a third part C comprising at least one additive F and which is distinct from parts A and B.
• the inhibitor D1 is an ⁇ - ⁇ '-acetylenic diol of formula (1) below:
• radicals R 1 , R 2 , R 3 and R 4 which are identical or different, represent, independently of one another, a linear or branched monovalent alkyl group, a cycloalkyl group, a (cycloalkyl) alkyl group, a group aromatic or arylalkyl group, and
• radicals R 1 , R 2 , R 3 and R 4 may be linked in pairs so as to form a 5-, 6-, 7- or 8-membered aliphatic ring optionally substituted by one or more substituents.
• the inhibitor D1 is selected from the group consisting of ⁇ - ⁇ '-acetylenic diols of
• the molar ratio [D1 inhibitor] / [D2 acid] is between 0.1 and 20 and preferably between 1 and 10 and even more preferably between 2.5 and 6.5.
• the acid D2 has in aqueous solution and at 25 ° C at least one pKa whose value is in the following interval: -0.9 p pKa ⁇ + 6.5.
• the acid D2 which are useful according to the invention are, for example, chosen from the group consisting of the following acids:
• the acid D 2 is chosen from the group consisting of: methanoic acid, orthophosphoric acid, heptanoic acid, trifluoroacetic acid and malonic acid.
• the molar ratio [inhibitor D1] / [catalyst C] is between 0 and 60 and the molar ratio [acid D2] / [catalyst C] is between 10 and 60.
• the proportions of the polyorganosiloxane V and of the organohydrogenpolysiloxane H are such that the molar ratio of the silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane H on the silicon-bonded alkenyl radicals in the organopolysiloxane V is between 0.4 and 10.
• the polyorganosiloxane V according to the invention has;
• T is an alkenyl group
• Z is a monovalent hydrocarbon group selected from the group consisting of alkyl groups having 1 to 8 carbon atoms inclusive, optionally substituted by 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
• Z has the same meaning as above and c is 0, 1, 2 or 3.
• the organopolysiloxane V has a viscosity at least equal to 50 mPa.s and preferably less than 200,000 mPa.s.
• hydrofluoropolysiloxane H according to the invention has:
• 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
• siloxyl units are units of formula (H.2):
• L has the same meaning as above and g is 0, 1, 2 or 3.
• the dynamic viscosity of organohydrogenpolysiloxane H is at least 10 mPa.s and preferably and 1000 mPa.s.
• the proportions of the polyorganosiloxane V and the polyorganosiloxane H are such that the molar ratio of the silicon-bonded hydrogen atoms in the polyorganosiloxane H to the silicon-bonded alkenyl radicals in the polyorganosiloxane V is between 0.4 and 10.
• the proportions of the siloxyl units (V.1) and (H.1) are such that the molar ratio of the silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane H to the silicon-bonded alkenyl radicals in the organopolysiloxane V is between 0.4 and 0.
• the silicone composition X according to the invention may comprise one or more additives that are conventional in the field of non-stick silicone coatings for solid support, for example made of 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 customary in this type of application such as. bactericides, antifreezes, wetting agents, defoamers, fillers, synthetic latices or dyes.
• an adhesion modulator system as well as additives customary in this type of application such as. bactericides, antifreezes, wetting agents, defoamers, fillers, synthetic latices or dyes.
• Another object of the invention is a composition siticone X 'obtained by mixtures of the parts of the composition X as described above.
• 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 bar systems. equalizer, on supports or flexible materials, then hardened by circulation in tunnel kilns heated to 70-200 ° C; the passage time in these furnaces is a function of the temperature; it is generally of the order of 5 to 15 seconds at a temperature of the order of 100 ° C and of the order of 1, 5 to 3 seconds at a temperature of about ⁇ ⁇ .
• 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.
• 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 diaikylvinylsiloxyl 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.
• NOLL Chomittry and Technology of Silicones
• 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,
• 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 at a temperature greater than 6G ° C and preferably between 70 ° C and 200th C or Y silicone elastomer according to the invention and as described above.
• the present invention also relates to a coating process on a flexible support
• said silicone composition X ' is deposited continuously or discontinuously on said flexible support S, and d) is crosslinked the silicone composition X 'by heating at a temperature above 60 ° C and preferably between 70 ° C and 200 D C.
• the flexible support S is made of paper, textile, cardboard, metal or plastic.
• the flexible support S may be of textile, paper, polyvinyl chloride (PVC), polyester, polypropylene, polyamide, polyethylene, polyurethane, non-woven fiberglass fabrics or polyethylene terephthalate (PET).
• PVC polyvinyl chloride
• PET polyethylene terephthalate
• At least one polyorganosiloxane V comprising, per molecule, at least two alkenyl radicals bonded to silicon atoms,
• At least one catalyst C composed of at least one metal belonging to the platinum group
• At least one inhibitor D1 which is an ⁇ - ⁇ '-acetylenic diol
• At least one organic acid or a mineral acid D2 with the proviso that the mineral acid does not contain platinum such as chloroplatinic acid
• composition is useful as part A of the composition X according to the invention.
• V.2 End-chain vinylated polydimethylsiloxane oil
• Inhibitor (D1.I1) (invention): 2,4J, 9-tetramethyl-5-decyne-4,7-diol (TMDD).
• Inhibitor (D1.C1) (Comparative): 1-Ethynyl-cyclohexanol (ECH).
• the inhibitor (D1.I1) is previously solubilized in the vinylated polydimethylsiloxane oil (V1) at 50 ° C. for 30 minutes before addition to the relevant parts A (parts A1 and A2).
• V1 vinylated polydimethylsiloxane oil
• the four mixtures (parts A1 to A4) are clear and colorless. They are then stirred at room temperature for 24 hours. and present the following aspects:
• Parts A3 and A4 (comparative) containing the ECH and the catalyst Pt took a yellow / brown color indicating the precipitation of a part platinum in the form of colloids.
• the addition of acid does not prevent the phenomenon of precipitation (Part A4).
• the formulation Part A2 (comparative) has a milky and opaque white appearance.
• Example 2 To each of the parts described in Example 1, a portion B containing 0.93 g of a polymethylhydrogensiloxane (H.1) oil was added. A sample for each composition is taken and analyzed in DSC ("Differential Scanning Calorimetry", METLER type device). The analysis is performed in the open aluminum capsule and using a temperature ramp from 25 to 200 * 0 with a gradient of 1 ⁇ ° C / min. The time required for the crosslinking at ambient temperature and the bath life are also measured. The thermal profiles, the characteristic data of the exothermic peaks (T ° C peak and ⁇ onset / endset ° C) are represented in the following Table 2.
• Table 2 The thermal profiles, the characteristic data of the exothermic peaks (T ° C peak and ⁇ onset / endset ° C) are represented in the following Table 2.
• Example 3 Demonstration of the improvement of room temperature to inhibit time for muting systems "diol ⁇ . ⁇ '-acetylenic ⁇ ⁇ acid" according to the invention.
• composition (C-4) 99 36 41
• T ° C for the compositions according to the invention (I-2), (I-3) and (I-2).
• 4) indicating a retarding effect of the acids.
• composition (C-4) we observe a lower ⁇ onset / endset for the compositions according to the invention indicating a decrease in trolling effects at the beginning and at the end of reaction.

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• 2011
  • 2011-12-20 WO PCT/FR2011/000665 patent/WO2012085364A1/fr active Application Filing
  • 2011-12-20 EP EP11808905.1A patent/EP2655517A1/fr not_active Withdrawn
  • 2011-12-20 BR BR112013016067A patent/BR112013016067A2/pt not_active IP Right Cessation
  • 2011-12-20 KR KR1020137019537A patent/KR101553456B1/ko not_active IP Right Cessation
  • 2011-12-20 CN CN201180066969.3A patent/CN103370376B/zh not_active Expired - Fee Related
  • 2011-12-20 US US13/997,612 patent/US20140004359A1/en not_active Abandoned
  • 2011-12-20 JP JP2013545455A patent/JP5753909B2/ja not_active Expired - Fee Related

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