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:

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Paints Or Removers (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=46516794

Family Applications (1)

Country Status (6)

Families Citing this family (9)

Family Cites Families (26)

• 2012
  • 2012-06-19 EP EP12735925.5A patent/EP2723816A1/de not_active Withdrawn
  • 2012-06-19 KR KR1020147001510A patent/KR101564857B1/ko not_active IP Right Cessation
  • 2012-06-19 CN CN201280036691.XA patent/CN103717678B/zh not_active Expired - Fee Related
  • 2012-06-19 WO PCT/FR2012/000249 patent/WO2012175825A1/fr active Application Filing
  • 2012-06-19 JP JP2014516409A patent/JP5945593B2/ja not_active Expired - Fee Related
  • 2012-06-19 US US14/128,414 patent/US9120935B2/en not_active Expired - Fee Related

Also Published As

Similar Documents

Legal Events