EP1429989B1 - Method for impregnating bottle corks - Google Patents

Method for impregnating bottle corks Download PDF

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Publication number
EP1429989B1
EP1429989B1 EP02777084A EP02777084A EP1429989B1 EP 1429989 B1 EP1429989 B1 EP 1429989B1 EP 02777084 A EP02777084 A EP 02777084A EP 02777084 A EP02777084 A EP 02777084A EP 1429989 B1 EP1429989 B1 EP 1429989B1
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EP
European Patent Office
Prior art keywords
organopolysiloxanes
silicone rubber
bonded hydrogen
sio
rubber compositions
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EP02777084A
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German (de)
French (fr)
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EP1429989A1 (en
Inventor
Klaus Angermaier
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Wacker Chemie AG
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Wacker Chemie AG
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B67—OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
    • B67B—APPLYING CLOSURE MEMBERS TO BOTTLES JARS, OR SIMILAR CONTAINERS; OPENING CLOSED CONTAINERS
    • B67B1/00—Closing bottles, jars or similar containers by applying stoppers
    • B67B1/03—Pretreatment of stoppers, e.g. cleaning, steaming, heating, impregnating or coating; Applying resilient rings to stoppers

Definitions

  • the invention relates to a process for the impregnation of Bottle corks with elastomers crosslinkable Silicone rubber compositions.
  • the object was a process for the impregnation of Bottle corks with elastomers crosslinkable To provide silicone rubber compositions in which the above described disadvantages are avoided and the Silicone rubber adheres to the surface of the corks and not can be rubbed off.
  • the object is achieved by the invention solved.
  • compositions of the invention with the components (1), (2), (3) and optionally (4) in the form provided by two-component masses, wherein the Components (2) and (3) are separated from each other.
  • Elastosil® M4600 contains as a crosslinker an Si-bonded hydrogen atoms having organopolysiloxane with 0.14 to 0.17 wt .-% Si-bonded Hydrogen.
  • cork stoppers for Closing beverage bottles, such as Wine bottles, to understand.
  • organopolysiloxanes (1) are preferably linear or branched organopolysiloxanes of units of the general formula R a R 1 b SiO 4-ab 2 wherein R is the same or different, a monovalent, optionally substituted hydrocarbon radical having 1 to 18 carbon atoms per radical and R 1 is the same or different, is a monovalent hydrocarbon radical having a terminal, aliphatic carbon-carbon multiple bond having 2 to 8 carbon atoms per radical, a 0, 1, 2 or 3, b 0, 1 or 2 and the sum a + b ⁇ 3, with the proviso that the organopolysiloxanes of the formula (I) contain at least 2 radicals R 1 per molecule.
  • R is preferably one of aliphatic carbon-carbon multiple bonds free hydrocarbon radical.
  • radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, Hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, Octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, Decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecy
  • substituted radicals R are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2 ', 2', 2'-hexafluoroisopropyl radical, Heptafluorisopropylrest and Halogenaryl, such as the o-, m- and p-chlorophenyl
  • the radical R is preferably a monovalent one Hydrocarbon radical having 1 to 6 carbon atoms, wherein the Methyl radical is particularly preferred.
  • radicals R 1 are alkenyl radicals, such as the vinyl, 5-hexenyl, cyclohexenyl, 1-propenyl, allyl, 3-butenyl and 4-pentenyl radicals, and alkynyl radicals, such as ethynyl, propargyl and 1 -Propinylrest.
  • the radical R 1 is preferably alkenyl radicals, with the vinyl radical being particularly preferred.
  • organopolysiloxane (1) It may be one kind of organopolysiloxane (1) or different Types of organopolysiloxanes (1) are used.
  • Preferred organopolysiloxanes (1) are those of the general formula R 1 g of R 3-g SiO (SiR 2 O) n (SiRR 1 O) m SiR 3-g R 1 g where R and R 1 have the meaning given above g is 0, 1, 2 or 3, preferably 1, m is 0 or an integer from 1 to 500 and n is an integer from 70 to 1,000, with the proviso that the organopolysiloxanes of the formula (II) contain at least 2 radicals R 1 per molecule.
  • formula (II) should be understood to mean that n units - (SiR 2 O) - and m units - (SiRR 1 O) - can be distributed in any desired manner, for example as a block or randomly, in the organopolysiloxane molecule.
  • the organopolysiloxanes (1) have an average Viscosity of preferably 100 to 100,000 mPa.s at 25 ° C, preferably 1 000 to 20 000 mPa.s at 25 ° C.
  • Organopolysiloxanes (2) are organopolysiloxanes (2) in the addition crosslinking of the silicone rubber compositions according to the invention.
  • Organopolysiloxanes (2) are preferably linear, cyclic or branched organopolysiloxanes of units of the general formula R e H f SiO 4-ef 2 in which R has the meaning given above, e 0, 1, 2 or 3, f 0, 1 or 2 and the sum of e + f ⁇ 3, with the proviso that the organopolysiloxanes of the formula (III) have 1.0 to 2.0 wt .-% Si-bonded hydrogen used.
  • Preferred organopolysiloxanes (2) are those of the general formula H h R 3-h SiO (SiR 2 O) o (SiR 2 -x H x O) p SiR 3-h H h where R has the meaning given above, h is 0, 1 or 2, preferably 0, o is 0 or an integer from 1 to 1,000, preferably 0, p is an integer from 1 to 1,000, preferably 40 to 70 and x is 1 or 2, preferably 1, with the proviso that the organopolysiloxanes of the formula (IV) have 1.0 to 2.0 wt .-%, preferably 1.5 to 1.7 wt .-%, Si-bonded hydrogen used.
  • formula (IV) is to be understood as meaning that o units (SiR 2 O) and p units (SiR 2 -x H x O) are distributed in the organopolysiloxane molecule in any desired manner, for example as a block or randomly could be.
  • organopolysiloxanes (2) are in particular Copolymers of dimethylhydrogensiloxane, Methylhydrogensiloxan-, dimethylsiloxane and Trimethylsiloxanticianen, copolymers of Trimethylsiloxane, dimethylhydrogensiloxane and Methylhydrogensiloxanticianen, copolymers of Trimethylsiloxane, dimethylsiloxane and Methylhydrogensiloxanticianen, copolymers of Methylhydrogensiloxane and trimethylsiloxane units, Copolymers of methylhydrogensiloxane, diphenylsiloxane and trimethylsiloxane units, copolymers of Methylhydrogensiloxane, dimethylhydrogensiloxane and Diphenylsiloxane units, copolymers of methylhydrogensiloxane, Phenylmethylsiloxane, trimethyl
  • organopolysiloxane (2) It may be one kind of organopolysiloxane (2) or different Types of organopolysiloxane (2) are used.
  • the organopolysiloxanes (2) have an average Viscosity of preferably 10 to 100,000 mPa.s at 25 ° C, preferably 10 to 500 mPa.s at 25 ° C, particularly preferably 10 to 30 mPa.s at 25 ° C.
  • compositions according to the invention can also be organopolysiloxanes (2 ') of the general formula H v R 3-v SiO (SiR 2 O) s (SiRHO) t SiR 3 -v H v where R has the meaning given above, v 0, 1 or 2, s 0 or an integer from 1 to 1,000 t is 0 or an integer from 1 to 1,000, with the proviso that the organopolysiloxanes of the formula (IV ') contain at least 2 Si-bonded hydrogen atoms per molecule but contain less than 1.0% by weight of Si-bonded hydrogen.
  • the organopolysiloxanes (2 ') have an average Viscosity of preferably 10 to 100,000 mPa.s at 25 ° C, preferably 10 to 500 mPa.s at 25 ° C.
  • Organopolysiloxane (2) is used in the inventive Silicone rubber compositions preferably in amounts of from 0.01 to 20 Wt .-%, based on the total weight of the organopolysiloxanes (1).
  • Organopolysiloxane (2 ') is used in the inventive Silicone rubber compositions preferably in amounts of 0 to 100 Wt .-%, based on the total weight of the organopolysiloxanes (1).
  • the same catalysts can be used in the silicone rubber compositions according to the invention, which could also be used to promote the addition of Si-bonded hydrogen to aliphatic multiple bond.
  • the catalysts are preferably a metal from the group of platinum metals or a compound or a complex from the group of platinum metals.
  • catalysts are metallic and finely divided platinum which may be supported on supports such as silica, alumina or activated carbon, compounds or complexes of platinum such as platinum halides, eg PtCl 4 , H 2 PtCl 6 .6H 2 O, Na 2 PtCl 4 * 4H 2 O, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products of H 2 PtCl 6 * 6H 2 O and cyclohexanone, platinum-vinyl-siloxane complexes such as platinum-1,3-divinyl-1,1,3,3-tetramethyl-disiloxane complexes with or without detectable inorganic halogenated content, bis- (gamma-picoline) platinum dichloride, trimethylenedipyridine platinum dichloride, dicyclopentad
  • the catalyst (3) is used in the inventive Silicone rubber compositions preferably in amounts of 0.001 to 0.1 Wt .-%, each calculated as elemental platinum and based on the total weight of the organopolysiloxanes (1) and (2), used.
  • inhibitors (4) can also in the inventive Silicone rubber compounds all inhibitors are used so far could be used for the same purpose.
  • inhibitors (4) are 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, benzotriazole, dialkylformamides, alkylthioureas, methyl ethyl ketoxime, organic or organosilicon compounds having a boiling point of at least 25 ° C.
  • the inhibitor (4) is used in amounts of preferably 0.001 to 10 Wt .-%, preferably, based on the total weight of Organopolysiloxanes (1) and (2) used.
  • the silicone rubber compositions according to the invention may contain further constituents such as fillers (5), such as reinforcing and non-reinforcing fillers and resinous organopolysiloxanes, such as MQ resins (6).
  • the further constituents may be contained in component (A) and / or (B).
  • reinforcing fillers (5a) are fumed silica, precipitated silica or silicon-aluminum mixed oxides having a BET surface area of more than 50 m 2 / g.
  • the fillers mentioned may be rendered hydrophobic, for example by treatment with organosilanes, silanes or siloxanes or by etherification of hydroxyl groups to alkoxy groups. Preference is given to pyrogenic silicas having a BET surface area of at least 100 m 2 / g
  • non-reinforcing fillers ie fillers having a BET surface area of less than 50 m 2 / g
  • Metal oxides such as iron oxide, zinc oxide, titanium dioxide and aluminum oxide or their mixed oxides, metal hydroxides such as aluminum hydroxide, metal carbonates such as calcium carbonate, magnesium carbonate and zinc carbonate, metal sulfates such as barium sulfate, gypsum, silicon nitride, silicon carbide, boron nitride, glass, carbon and plastic powder and glass and plastic hollow spheres.
  • the silicone rubber compositions of the invention do not contain reinforcing fillers in amounts of preferably 0 to 50 Wt .-%.
  • It can be a type of filler, but it can also be a mixture of at least two fillers are used.
  • the resinous organopolysiloxanes preferably contain monofunctional (M) and tri- (T) and / or tetrafunctional (Q) units, optionally also difunctional (D) units.
  • MQ resins (6) which consist of monofunctional and tetrafunctional units.
  • the monofunctional units may contain as functional groups unsaturated hydrocarbon radicals, such as alkenyl groups or Si-bonded hydrogen.
  • MQ resins (6) from units of the formulas R 5 R 2 SiO 1/2 and SiO 4/2 wherein R 5 is a radical R, a hydrogen atom or a radical R 1 and R and R 1 have the meaning given above, and the units of the formula R 5 R 2 SiO 1/2 may be the same or different.
  • the ratio of M units of the formula R 5 R 2 SiO 1/2 to Q units of the formula SiO 4/2 is preferably 4: 1 to 1: 2.
  • MQ resins (6a) with unsaturated M units are those of units of the formulas SiO 4/2 and R 1 R 2 SiO 1/2 and optionally R 3 SiO 1/2 , ie MQ resins with exclusively unsaturated M units or MQ resins with saturated and unsaturated M units wherein R and R 1 have the meaning given above and the ratio of M units R 1 R 2 SiO 1/2 and optionally R 3 SiO 1/2 to Q units SiO 4/2 preferably 4: 1 to 1: 2 and the ratio of saturated M units R 3 SiO 1/2 to unsaturated M units R 1 R 2 SiO 1/2 is preferably 10: 1 to 0: 1.
  • the MQ resins (6a) are preferably in amounts of 0 to 100 Wt .-%, based on the total weight of the organopolysiloxanes (1).
  • M-resins (6b) having Si-bonded hydrogen M units are those of units of the formulas SiO 4/2 and HR 2 SiO 1/2 and optionally R 3 SiO 1/2 , ie MQ resins containing only M units with Si-bonded hydrogen, or MQ resins containing M units with and without Si-bonded hydrogen, which are preferably contained in the component (B), wherein R has the meaning given above and the ratio of M units HR 2 SiO 1/2 and optionally R 3 SiO 1/2 to Q units SiO 4/2 is preferably 4: 1 to 1: 2, and the ratio of M units R 3 SiO 1/2 to M units HR 2 SiO 1/2 is preferably 10: 1 to 0: 1.
  • the MQ resins (6b) are preferably in amounts of 0 to 20 Wt .-%, based on the total weight of the organopolysiloxanes (1).
  • the components (A) and (B) are in a weight ratio of preferably 100: 1 to 1: 100, preferably 1: 1 used.
  • the silicone rubber compositions according to the invention have a Viscosity of preferably 500 to 20,000 mPa ⁇ s at 25 ° C, preferably 1 500 to 10 000 mPa ⁇ s at 25 ° C.
  • the silicone rubber compositions according to the invention have a Pot life at 25 ° C, preferably 12 hours to 2 weeks, preferably 1 to 5 days.
  • the treatment of the bottle corks is preferably carried out according to the method described in the aforementioned EP-A 773 090 (incorporated by reference).
  • bottle corks are commercially available bottle corks with a weight of preferably 2.5 to 4.0 g used.
  • the silicone rubber compositions of the invention can without further dilution with organic solvents used become.
  • the coating of the bottle cork is carried out according to the in the Prior art conventional methods for Vakuumim Weggniermaschine.
  • the bottle cork When diving the bottle cork is a vacuum of preferably applied 0.1 to 0.005 bar. The diving takes place preferably in a period of 5 to 20 minutes. After that the vacuum is broken.
  • Excess silicone rubber composition is mechanically, e.g. by Stripping, removed from the surface of the bottle cork.
  • the layer thickness of Silicone rubber on the surface is preferably 10 to 30 ⁇ m.
  • the amount of silicone rubber composition incorporated is essentially dictated by the nature of the bottle cork, ie, the proportion of voids, the process parameters selected in coating, and the efficiency of the method chosen for mechanically removing excess silicone rubber mass from the surface of the bottle cork.
  • the bottle corks preferably take up 0.5 to 1.0 g of silicone rubber composition, ie, the weight increase of the bottle cork is preferably 10 to 40 wt .-%.
  • the crosslinking of the silicone rubber compositions according to the invention is preferably carried out at the pressure of the surrounding atmosphere, ie at about 1020 hPa, but it can also be higher or higher lower pressures are performed.
  • the crosslinking is preferably carried out at a temperature of 50 ° C to 70 ° C, preferably from 60 ° C carried out.
  • the curing time of the silicone rubber compositions according to the invention is preferably 30 to 300 minutes, preferably 90 to 180 Minutes, at the above temperature.
  • the vulcanization reactivity of the invention Silicone rubber compositions is so on the process agreed that on the one hand a sufficiently long pot life for processing on the other a sufficiently rapid Have curing rate.
  • the inventive method has the advantage that Bottle corks obtained with good sealing properties become. Furthermore, the inventive method has the Advantage that the silicone rubber of the invention on the Surface of the bottle cork sticks well and when inserting the cork is not rubbed into the bottle.
  • the respectively obtained components A and B are then mixed in a ratio of 1: 1.
  • Organopolysiloxane of the formula: ViMe 2 SiO (Me 2 SiO) n 1 SiMe 2 Vi n 1 200 with a viscosity of 1000 mPa ⁇ s at 25 ° C.
  • Organopolysiloxane of the formula: ViMe 2 SiO (Me 2 SiO) n 2 SiMe 2 Vi n 2 450 with a viscosity of 7 000 mPa ⁇ s at 25 ° C.
  • Organopolysiloxane of the formula: ViMe 2 SiO (Me 2 SiO) n 3 SiMe 2 Vi n 3 600 with a viscosity of 20,000 mPa ⁇ s at 25 ° C.
  • Organopolysiloxane of the formula: Me 3 SiO (MeHSiO) n 4 SiMe 3 n 4 50 with a viscosity of 1,000 mPa ⁇ s at 25 ° C. and 1.6% by weight of Si-bonded hydrogen.
  • Organopolysiloxane of the formula: HMe 2 SiO (Me 2 SiO) n 5 SiMe 2 H n 200 with a viscosity of 1000 mPa ⁇ s at 25 ° C and 0.013 wt .-% Si-bonded hydrogen.
  • An addition-crosslinking two-component silicone rubber composition obtainable under the trade name Elastosil® M4600 from Wacker-Chemie GmbH is used.
  • Components A and B are mixed in a ratio of 10: 1.
  • Two corks treated with the silicone rubber compositions according to the invention are rubbed against one another with their lateral surfaces.
  • the corks have no abrasion.
  • the silicone rubber does not rub off the cork surface.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
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Abstract

Disclosed is a novel method for impregnating bottle corks, wherein the bottle corks are treated with silicon rubber materials, which can be cross-linked to form elastomers, containing organopolysiloxanes comprising (1) radicals with aliphatic carbon-carbon multiple bonds, (2) organopolysiloxanes with Si-bonded hydrogen atoms (3), catalysts promoting the attachment of Si-bonded hydrogen to aliphatic multiple bonds, and optionally (4) agents which delay the attachment of Si-bonded hydrogen to aliphatic multiple bonds, characterized in that the organopolysiloxanes (2) contain 1.02.0 wt. % Si-bonded hydrogen.

Description

Die Erfindung betrifft ein Verfahren zur Imprägnierung von Flaschenkorken mit zu Elastomeren vernetzbaren Siliconkautschukmassen.The invention relates to a process for the impregnation of Bottle corks with elastomers crosslinkable Silicone rubber compositions.

In EP-A 773 090 werden Flaschenkorken mit einem Zweikomponenten-Siliconkautschuk in einem Vakuumverfahren imprägniert. Der Vorteil dieses Verfahrens ist es, Korken minderer Qualität mit verbesserten Dichtungseigenschaften auszustatten, sowie die Extraktion aromatischer, den Geschmack des Getränks beeinträchtigende Korkbestandteile, wie Trichloranisol, zu reduzieren, und den Korken dadurch aufzuwerten. Der Nachteil dieses Verfahrens ist, dass der Siliconkautschuk keine Haftung zum Korken besitzt. Der Siliconkautschuk wird beim Einbringen in den Flaschenhals abgerieben. Die Siliconstücke verbleiben sichtbar im Getränk und machen den Korken daher unbrauchbar.In EP-A 773 090 bottle corks are with a Two-component silicone rubber in a vacuum process impregnated. The advantage of this method is corks inferior quality with improved sealing properties equip, as well as the extraction of aromatic, the taste cork ingredients affecting the beverage, such as Trichloranisol, reduce, and the cork thereby upgrade. The disadvantage of this procedure is that of Silicone rubber has no liability to the cork. Of the Silicone rubber becomes when inserting into the bottleneck abraded. The silicone pieces remain visible in the drink and therefore make the cork useless.

Es bestand die Aufgabe ein Verfahren zur Imprägnierung von Flaschenkorken mit zu Elastomeren vernetzbaren Siliconkautschukmassen bereitzustellen, bei dem die oben beschriebenen Nachteile vermieden werden und der Siliconkautschuk an der Oberfläche der Korken haftet und nicht abgerieben werden kann. Die Aufgabe wird durch die Erfindung gelöst.The object was a process for the impregnation of Bottle corks with elastomers crosslinkable To provide silicone rubber compositions in which the above described disadvantages are avoided and the Silicone rubber adheres to the surface of the corks and not can be rubbed off. The object is achieved by the invention solved.

Gegenstand der Erfindung ist ein Verfahren zur Imprägnierung von Flaschenkorken, bei dem die Flaschenkorken mit zu Elastomeren vernetzbaren Siliconkautschukmassen enthaltend

  • (1) Organopolysiloxane, die Reste mit aliphatischen Kohlenstoff-Kohlenstoff-Mehrfachbindungen aufweisen,
  • (2) Organopolysiloxane mit Si-gebundenen Wasserstoffatomen
  • (3) die Anlagerung von Si-gebundenen Wasserstoff an aliphatische Mehrfachbindungen fördernde Katalysatoren und gegebenenfalls
  • (4) die Anlagerung von Si-gebundenen Wasserstoff an aliphatische Mehrfachbindungen verzögernde Mittel, sogenannte Inhibitoren,
    • behandelt werden,
    dadurch gekennzeichnet, dass die Organopolysiloxane (2) 1,0 bis 2,0 Gew.-% Si-gebundenen Wasserstoff aufweisen.The invention relates to a process for the impregnation of bottle corks, wherein the bottle corks containing crosslinkable to elastomeric silicone rubber compositions containing
  • (1) organopolysiloxanes having radicals having aliphatic carbon-carbon multiple bonds,
  • (2) organopolysiloxanes having Si-bonded hydrogen atoms
  • (3) the addition of Si-bonded hydrogen to aliphatic multiple bonds promoting catalysts and optionally
  • (4) the addition of Si-bonded hydrogen to aliphatic multiple bonds delaying agents, so-called inhibitors,
    • be treated,
    characterized in that the organopolysiloxanes (2) have 1.0 to 2.0 wt .-% Si-bonded hydrogen.

    Vorzugsweise werden die erfindungsgemäßen Zusammensetzungen mit den Bestandteilen (1), (2), (3) und gegebenenfalls (4) in Form von Zweikomponenten-Massen bereitgestellt, wobei die Bestandteile (2) und (3) von einander getrennt werden.Preferably, the compositions of the invention with the components (1), (2), (3) and optionally (4) in the form provided by two-component masses, wherein the Components (2) and (3) are separated from each other.

    Die zu Elastomeren vernetzbaren Siliconkautschukmassen sind daher bevorzugt Zweikomponenten-Massen, wobei

  • Komponente (A) Organopolysiloxan (1), Katalysator (3) und gegebenenfalls Inhibitor (4) und
  • Komponente (B) Organopolysiloxan (2) und gegebenenfalls noch zusätzlich Organopolysiloxan (1) und gegebenenfalls Inhibitor (4) enthält.
    • The elastomeric crosslinkable silicone rubber compositions are therefore preferably two-component materials,
  • Component (A) organopolysiloxane (1), catalyst (3) and optionally inhibitor (4) and
  • Component (B) organopolysiloxane (2) and optionally additionally organopolysiloxane (1) and optionally inhibitor (4).

    • Die in der eingangs erwähnten EP-A 773 090 verwendete additionsvernetzende Siliconkautschukmasse Elastosil® M4600 enthält als Vernetzer ein Si-gebundene Wasserstoffatome aufweisendes Organopolysiloxan mit 0,14 bis 0,17 Gew.-% Si-gebundenen Wasserstoff.The used in the aforementioned EP-A 773 090 addition-curing silicone rubber compound Elastosil® M4600 contains as a crosslinker an Si-bonded hydrogen atoms having organopolysiloxane with 0.14 to 0.17 wt .-% Si-bonded Hydrogen.

    Unter Flaschenkorken sind Stopfen aus Korkmaterial zum Verschließen von Getränkeflaschen, wie beispielsweise Weinflaschen, zu verstehen.Under corks are cork stoppers for Closing beverage bottles, such as Wine bottles, to understand.

    Als Organopolysiloxane (1) werden vorzugsweise lineare oder verzweigte Organopolysiloxane aus Einheiten der allgemeinen Formel RaR1 bSiO 4-a-b2 wobei R gleich oder verschieden ist, einen einwertigen, gegebenenfalls substituierten Kohlenwasserstoffrest mit 1 bis 18 Kohlenstoffatom(en) je Rest und
    R1 gleich oder verschieden ist, einen einwertigen Kohlenwasserstoffrest mit terminaler, aliphatischer Kohlenstoff-Kohlenstoff-Mehrfachbindung mit 2 bis 8 Kohlenstoffatomen je Rest bedeutet,
    a 0, 1, 2 oder 3,
    b 0, 1 oder 2
    und die Summe a+b<3 ist,
    mit der Maßgabe, daß die Organopolysiloxane der Formel (I) pro Molekül mindestens 2 Reste R1 enthalten, verwendet.    As organopolysiloxanes (1) are preferably linear or branched organopolysiloxanes of units of the general formula R a R 1 b SiO 4-ab 2 wherein R is the same or different, a monovalent, optionally substituted hydrocarbon radical having 1 to 18 carbon atoms per radical and
    R 1 is the same or different, is a monovalent hydrocarbon radical having a terminal, aliphatic carbon-carbon multiple bond having 2 to 8 carbon atoms per radical,
    a 0, 1, 2 or 3,
    b 0, 1 or 2
    and the sum a + b <3,
    with the proviso that the organopolysiloxanes of the formula (I) contain at least 2 radicals R 1 per molecule.

    R ist vorzugsweise ein von aliphatischen Kohlenstoff-Kohlenstoff-Mehrfachbindungen freier Kohlenwasserstoffrest. Beispiele für Reste R sind Alkylreste, wie der Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl-, tert.-Butyl-, n-Pentyl-, iso-Pentyl-, neo-Pentyl-, tert.-Pentylrest, Hexylreste, wie der n-Hexylrest, Heptylreste, wie der n-Heptylrest, Octylreste, wie der n-Octylrest und iso-Octylreste, wie der 2,2,4-Trimethylpentylrest, Nonylreste, wie der n-Nonylrest, Decylreste, wie der n-Decylrest, Dodecylreste, wie der n-Dodecylrest, und Octadecylreste, wie der n-Octadecylrest; Cycloalkylreste, wie Cyclopentyl-, Cyclohexyl-, Cycloheptyl- und Methylcyclohexylreste; Arylreste, wie der Phenyl-, Naphthyl-, Anthryl- und Phenanthrylrest; Alkarylreste, wie o-, m-, p-Tolylreste, Xylylreste und Ethylphenylreste; und Aralkylreste, wie der Benzylrest, der α- und der β-Phenylethylrest.R is preferably one of aliphatic carbon-carbon multiple bonds free hydrocarbon radical. Examples of radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, Hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n-heptyl radical, Octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as the n-nonyl radical, Decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals; Aryl radicals, such as the phenyl, Naphthyl, anthryl and phenanthryl; Alkaryl radicals, such as o-, m, p-tolyl, xylyl and ethylphenyl; and Aralkyl radicals, such as the benzyl radical, the α- and the β-phenylethyl radical.

    Beispiele für substituierte Reste R sind Halogenalkylreste, wie der 3,3,3-Trifluor-n-propylrest, der 2,2,2,2',2',2'-Hexafluorisopropylrest, der Heptafluorisopropylrest und Halogenarylreste, wie der o-, m- und p-Chlorphenylrest Bevorzugt handelt es sich bei dem Rest R um einen einwertigen Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen, wobei der Methylrest besonders bevorzugt ist.Examples of substituted radicals R are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2 ', 2', 2'-hexafluoroisopropyl radical, Heptafluorisopropylrest and Halogenaryl, such as the o-, m- and p-chlorophenyl The radical R is preferably a monovalent one Hydrocarbon radical having 1 to 6 carbon atoms, wherein the Methyl radical is particularly preferred.

    Beispiele für Reste R1 sind Alkenylreste, wie der Vinyl-, 5-Hexenyl-, Cyclohexenyl-, 1-Propenyl-, Allyl-, 3-Butenyl- und 4-Pentenylrest, und Alkinylreste, wie der Ethinyl-, Propargyl- und 1-Propinylrest.Examples of radicals R 1 are alkenyl radicals, such as the vinyl, 5-hexenyl, cyclohexenyl, 1-propenyl, allyl, 3-butenyl and 4-pentenyl radicals, and alkynyl radicals, such as ethynyl, propargyl and 1 -Propinylrest.

    Bevorzugt handelt es sich bei dem Rest R1 um Alkenylreste, wobei der Vinylrest besonders bevorzugt ist.The radical R 1 is preferably alkenyl radicals, with the vinyl radical being particularly preferred.

    Es kann eine Art von Organopolysiloxan (1) oder verschiedene Arten von Organopolysiloxanen (1) eingesetzt werden.It may be one kind of organopolysiloxane (1) or different Types of organopolysiloxanes (1) are used.

    Bevorzugt als Organopolysiloxane (1) sind solche der allgemeinen Formel R1 gR3-gSiO(SiR2O)n(SiRR1O)mSiR3-gR1 g wobei R und R1 die oben dafür angegebene Bedeutung haben
    g 0, 1, 2 oder 3, bevorzugt 1 , bedeutet,
    m 0 oder eine ganze Zahl von 1 bis 500 ist und
    n eine ganze Zahl von 70 bis 1 000 ist,
    mit der Maßgabe, daß die Organopolysiloxane der Formel (II) pro Molekül mindestens 2 Reste R1 enthalten.    Preferred organopolysiloxanes (1) are those of the general formula R 1 g of R 3-g SiO (SiR 2 O) n (SiRR 1 O) m SiR 3-g R 1 g where R and R 1 have the meaning given above
    g is 0, 1, 2 or 3, preferably 1,
    m is 0 or an integer from 1 to 500 and
    n is an integer from 70 to 1,000,
    with the proviso that the organopolysiloxanes of the formula (II) contain at least 2 radicals R 1 per molecule.

    Im Rahmen dieser Erfindung soll Formel (II) so verstanden werden, daß n Einheiten -(SiR2O)- und m Einheiten -(SiRR1O)- in beliebiger Weise, beispielsweise als Block oder statistisch, im Organopolysiloxanmolekül verteilt sein können.In the context of this invention formula (II) should be understood to mean that n units - (SiR 2 O) - and m units - (SiRR 1 O) - can be distributed in any desired manner, for example as a block or randomly, in the organopolysiloxane molecule.

    Die Organopolysiloxane (1) besitzen eine durchschnittliche Viskosität von vorzugsweise 100 bis 100 000 mPa.s bei 25°C, bevorzugt 1 000 bis 20 000 mPa.s bei 25°C. The organopolysiloxanes (1) have an average Viscosity of preferably 100 to 100,000 mPa.s at 25 ° C, preferably 1 000 to 20 000 mPa.s at 25 ° C.

    Als Vernetzer werden Organopolysiloxane (2) bei der Additionsvernetzung der erfindungsgemäßen Siliconkautschukmassen eingesetzt.
    Als Organopolysiloxane (2) werden vorzugsweise lineare, cyclische oder verzweigte Organopolysiloxane aus Einheiten der allgemeinen Formel ReHfSiO 4-e-f2 wobei
    R die oben dafür angegebene Bedeutung hat,
    e 0, 1, 2 oder 3,
    f 0, 1 oder 2
    und die Summe von e+f≤3 ist,
    mit der Maßgabe, daß die Organopolysiloxane der Formel (III) 1,0 bis 2,0 Gew.-% Si-gebundenen Wasserstoff aufweisen, verwendet.    The crosslinkers used are organopolysiloxanes (2) in the addition crosslinking of the silicone rubber compositions according to the invention.
    Organopolysiloxanes (2) are preferably linear, cyclic or branched organopolysiloxanes of units of the general formula R e H f SiO 4-ef 2 in which
    R has the meaning given above,
    e 0, 1, 2 or 3,
    f 0, 1 or 2
    and the sum of e + f≤3,
    with the proviso that the organopolysiloxanes of the formula (III) have 1.0 to 2.0 wt .-% Si-bonded hydrogen used.

    Bevorzugt werden als Organopolysiloxane (2) solche der allgemeinen Formel HhR3-hSiO(SiR2O)o(SiR2-xHxO)pSiR3-hHh wobei R die oben dafür angegebene Bedeutung hat,
    h 0, 1 oder 2, vorzugsweise 0,
    o 0 oder eine ganze Zahl von 1 bis 1 000, vorzugsweise 0,
    p eine ganze Zahl von 1 bis 1 000, vorzugsweise 40 bis 70 und,
    x 1 oder 2, vorzugsweise 1, ist,
    mit der Maßgabe, daß die Organopolysiloxane der Formel (IV) 1,0 bis 2,0 Gew.-%, vorzugsweise 1,5 bis 1,7 Gew.-%, Si-gebundenen Wasserstoff aufweisen, verwendet.    Preferred organopolysiloxanes (2) are those of the general formula H h R 3-h SiO (SiR 2 O) o (SiR 2 -x H x O) p SiR 3-h H h where R has the meaning given above,
    h is 0, 1 or 2, preferably 0,
    o is 0 or an integer from 1 to 1,000, preferably 0,
    p is an integer from 1 to 1,000, preferably 40 to 70 and
    x is 1 or 2, preferably 1,
    with the proviso that the organopolysiloxanes of the formula (IV) have 1.0 to 2.0 wt .-%, preferably 1.5 to 1.7 wt .-%, Si-bonded hydrogen used.

    Im Rahmen dieser Erfindung soll Formel (IV) so verstanden werden, daß o Einheiten -(SiR2O)- und p Einheiten -(SiR2-xHxO)-in beliebiger Weise, beispielsweise als Block oder statistisch, im Organopolysiloxanmolekül verteilt sein können. In the context of this invention, formula (IV) is to be understood as meaning that o units (SiR 2 O) and p units (SiR 2 -x H x O) are distributed in the organopolysiloxane molecule in any desired manner, for example as a block or randomly could be.

    Beispiele für Organopolysiloxane (2) sind insbesondere Mischpolymerisate aus Dimethylhydrogensiloxan-, Methylhydrogensiloxan-, Dimethylsiloxan- und Trimethylsiloxaneinheiten, Mischpolymerisate aus Trimethylsiloxan-, Dimethylhydrogensiloxan- und Methylhydrogensiloxaneinheiten, Mischpolymerisate aus Trimethylsiloxan-, Dimethylsiloxan- und Methylhydrogensiloxaneinheiten, Mischpolymerisate aus Methylhydrogensiloxan- und Trimethylsiloxaneinheiten, Mischpolymerisate aus Methylhydrogensiloxan-, Diphenylsiloxan- und Trimethylsiloxaneinheiten, Mischpolymerisate aus Methylhydrogensiloxan-, Dimethylhydrogensiloxan- und Diphenylsiloxaneinheiten, Mischpolymerisate aus Methylhydrogensiloxan-, Phenylmethylsiloxan-, Trimethylsiloxan- und/oder Dimethylhydrogensiloxaneinheiten, Mischpolymerisate aus Methylhydrogensiloxan-, Dimethylsiloxan-, Diphenylsiloxan-, Trimethylsiloxan- und/oder Dimethylhydrogensiloxaneinheiten sowie Mischpolymerisate aus Dimethylhydrogensiloxan-, Trimethylsiloxan-, Phenylhydrogensiloxan-, Dimethylsiloxan- und/oder Phenylmethylsiloxaneinheiten.Examples of organopolysiloxanes (2) are in particular Copolymers of dimethylhydrogensiloxane, Methylhydrogensiloxan-, dimethylsiloxane and Trimethylsiloxaneinheiten, copolymers of Trimethylsiloxane, dimethylhydrogensiloxane and Methylhydrogensiloxaneinheiten, copolymers of Trimethylsiloxane, dimethylsiloxane and Methylhydrogensiloxaneinheiten, copolymers of Methylhydrogensiloxane and trimethylsiloxane units, Copolymers of methylhydrogensiloxane, diphenylsiloxane and trimethylsiloxane units, copolymers of Methylhydrogensiloxane, dimethylhydrogensiloxane and Diphenylsiloxane units, copolymers of methylhydrogensiloxane, Phenylmethylsiloxane, trimethylsiloxane and / or Dimethylhydrogensiloxaneinheiten, copolymers of Methylhydrogensiloxane, dimethylsiloxane, diphenylsiloxane, Trimethylsiloxane and / or Dimethylhydrogensiloxaneinheiten and copolymers of dimethylhydrogensiloxane, Trimethylsiloxane, phenylhydrogensiloxane, dimethylsiloxane and / or phenylmethylsiloxane units.

    Es kann eine Art von Organopolysiloxan (2) oder verschiedene Arten von Organopolysiloxan (2) eingesetzt werden.It may be one kind of organopolysiloxane (2) or different Types of organopolysiloxane (2) are used.

    Die Organopolysiloxane (2) besitzen eine durchschnittliche Viskosität von vorzugsweise 10 bis 100 000 mPa.s bei 25°C, bevorzugt 10 bis 500 mPa.s bei 25°C, besonders bevorzugt 10 bis 30 mPa.s bei 25 °C.The organopolysiloxanes (2) have an average Viscosity of preferably 10 to 100,000 mPa.s at 25 ° C, preferably 10 to 500 mPa.s at 25 ° C, particularly preferably 10 to 30 mPa.s at 25 ° C.

    Neben den an Si-gebundenen Wasserstoff reichen Organopolysiloxanen (2) können die erfindungsgemäßen Massen auch Organopolysiloxane (2') der allgemeinen Formel HvR3-vSiO(SiR2O)s(SiRHO)tSiR3-vHv wobei R die oben dafür angegebene Bedeutung hat,
    v 0, 1 oder 2,
    s 0 oder eine ganze Zahl von 1 bis 1 000
    t 0 oder eine ganze Zahl von 1 bis 1 000 ist,
    mit der Maßgabe, daß die Organopolysiloxane der Formel (IV') mindestens 2 Si-gebundene Wasserstoffatome pro Molekül enthalten aber weniger als 1,0 Gew.-% Si-gebundenen Wasserstoff aufweisen, enthalten.    In addition to the organopolysiloxanes (2) rich in Si-bonded hydrogen, the compositions according to the invention can also be organopolysiloxanes (2 ') of the general formula H v R 3-v SiO (SiR 2 O) s (SiRHO) t SiR 3 -v H v where R has the meaning given above,
    v 0, 1 or 2,
    s 0 or an integer from 1 to 1,000
    t is 0 or an integer from 1 to 1,000,
    with the proviso that the organopolysiloxanes of the formula (IV ') contain at least 2 Si-bonded hydrogen atoms per molecule but contain less than 1.0% by weight of Si-bonded hydrogen.

    Mit v=1 und t=0 in Formel (IV') handelt es sich beispielsweise um α,ω-Dihydrogenorganopolysiloxane, die als Kettenverlängerer agieren.For example, v = 1 and t = 0 in formula (IV ') to α, ω-dihydrogenorganopolysiloxanes used as chain extenders act.

    Die Organopolysiloxane (2') besitzen eine durchschnittliche Viskosität von vorzugsweise 10 bis 100 000 mPa.s bei 25°C, bevorzugt 10 bis 500 mPa.s bei 25°C.The organopolysiloxanes (2 ') have an average Viscosity of preferably 10 to 100,000 mPa.s at 25 ° C, preferably 10 to 500 mPa.s at 25 ° C.

    Organopolysiloxan (2) wird bei den erfindungsgemäßen Siliconkautschukmassen vorzugsweise in Mengen von 0,01 bis 20 Gew.-%, bezogen auf das Gesamtgewicht der Organopolysiloxane (1), eingesetzt.Organopolysiloxane (2) is used in the inventive Silicone rubber compositions preferably in amounts of from 0.01 to 20 Wt .-%, based on the total weight of the organopolysiloxanes (1).

    Organopolysiloxan (2') wird bei den erfindungsgemäßen Siliconkautschukmassen vorzugsweise in Mengen von 0 bis 100 Gew.-%, bezogen auf das Gesamtgewicht der Organopolysiloxane (1), eingesetzt.Organopolysiloxane (2 ') is used in the inventive Silicone rubber compositions preferably in amounts of 0 to 100 Wt .-%, based on the total weight of the organopolysiloxanes (1).

    Als die Anlagerung von Si-gebundenem Wasserstoff an aliphatische Mehrfachbindung fördernde Katalysatoren (3), können auch bei den erfindungsgemäßen Siliconkautschukmassen die gleichen Katalysatoren eingesetzt werden, die auch bisher zur Förderung der Anlagerung von Si-gebundenem Wasserstoff an aliphatische Mehrfachbindung eingesetzt werden konnten. Bei den Katalysatoren handelt es sich vorzugsweise um ein Metall aus der Gruppe der Platinmetalle oder um eine Verbindung oder einen Komplex aus der Gruppe der Platinmetalle. Beispiele für solche Katalysatoren sind metallisches und feinverteiltes Platin, das sich auf Trägern, wie Siliciumdioxyd, Aluminiumoxyd oder Aktivkohle befinden kann, Verbindungen oder Komplexe von Platin, wie Platinhalogenide, z.B. PtCl4, H2PtCl6*6H2O, Na2PtCl4*4H2O, Platin-Olefin-Komplexe, Platin-Alkohol-Komplexe, Platin-Alkoholat-Komplexe, Platin-Ether-Komplexe, Platin-Aldehyd-Komplexe, Platin-Keton-Komplexe, einschließlich Umsetzungs-produkten aus H2PtCl6*6H2O und Cyclohexanon, Platin-Vinyl-siloxankomplexe, wie Platin-1,3-Divinyl-1,1,3,3-tetramethyl-disiloxankomplexe mit oder ohne Gehalt an nachweisbarem anorganisch gebundenem Halogen, Bis-(gamma-picolin)-platindichlorid, Trimethylendipyridinplatindichlorid, Dicyclopentadienplatindichlorid, Dimethylsulfoxydethylenplatin-(II)-di-chlorid, Cyclooctadien-Platindichlorid, Norbornadien-Platindichlorid, Gamma-picolin-Platindichlorid, Cyclopentadien-Platindichlorid, sowie Umsetzungsprodukte von Platintetrachlorid mit Olefin und primärem Amin oder sekundärem Amin oder primärem und sekundärem Amin, wie das Umsetzungsprodukt aus in 1-Octen gelöstem Platintetrachlorid mit sec.-Butylamin oder Ammonium-Platinkomplexe.As the addition of Si-bonded hydrogen to aliphatic multiple bond promoting catalysts (3), the same catalysts can be used in the silicone rubber compositions according to the invention, which could also be used to promote the addition of Si-bonded hydrogen to aliphatic multiple bond. The catalysts are preferably a metal from the group of platinum metals or a compound or a complex from the group of platinum metals. Examples of such catalysts are metallic and finely divided platinum which may be supported on supports such as silica, alumina or activated carbon, compounds or complexes of platinum such as platinum halides, eg PtCl 4 , H 2 PtCl 6 .6H 2 O, Na 2 PtCl 4 * 4H 2 O, platinum-olefin complexes, platinum-alcohol complexes, platinum-alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, including reaction products of H 2 PtCl 6 * 6H 2 O and cyclohexanone, platinum-vinyl-siloxane complexes such as platinum-1,3-divinyl-1,1,3,3-tetramethyl-disiloxane complexes with or without detectable inorganic halogenated content, bis- (gamma-picoline) platinum dichloride, trimethylenedipyridine platinum dichloride, dicyclopentadiene platinum dichloride, dimethylsulfoxydethylenepatin (II) di-chloride, cyclooctadiene-platinum dichloride, norbornadiene-platinum dichloride, gamma-picoline-platinum dichloride, cyclopentadiene-platinum dichloride, and reaction products of platinum tetrachloride with O. lefin and primary amine or secondary amine or primary and secondary amine, such as the reaction product of dissolved in 1-octene platinum tetrachloride with sec-butylamine or ammonium-platinum complexes.

    Der Katalysator (3) wird bei den erfindungsgemäßen Siliconkautschukmassen vorzugsweise in Mengen von 0,001 bis 0,1 Gew.-%, jeweils berechnet als elementares Platin und bezogen auf das Gesamtgewicht der Organopolysiloxane (1) und (2), eingesetzt.The catalyst (3) is used in the inventive Silicone rubber compositions preferably in amounts of 0.001 to 0.1 Wt .-%, each calculated as elemental platinum and based on the total weight of the organopolysiloxanes (1) and (2), used.

    Als Inhibitoren (4) können auch bei den erfindungsgemäßen Siliconkautschukmassen alle Inhibitoren verwendet werden, die auch bisher für den gleichen Zweck verwendet werden konnten.As inhibitors (4) can also in the inventive Silicone rubber compounds all inhibitors are used so far could be used for the same purpose.

    Beispiele für Inhibitoren (4) sind 1,3-Divinyl-1,1,3,3-tetramethyldisiloxan, Benzotriazol, Dialkylformamide, Alkylthioharnstoffe, Methylethylketoxim, organische oder siliciumorganische Verbindungen mit einem Siedepunkt von mindestens 25°C bei 1012 mbar (abs.) und mindestens einer aliphatischen Dreifachbindung, wie 1-Ethinylcyclohexan-1-ol, 2-Methyl-3-butin-2-ol, 3-Methyl-1-pentin-3-ol, 2,5-Dimethyl-3-hexin-2,5-diol und 3,5-Dimethyl-1-hexin-3-ol, 3,7-Dimethyl-oct-1-in-6-en-3-ol, eine Mischung aus Diallylmaleinat und Vinylacetat, Maleinsäuremonoester, und Inhibitoren wie die Verbindung der Formel HC=C-C(CH3) (OH)-CH2-CH2-CH=C(CH3)2, käuflich erwerblich unter dem Handelsnamen "Dehydrolinalool" bei der Fa. BASF.Examples of inhibitors (4) are 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, benzotriazole, dialkylformamides, alkylthioureas, methyl ethyl ketoxime, organic or organosilicon compounds having a boiling point of at least 25 ° C. at 1012 mbar (abs.) and at least one aliphatic triple bond such as 1-ethynylcyclohexan-1-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyne-3-ol, 2,5-dimethyl-3-hexyne-2 , 5-diol and 3,5-dimethyl-1-hexyn-3-ol, 3,7-dimethyl-oct-1-yn-6-en-3-ol, a mixture of diallyl maleate and vinyl acetate, maleic acid monoesters, and inhibitors as the compound of formula HC = CC (CH 3 ) (OH) -CH 2 -CH 2 -CH = C (CH 3 ) 2 , commercially available under the trade name "dehydrolinalool" from BASF.

    Der Inhibitor (4) wird in Mengen von vorzugsweise 0,001 bis 10 Gew.-%, bevorzugt, bezogen auf das Gesamtgewicht der Organopolysiloxane (1) und (2), eingesetzt.The inhibitor (4) is used in amounts of preferably 0.001 to 10 Wt .-%, preferably, based on the total weight of Organopolysiloxanes (1) and (2) used.

    Die erfindungsgemäßen Siliconkautschukmassen können weitere Bestandteile wie Füllstoffe (5), wie verstärkende und nicht verstärkende Füllstoffe und harzartige Organopolysiloxane, wie MQ-Harze (6), enthalten.
    Die weiteren Bestandteile können in der Komponente (A) und/oder (B) enthalten sein.    The silicone rubber compositions according to the invention may contain further constituents such as fillers (5), such as reinforcing and non-reinforcing fillers and resinous organopolysiloxanes, such as MQ resins (6).
    The further constituents may be contained in component (A) and / or (B).

    Beispiele für verstärkende Füllstoffe (5a), also Füllstoffe mit einer BET-Oberfläche von mindestens 50 m2/g, sind pyrogen hergestellte Kieselsäure, gefällte Kieselsäure oder Silicium-Aluminium-Mischoxide mit einer BET-Oberfläche von mehr als 50 m2/g. Die genannten Füllstoffe können hydrophobiert sein, beispielsweise durch Behandlung mit Organosilanen, -silazanen oder -siloxanen oder durch Veretherung von Hydroxylgruppen zu Alkoxygruppen. Bevorzugt sind pyrogen hergestellte Kieselsäuren mit einer BET-Oberfläche von mindestens 100 m2/gExamples of reinforcing fillers (5a), ie fillers having a BET surface area of at least 50 m 2 / g, are fumed silica, precipitated silica or silicon-aluminum mixed oxides having a BET surface area of more than 50 m 2 / g. The fillers mentioned may be rendered hydrophobic, for example by treatment with organosilanes, silanes or siloxanes or by etherification of hydroxyl groups to alkoxy groups. Preference is given to pyrogenic silicas having a BET surface area of at least 100 m 2 / g

    Die erfindungsgemäßen Siliconkautschukmassen enthalten verstärkende Füllstoffe (5a) in Mengen von vorzugsweise 0 bis 20 Gew.-%.Contain the silicone rubber compositions of the invention reinforcing fillers (5a) in amounts of preferably 0 to 20% by weight.

    Beispiele für nicht verstärkenden Füllstoffe (5b), also Füllstoffe mit einer BET-Oberfläche von weniger als 50 m2/g, sind Pulver aus Quarz, Cristobalit, Diatomeenerde, Calciumsilikat, Zirkoniumsilikat, Montmorillonite, wie Bentonite, Zeolithe einschließlich der Molekularsiebe, wie Natriumaluminiumsilikat, Metalloxide, wie Eisenoxid, Zinkoxid, Titandioxid und Aluminiumoxid bzw. deren Mischoxide, Metallhydroxide, wie Aluminiumhydroxid, Metallcarbonate, wie Calciumcarbonat, Magnesiumcarbonat und Zinkcarbonat, Metallsulfate, wie Bariumsulfat, Gips, Siliciumnitrid, Siliciumcarbid, Bornitrid, Glas-, Kohle- und Kunststoffpulver und Glas- und Kunststoffhohlkugeln.Examples of non-reinforcing fillers (5b), ie fillers having a BET surface area of less than 50 m 2 / g, are powders of quartz, cristobalite, diatomaceous earth, calcium silicate, zirconium silicate, montmorillonites such as bentonites, zeolites including molecular sieves such as sodium aluminosilicate , Metal oxides such as iron oxide, zinc oxide, titanium dioxide and aluminum oxide or their mixed oxides, metal hydroxides such as aluminum hydroxide, metal carbonates such as calcium carbonate, magnesium carbonate and zinc carbonate, metal sulfates such as barium sulfate, gypsum, silicon nitride, silicon carbide, boron nitride, glass, carbon and plastic powder and glass and plastic hollow spheres.

    Die erfindungsgemäßen Siliconkautschukmassen enthalten nicht verstärkende Füllstoffe in Mengen von vorzugsweise 0 bis 50 Gew.-%.The silicone rubber compositions of the invention do not contain reinforcing fillers in amounts of preferably 0 to 50 Wt .-%.

    Es kann eine Art von Füllstoff, es kann aber auch ein Gemisch von mindestens zwei Füllstoffen eingesetzt werden.It can be a type of filler, but it can also be a mixture of at least two fillers are used.

    Die harzartigen Organopolysiloxane enthalten vorzugsweise monofunktionelle (M) und tri- (T) und/oder tetrafunktionelle (Q) Einheiten, gegebenenfalls auch difunktionelle (D) Einheiten. Bevorzugt sind die sogenannten MQ-Harze (6), die aus monofunktionellen und tetrafunktionellen Einheiten bestehen. Die monofunktionellen Einheiten können als funktionelle Gruppen ungesättigte Kohlenwasserstoffreste, wie Alkenylgruppen oder Si-gebundenen Wasserstoff enthalten. Bevorzugt sind MQ-Harze (6) aus Einheiten der Formeln
    R5R2SiO1/2 und SiO4/2
    wobei R5 ein Rest R, ein Wasserstoffatom oder ein Rest R1 ist und R und R1 die oben dafür angegebene Bedeutung haben, und die Einheiten der Formel R5R2SiO1/2 gleich oder verschieden sein können.    The resinous organopolysiloxanes preferably contain monofunctional (M) and tri- (T) and / or tetrafunctional (Q) units, optionally also difunctional (D) units. Preference is given to the so-called MQ resins (6), which consist of monofunctional and tetrafunctional units. The monofunctional units may contain as functional groups unsaturated hydrocarbon radicals, such as alkenyl groups or Si-bonded hydrogen. Preference is given to MQ resins (6) from units of the formulas
    R 5 R 2 SiO 1/2 and SiO 4/2
    wherein R 5 is a radical R, a hydrogen atom or a radical R 1 and R and R 1 have the meaning given above, and the units of the formula R 5 R 2 SiO 1/2 may be the same or different.

    Das Verhältnis von M-Einheiten der Formel R5R2SiO1/2 zu Q-Einheiten der Formel SiO4/2 beträgt vorzugsweise 4:1 bis 1:2.The ratio of M units of the formula R 5 R 2 SiO 1/2 to Q units of the formula SiO 4/2 is preferably 4: 1 to 1: 2.

    Beispiele für MQ-Harze (6a) mit ungesättigten M-Einheiten sind solche aus Einheiten der Formeln
    SiO4/2 und R1R2SiO1/2 und gegebenenfalls R3SiO1/2,
    d.h. MQ-Harze mit ausschließlich ungesättigten M-Einheiten oder MQ-Harze mit gesättigten und ungesättigten M-Einheiten
    wobei R und R1 die oben dafür angegebene Bedeutung haben und das Verhältnis von M-Einheiten R1R2SiO1/2 und gegebenenfalls R3SiO1/2 zu Q-Einheiten SiO4/2 vorzugsweise 4:1 bis 1:2 beträgt und das Verhältnis von gesättigten M-Einheiten R3SiO1/2 zu ungesättigten M-Einheiten R1R2SiO1/2 vorzugsweise 10:1 bis 0:1.    Examples of MQ resins (6a) with unsaturated M units are those of units of the formulas
    SiO 4/2 and R 1 R 2 SiO 1/2 and optionally R 3 SiO 1/2 ,
    ie MQ resins with exclusively unsaturated M units or MQ resins with saturated and unsaturated M units
    wherein R and R 1 have the meaning given above and the ratio of M units R 1 R 2 SiO 1/2 and optionally R 3 SiO 1/2 to Q units SiO 4/2 preferably 4: 1 to 1: 2 and the ratio of saturated M units R 3 SiO 1/2 to unsaturated M units R 1 R 2 SiO 1/2 is preferably 10: 1 to 0: 1.

    Die MQ-Harze (6a), werden vorzugsweise in Mengen von 0 bis 100 Gew.-%, bezogen auf das Gesamtgewicht der Organopolysiloxane (1), eingesetzt.The MQ resins (6a) are preferably in amounts of 0 to 100 Wt .-%, based on the total weight of the organopolysiloxanes (1).

    Weitere Beispiele für MQ-Harze (6b) mit Si-gebundenem Wasserstoff aufweisenden M-Einheiten sind solche aus Einheiten der Formeln
    SiO4/2 und HR2SiO1/2 und gegebenenfalls R3SiO1/2,
    d.h. MQ-Harze, die nur M-Einheiten mit Si-gebundenem Wasserstoff enthalten,
    oder MQ-Harze, die M-Einheiten mit und ohne Si-gebundenem Wasserstoff enthalten, die vorzugsweise in der Komponente (B) enthalten sind, wobei R die oben dafür angegebene Bedeutung hat und das Verhältnis von M-Einheiten HR2SiO1/2 und gegebenenfalls R3SiO1/2 zu Q-Einheiten SiO4/2 vorzugsweise 4:1 bis 1:2, beträgt und das Verhältnis von M-Einheiten R3SiO1/2 zu M-Einheiten HR2SiO1/2 vorzugsweise 10:1 bis 0:1 beträgt.    Further examples of M-resins (6b) having Si-bonded hydrogen M units are those of units of the formulas
    SiO 4/2 and HR 2 SiO 1/2 and optionally R 3 SiO 1/2 ,
    ie MQ resins containing only M units with Si-bonded hydrogen,
    or MQ resins containing M units with and without Si-bonded hydrogen, which are preferably contained in the component (B), wherein R has the meaning given above and the ratio of M units HR 2 SiO 1/2 and optionally R 3 SiO 1/2 to Q units SiO 4/2 is preferably 4: 1 to 1: 2, and the ratio of M units R 3 SiO 1/2 to M units HR 2 SiO 1/2 is preferably 10: 1 to 0: 1.

    Die MQ-Harze (6b), werden vorzugsweise in Mengen von 0 bis 20 Gew.-%, bezogen auf das Gesamtgewicht der Organopolysiloxane (1), eingesetzt.The MQ resins (6b) are preferably in amounts of 0 to 20 Wt .-%, based on the total weight of the organopolysiloxanes (1).

    Erfindungsgemäßes Organopolysiloxan (2) ist in einer solchen Menge in der vernetzbaren Siliconkautschukmasse enthalten, dass das Molverhältnis von SiH-Gruppen in Organopolysiloxan (2) zu Si-gebundenem Rest R1 mit aliphatischer Kohlenstoff-Kohlenstoff-Mehrfachbindung in Organopolysiloxan (1) und MQ-Harz (6a) (Verhältnis SiHsiloxan(2)/C=Cgesamt) vorzugsweise 0,01 bis 10,0, bevorzugt 0,1 bis 2,0 beträgt.Organopolysiloxane (2) according to the invention is present in the crosslinkable silicone rubber composition in such an amount that the molar ratio of SiH groups in organopolysiloxane (2) to Si-bonded radical R 1 with aliphatic carbon-carbon multiple bond in organopolysiloxane (1) and MQ- Resin (6a) (ratio SiH siloxane (2) / C = C total ) is preferably 0.01 to 10.0, preferably 0.1 to 2.0.

    Die Gesamtmenge aller SiH-Gruppen in den erfindungsgemäßen Siliconkautschukmassen ist derart, dass das Molverhältnis von SiH-Gruppen in Organopolysiloxan (2), (2') und MQ-Harz (6b) zu Si-gebundenem Rest R1 mit aliphatischer Kohlenstoff-Kohlenstoff-Mehrfachbindung in Organopolysiloxan (1) und MQ-Harz (6a) (Verhältnis SiHgesamt/C=Cgesamt) vorzugsweise 1,0 bis 10,0, bevorzugt 1,7 bis 5,0 beträgt.The total amount of all SiH groups in the silicone rubber compositions according to the invention is such that the molar ratio of SiH groups in organopolysiloxane (2), (2 ') and MQ resin (6b) to Si-bonded radical R 1 with aliphatic carbon-carbon Multiple bond in organopolysiloxane (1) and MQ resin (6a) (SiH total ratio / C = C total ) is preferably 1.0 to 10.0, preferably 1.7 to 5.0.

    Die Komponenten (A) und (B) werden in einem Gewichtsverhältnis von vorzugsweise 100:1 bis 1:100, bevorzugt 1:1, verwendet.The components (A) and (B) are in a weight ratio of preferably 100: 1 to 1: 100, preferably 1: 1 used.

    Die erfindungsgemäßen Siliconkautschukmassen besitzen eine Viskosität von vorzugsweise 500 bis 20 000 mPa·s bei 25°C, bevorzugt 1 500 bis 10 000 mPa·s bei 25°C.The silicone rubber compositions according to the invention have a Viscosity of preferably 500 to 20,000 mPa · s at 25 ° C, preferably 1 500 to 10 000 mPa · s at 25 ° C.

    Die erfindungsgemäßen Siliconkautschukmassen weisen eine Topfzeit bei 25°C von vorzugsweise 12 Stunden bis 2 Wochen, bevorzugt 1 bis 5 Tage auf.The silicone rubber compositions according to the invention have a Pot life at 25 ° C, preferably 12 hours to 2 weeks, preferably 1 to 5 days.

    Die Behandlung der Flaschenkorken erfolgt vorzugsweise gemäß dem Verfahren, das in der eingangs erwähnten EP-A 773 090 (incorporated by reference) beschriebenen ist.The treatment of the bottle corks is preferably carried out according to the method described in the aforementioned EP-A 773 090 (incorporated by reference).

    Als Flaschenkorken werden handelsübliche Flaschenkorken mit einem Gewicht von vorzugsweise 2,5 bis 4,0 g verwendet.As bottle corks are commercially available bottle corks with a weight of preferably 2.5 to 4.0 g used.

    Die Behandlung der Flaschenkorken umfasst vorzugsweise

  • (a) Tauchen der Flaschenkorken in die erfindungsgemäßen zu Elastomeren vernetzbaren Siliconkautschukmassen,
  • (b) Mechanisches Entfernen von überschüssigen Siliconkautschukmassen von den Flaschenkorken und
  • (c) Vernetzung der Siliconkautschukmassen.
    • The treatment of the bottle cork preferably comprises
  • (a) dipping the bottle corks into the elastomeric silicone rubber compositions according to the invention,
  • (b) Mechanical removal of excess silicone rubber compositions from bottle corks and
  • (c) Crosslinking of the silicone rubber compositions.

    • Die erfindungsgemäßen Siliconkautschukmassen können ohne weitere Verdünnung mit organischen Lösungsmittel eingesetzt werden.The silicone rubber compositions of the invention can without further dilution with organic solvents used become.

    Die Beschichtung der Flaschenkorken erfolgt gemäß den in dem Stand der Technik üblichen Methoden für Vakuumimprägnierverfahren.The coating of the bottle cork is carried out according to the in the Prior art conventional methods for Vakuumimprägnierverfahren.

    Beim Tauchen der Flaschenkorken wird ein Vakuum von vorzugsweise 0,1 bis 0,005 bar angelegt. Das Tauchen erfolgt vorzugsweise in einem Zeitraum von 5 bis 20 Minuten. Danach wird das Vakuum gebrochen.When diving the bottle cork is a vacuum of preferably applied 0.1 to 0.005 bar. The diving takes place preferably in a period of 5 to 20 minutes. After that the vacuum is broken.

    Überschüssige Siliconkautschukmasse wird mechanisch, z.B. durch Abstreifen, von der Oberfläche der Flaschenkorken entfernt.Excess silicone rubber composition is mechanically, e.g. by Stripping, removed from the surface of the bottle cork.

    An der Oberfläche der Flaschenkorken verbleibt daher vorzugsweise eine geringe Menge von höchstens 0,1 g Siliconkautschukmasse, d.h. die Schichtdicke des Siliconkautschuks an der Oberfläche beträgt vorzugsweise 10 bis 30 µm.Therefore remains on the surface of the bottle cork preferably a small amount of at most 0.1 g Silicone rubber composition, i. the layer thickness of Silicone rubber on the surface is preferably 10 to 30 μm.

    Die Menge an aufgenommener Siliconkautschukmasse ist im wesentlichen durch die Beschaffenheit des Flaschenkorkens, d.h. den Anteil an Hohlräumen, die gewählten verfahrenstechnischen Parameter beim Beschichten und die Effizienz des gewählten Verfahrens zur mechanischen Entfernung von überschüssiger Siliconkautschukmasse von der Oberfläche der Flaschenkorken gegeben.
    Die Flaschenkorken nehmen vorzugsweise 0,5 bis 1,0 g Siliconkautschukmasse auf, d.h. die Gewichtszunahme der Flaschenkorken beträgt vorzugsweise 10 bis 40 Gew.-%.    The amount of silicone rubber composition incorporated is essentially dictated by the nature of the bottle cork, ie, the proportion of voids, the process parameters selected in coating, and the efficiency of the method chosen for mechanically removing excess silicone rubber mass from the surface of the bottle cork.
    The bottle corks preferably take up 0.5 to 1.0 g of silicone rubber composition, ie, the weight increase of the bottle cork is preferably 10 to 40 wt .-%.

    Die Vernetzung der erfindungsgemäßen Siliconkautschukmassen erfolgt vorzugsweise beim Druck der umgebenden Atmosphäre, also etwa bei 1020 hPa, sie kann aber auch bei höheren oder niedrigeren Drücken durchgeführt werden. The crosslinking of the silicone rubber compositions according to the invention is preferably carried out at the pressure of the surrounding atmosphere, ie at about 1020 hPa, but it can also be higher or higher lower pressures are performed.

    Die Vernetzung wird vorzugsweise bei einer Temperatur von 50°C bis 70°C, bevorzugt von 60°C, durchgeführt.The crosslinking is preferably carried out at a temperature of 50 ° C to 70 ° C, preferably from 60 ° C carried out.

    Die Härtungszeit der erfindungsgemäßen Siliconkautschukmassen beträgt vorzugsweise 30 bis 300 Minuten, bevorzugt 90 bis 180 Minuten, bei der oben genannten Temperatur.The curing time of the silicone rubber compositions according to the invention is preferably 30 to 300 minutes, preferably 90 to 180 Minutes, at the above temperature.

    Die Vulkanisationsreaktivität der erfindungsgemäßen Siliconkautschukmassen wird derart auf das Verfahren abgestimmt, dass sie zum einen eine hinreichend lange Topfzeit zur Verarbeitung zum anderen eine hinreichend rasche Härtungsgeschwindigkeit aufweisen.The vulcanization reactivity of the invention Silicone rubber compositions is so on the process agreed that on the one hand a sufficiently long pot life for processing on the other a sufficiently rapid Have curing rate.

    Das erfindungsgemäße Verfahren hat den Vorteil, dass Flaschenkorken mit guten Dichtungseigenschaften erhalten werden. Weiterhin hat das erfindungsgemäße Verfahren den Vorteil, dass der erfindungsgemäße Siliconkautschuk auf der Oberfläche der Flaschenkorken gut haftet und beim Einbringen des Korken in die Flasche nicht abgerieben wird.The inventive method has the advantage that Bottle corks obtained with good sealing properties become. Furthermore, the inventive method has the Advantage that the silicone rubber of the invention on the Surface of the bottle cork sticks well and when inserting the cork is not rubbed into the bottle.

    Beispiele 1 bis 4:Examples 1 to 4:

    Die in den Tabellen 1 bis 4 angegebenen Bestandteilen werden gemischt und es wird jeweils eine Komponente A und B hergestellt.The ingredients given in Tables 1 to 4 are mixed and there is a component A and B respectively produced.

    Die jeweils erhaltenen Komponenten A und B werden dann im Verhältnis 1:1 gemischt. Komponente A Gew.-teile Komponente B Gew.-teile Vi-Polymer 20.000 535 Vi-Polymer 20.000 300 Vi-Polymer 1.000 535 Vi-Polymer 1.000 300 HDK 30 H 1000 500 Pt Katalysator 4,2 H-Siloxan 2 Inhibitor 0,6 Topfzeit der Mischung A+B beträgt 48 Stunden bei 25°C. Komponente A Gew.-teile Komponente B Gew.-teile Vi-Polymer 1.000 500 Vi-Polymer 1.000 520 HDK 30 QM-H Harz 10 Pt Katalysator 2,1 H-Siloxan 0,5 Inhibitor 0,4 Topfzeit der Mischung A+B beträgt 38 Stunden bei 25°C. Komponente A Gew.-teile Komponente B Gew.-teile Vi-Polymer 7.000 400 Vi-Polymer 7.000 500 QM-Vi Harz 100 Metalloxide 2 Pt Katalysator 6,4 H-Siloxan 4 Inhibitor 1,0 Topfzeit der Mischung A+B beträgt 72 Stunden bei 25°C. Komponente A Gew.-teile Komponente B Gew.-teile Vi-Polymer 20.000 210 Vi-Polymer 20.000 195 Vi-Polymer 1.000 725 Vi-Polymer 1.000 610 QM-Vi Harz 140 QM-Vi Harz 120 Metalloxide 20 Vernetzer 525 162 Pt Katalysator 2,0 H-Siloxan 10 Inhibitor 0,3 Topfzeit der Mischung A+B beträgt 30 Stunden bei 25°C. The respectively obtained components A and B are then mixed in a ratio of 1: 1. Component A Parts by weight Component B Parts by weight Vi-Polymer 20,000 535 Vi-Polymer 20,000 300 Vi-polymer 1,000 535 Vi-polymer 1,000 300 HDK 30 H 1000 500 Pt catalyst 4.2 H-siloxane 2 inhibitor 0.6 Pot life of mixture A + B is 48 hours at 25 ° C. Component A Parts by weight Component B Parts by weight Vi-polymer 1,000 500 Vi-polymer 1,000 520 HDK 30 QM-H resin 10 Pt catalyst 2.1 H-siloxane 0.5 inhibitor 0.4 Pot life of mixture A + B is 38 hours at 25 ° C. Component A Parts by weight Component B Parts by weight Vi-Polymer 7,000 400 Vi-Polymer 7,000 500 QM-Vi resin 100 metal oxides 2 Pt catalyst 6.4 H-siloxane 4 inhibitor 1.0 Pot life of mixture A + B is 72 hours at 25 ° C. Component A Parts by weight Component B Parts by weight Vi-Polymer 20,000 210 Vi-Polymer 20,000 195 Vi-polymer 1,000 725 Vi-polymer 1,000 610 QM-Vi resin 140 QM-Vi resin 120 metal oxides 20 Crosslinker 525 162 Pt catalyst 2.0 H-siloxane 10 inhibitor 0.3 Pot life of mixture A + B is 30 hours at 25 ° C.

    Bei den in Tabelle 1 bis 4 angegebenen Bestandteile handelt es sich um folgende Verbindungen, wobei Me=Methylrest und Vi=Vinylrest:The components listed in Tables 1 to 4 are the following compounds, wherein Me = methyl and Vi = vinyl radical:

    Vi-Polymer 1.000:Vi-Polymer 1.000:

    Organopolysiloxan der Formel: ViMe2SiO(Me2SiO)n 1SiMe2Vi   n1=200 mit einer Viskosität von 1 000 mPa·s bei 25°C Organopolysiloxane of the formula: ViMe 2 SiO (Me 2 SiO) n 1 SiMe 2 Vi n 1 = 200 with a viscosity of 1000 mPa · s at 25 ° C.

    Vi-Polymer 7.000:Vi-Polymer 7,000:

    Organopolysiloxan der Formel: ViMe2SiO(Me2SiO)n 2SiMe2Vi   n2=450 mit einer Viskosität von 7 000 mPa·s bei 25°COrganopolysiloxane of the formula: ViMe 2 SiO (Me 2 SiO) n 2 SiMe 2 Vi n 2 = 450 with a viscosity of 7 000 mPa · s at 25 ° C.

    Vi-Polymer 20.000:Vi-Polymer 20,000:

    Organopolysiloxan der Formel: ViMe2SiO(Me2SiO)n 3SiMe2Vi   n3=600 mit einer Viskosität von 20 000 mPa·s bei 25°COrganopolysiloxane of the formula: ViMe 2 SiO (Me 2 SiO) n 3 SiMe 2 Vi n 3 = 600 with a viscosity of 20,000 mPa · s at 25 ° C.

    H-Siloxan:H-siloxane:

    Organopolysiloxan der Formel: Me3SiO(MeHSiO)n 4SiMe3   n4=50 mit einer Viskosität von 1 000 mPa·s bei 25°C und 1,6 Gew.-% Si-gebundenem Wasserstoff.Organopolysiloxane of the formula: Me 3 SiO (MeHSiO) n 4 SiMe 3 n 4 = 50 with a viscosity of 1,000 mPa · s at 25 ° C. and 1.6% by weight of Si-bonded hydrogen.

    H 1000:H 1000:

    Organopolysiloxan der Formel: HMe2SiO(Me2SiO)n 5SiMe2H   n=200 mit einer Viskosität von 1 000 mPa·s bei 25°C und 0,013 Gew.-% Si-gebundenem Wasserstoff.Organopolysiloxane of the formula: HMe 2 SiO (Me 2 SiO) n 5 SiMe 2 H n = 200 with a viscosity of 1000 mPa · s at 25 ° C and 0.013 wt .-% Si-bonded hydrogen.

    Vernetzer 525:Crosslinker 525:

    Organopolysiloxan der Formel:
    Me3SiO(MeHSiO)n 6(Me2SiO)n 7SiMe3   n6+n7=200,   n6:n7=1:2
    mit einer Viskosität von 400 mPa·s bei 25°C und 0,5 Gew.-% Si-gebundenem Wasserstoff.    Organopolysiloxane of the formula:
    Me 3 SiO (MeHSiO) n 6 (Me 2 SiO) n 7 SiMe 3 n 6 + n 7 = 200, n 6 : n 7 = 1: 2
    with a viscosity of 400 mPa · s at 25 ° C and 0.5 wt .-% Si-bonded hydrogen.

    QM-Vi Harz:QM-Vi resin:

    Harz aus Einheiten der Formel
    SiO4/2 (Q) , Me3SiO1/2 (M) und ViMe2SiO1/2 (MV),
    mit einem Verhältnis von Q : M : MV = 1 : 0,1 : 0,6    Resin of units of the formula
    SiO 4/2 (Q), Me 3 SiO 1/2 (M) and ViMe 2 SiO 1/2 (M V ),
    with a ratio of Q: M: M V = 1: 0.1: 0.6

    QM-H Harz:QM-H resin:

    Harz aus Einheiten der Formel
    SiO4/2 (Q), HMe2SiO1/2 (MH),
    mit einem Verhältnis von Q : MH = 1 : 2     Resin of units of the formula
    SiO 4/2 (Q), HMe 2 SiO 1/2 (M H ),
    with a ratio of Q: M H = 1: 2

    HDK:HDK:

    Pyrogen hergestellte Kieselsäure mit einer BET-Oberfläche von 125 m2/g (käuflich erwerblich unter dem Handelsnamen WACKER HDK®S13 bei der Firma Wacker-Chemie GmbH).Pyrogenic silica with a BET surface area of 125 m 2 / g (commercially available under the trade name WACKER HDK®S13 from Wacker-Chemie GmbH).

    Metalloxide:Metal oxides:

    Mischung aus verschiedenen Metalloxiden enthaltend Titandioxid und Eisenoxiden käuflich erwerblich unter den Handelsnamen Kronos® 2056 bei der Firma Kronos Titan, SICOTAN® Gelb K 1011 bei der Firma BASF AG und BAYFERROX® 610 bei der Firma Bayer AG.
    Das Mischungsverhältnis dieser drei Stoffe beträgt 10:10:1. Das Mischungsverhältnis wurde so gewählt, um einen dem Naturkorken möglichst ähnlichen Farbton zu erreichen.    Mixture of various metal oxides containing titanium dioxide and iron oxides commercially available under the trade names Kronos® 2056 from Kronos Titan, SICOTAN® Yellow K 1011 from BASF AG and BAYFERROX® 610 from Bayer AG.
    The mixing ratio of these three substances is 10: 10: 1. The mixing ratio was chosen so as to achieve a natural color cork as closely as possible hue.

    Inhibitor: EthinylcyclohexanolInhibitor: ethynylcyclohexanol Pt-Katalysator:Pt catalyst:

    Lösung eines Platin-1,3-Divinyl-1,1,3,3-tetramethyldisiloxan-Komplexes in Dimethylpolysiloxan mit einem Platingehalt dieser Lösung von 1 Gew.-%Solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in dimethylpolysiloxane having a platinum content thereof Solution of 1% by weight

    Vergleichsmasse gemäß EP-A 773 090:Comparative mass according to EP-A 773 090:

    Es wird eine additionsvernetzende Zweikomponenten-Siliconkautschukmasse erhältlich unter dem Handelsnamen Elastosil® M4600 bei der Wacker-Chemie GmbH verwendet. Der Vernetzer, ein lineares H-Siloxan mit seitenständigen Si-gebundenen Wasserstoffatomen, der Formel
    Me3SiO(MeHSiO)y(Me2SiO)zSiMe3   mit y:z=1:10
    besitzt einen Gehalt an Si-gebundenen Wasserstoff von 0,14 bis 0,17 Gew.-%.    An addition-crosslinking two-component silicone rubber composition obtainable under the trade name Elastosil® M4600 from Wacker-Chemie GmbH is used. The crosslinker, a linear H-siloxane with pendant Si-bonded hydrogen atoms, of the formula
    Me 3 SiO (MeHSiO) y (Me 2 SiO) z SiMe 3 with y: z = 1: 10
    has a content of Si-bonded hydrogen of 0.14 to 0.17 wt .-%.

    Die Komponente A und B werden im Verhältnis 10:1 gemischt. Components A and B are mixed in a ratio of 10: 1.

    Beispiel 5 und Vergleichsversuch:Example 5 and comparative experiment:

    Handelsübliche Flaschenkorken mit einem Gewicht von 3,3 g, einem Durchmesser von 24 mm und einer Länge von 45 mm werden jeweils in die Siliconkautschukmischungen gemäß den Beispielen 1 bis 4 bzw. in die Vergleichsmasse gemäß EP-A 773 09 getaucht und einer Vakuumimprägnierung bei 10 mbar für 15 Minuten unterworfen. Nach dem Entfernen des Vakuums wird überschüssige Siliconkautschukmischung von der Oberfläche der Flaschenkorken mechanisch entfernt. Die beschichteten Flaschenkorken werden im Ofen bei 60°C 120 Minuten gehärtet.Commercially available bottle corks weighing 3.3 g, a diameter of 24 mm and a length of 45 mm each in the silicone rubber mixtures according to the examples 1 to 4 or immersed in the comparative composition according to EP-A 773 09 and vacuum impregnation at 10 mbar for 15 minutes subjected. After removal of the vacuum becomes excess Silicone rubber compound from the surface of the bottle cork mechanically removed. The coated bottle corks are in the Oven hardened at 60 ° C for 120 minutes.

    Die Haftung des Siliconkautschuks auf der Korkenoberfläche wird folgendermaßen geprüft:The adhesion of the silicone rubber on the cork surface becomes checked as follows:

    Zwei mit den erfindungsgemäßen Siliconkautschukmassen behandelte Korken werden mit ihren Mantelflächen gegeneinander gerieben. Die Korken weisen keinerlei Abrieb auf.
    Beim Verschließen der Flaschen mit diesen Korken kommt es nicht zum Abrieb des Siliconkautschuks von der Korkenoberfläche.    Two corks treated with the silicone rubber compositions according to the invention are rubbed against one another with their lateral surfaces. The corks have no abrasion.
    When sealing the bottles with these corks, the silicone rubber does not rub off the cork surface.

    Analog werden zwei Korken, die mit der Siliconkautschukmasse gemäß Vergleichsversuch behandelte wurden, mit ihren Mantelflächen gegeneinander gerieben. Es kommt zum Abrieb des vulkanisierten Siliconkautschuks in Form kleiner Partikel. Beim Verschließen der Flaschen mit solchen Korken kommt es zum Abrieb des Siliconkautschuks von der Oberfläche der Korken, welcher in Form kleiner Vulkanisatpartikel den Flascheninhalt kontaminiert.Analogously, two corks are made with the silicone rubber compound were treated according to comparative experiment, with their Lateral surfaces rubbed against each other. It comes to the abrasion of Vulcanized silicone rubber in the form of small particles. At the Closing the bottles with such corks it comes to Abrasion of the silicone rubber from the surface of the corks, which in the form of small Vulkanisatpartikel the bottle contents contaminated.

    Claims (5)

    1. Process for impregnating bottle corks wherein the bottle corks are treated with silicone rubber compositions which can be crosslinked to elastomers and comprise
      (1) organopolysiloxanes having residues containing aliphatic carbon-carbon multiple bonds,
      (2) organopolysiloxanes containing Si-bonded hydrogen atoms,
      (3) catalysts which promote the addition of Si-bonded hydrogen to aliphatic multiple bonds, and, if desired,
      (4) agents known as inhibitors, which retard the addition of Si-bonded hydrogen to aliphatic multiple bonds,
      characterized in that the organopolysiloxanes (2) contain from 1.0 to 2.0% by weight of Si-bonded hydrogen.
    2. Process of Claim 1, characterized in that the silicone rubber compositions which can be crosslinked to elastomers are two-component compositions wherein component (A) comprises organopolysiloxane (1), catalyst (3), and, if desired, inhibitor (4) and component (B) comprises organopolysiloxane (2) and also, if desired, additional organopolysiloxane (1) and, if desired, inhibitor (4).
    3. Process of Claim 1 or 2, characterized in that organopolysiloxanes (1) used are those of the general formula R1 gR3-gSiO(SiR2O)n(SiRR1O)mSiR3-gR1 g where each R is identical or different and is a monovalent, optionally halogenated hydrocarbon radical having 1 to 18 carbon atom(s) per radical, and
      each R1 is identical or different and is a monovalent hydrocarbon radical having a terminal aliphatic carbon-carbon multiple bond with from 2 to 8 carbon atoms per radical,
      g is 0, 1, 2 or 3,
      m is 0 or an integer from 1 to 500, and
      n is or an integer from 70 to 1 000,
      with the proviso that the organopolysiloxanes of the formula (II) contain per molecule at least 2 radicals R1.
    4. Process of Claim 1, 2 or 3, characterized in that organopolysiloxanes (2) used are those of the general formula HhR3-hSiO(SiR2O)o(SiR2-xHxO)pSiR3-hHh where R is as defined in Claim 3,
      h is 0, 1 or 2,
      o is 0 or an integer from 1 to 1 000,
      p is an integer from 1 to 1 000, and
      x is 1 or 2,
      with the proviso that the organopolysiloxanes of the formula (IV) contain from 1.0 to 2.0% by weight of Si-bonded hydrogen.
    5. Process of one of Claims 1 to 4, characterized in that the treatment comprises
      (a) dipping the bottle corks in the silicone rubber compositions which can be crosslinked to elastomers, according to one of Claims 1 to 4, under vacuum,
      (b) mechanically removing excess silicone rubber compositions from the bottle corks, and
      (c) crosslinking the silicone rubber compositions.
    EP02777084A 2001-09-27 2002-09-12 Method for impregnating bottle corks Expired - Lifetime EP1429989B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE10147626A DE10147626A1 (en) 2001-09-27 2001-09-27 Process for impregnating bottle corks
    DE10147626 2001-09-27
    PCT/EP2002/010261 WO2003029130A1 (en) 2001-09-27 2002-09-12 Method for impregnating bottle corks

    Publications (2)

    Publication Number Publication Date
    EP1429989A1 EP1429989A1 (en) 2004-06-23
    EP1429989B1 true EP1429989B1 (en) 2005-05-25

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    Application Number Title Priority Date Filing Date
    EP02777084A Expired - Lifetime EP1429989B1 (en) 2001-09-27 2002-09-12 Method for impregnating bottle corks

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    US (1) US20040241334A1 (en)
    EP (1) EP1429989B1 (en)
    AT (1) ATE296258T1 (en)
    AU (1) AU2002338678B2 (en)
    DE (2) DE10147626A1 (en)
    ES (1) ES2240820T3 (en)
    PT (1) PT1429989E (en)
    WO (1) WO2003029130A1 (en)
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    DE102004008109B4 (en) * 2004-02-18 2007-07-12 Sebastian Heintges Artificial cork
    DE102004047709A1 (en) * 2004-09-30 2006-04-06 Wacker Chemie Ag Bottle caps with reduced trichloroanisole release and process for its preparation
    FR2956058B1 (en) * 2010-02-08 2012-02-03 Jacques Granger TREATMENT OF NATURAL CORK STOP PLUGS AND PLUGS OBTAINED THEREBY

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    DE1927397A1 (en) * 1969-05-29 1970-12-10 Grants Of St James S Ltd Bottle corks treated to avoidcontamination and liquid seepa - and liquid seapage
    DE2654893A1 (en) * 1976-12-03 1978-06-15 Wacker Chemie Gmbh PROCESS FOR PRODUCING STICKY FABRIC REPELLENT COATING
    DE2736499C2 (en) * 1977-08-12 1990-03-29 Wacker-Chemie GmbH, 8000 München Process for the production of coatings which repel tacky substances
    IT1253568B (en) * 1991-12-12 1995-08-08 Tecnochimica Srl METHOD OF LUBRICATION AND SEALING OF THE CAPS WITH SILICO-PARAFFINIC AND PLASTO-SILICO-PARAFFINIC COMPOUNDS
    GB9519972D0 (en) * 1995-09-28 1995-11-29 Ag Patents Ltd Improved container stoppers
    ES2205005T3 (en) * 1995-11-07 2004-05-01 Portocork Internacional, S.A. MANUFACTURING PROCEDURE OF CORK PLUGS FOR BOTTLES.
    JP3796554B2 (en) * 1996-02-29 2006-07-12 内山工業株式会社 Cork grain-containing addition-curable silicone composition and molded plug
    DE19653167A1 (en) * 1996-12-19 1998-10-01 Wacker Chemie Gmbh Organopolysiloxane containing unsaturated aliphatic groups
    AUPP989499A0 (en) * 1999-04-22 1999-05-13 Vinpac International Pty Ltd Treated closures 3

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    DE10147626A1 (en) 2003-04-24
    US20040241334A1 (en) 2004-12-02
    PT1429989E (en) 2005-08-31
    EP1429989A1 (en) 2004-06-23
    DE50203217D1 (en) 2005-06-30
    AU2002338678B2 (en) 2005-09-22
    ZA200400560B (en) 2004-11-01
    ES2240820T3 (en) 2005-10-16
    ATE296258T1 (en) 2005-06-15

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