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EP3110889A1 - Addition cross-linking silicone composition with a high water-absorption capacity - Google Patents

Addition cross-linking silicone composition with a high water-absorption capacity

Info

Publication number
EP3110889A1
EP3110889A1 EP15706231.6A EP15706231A EP3110889A1 EP 3110889 A1 EP3110889 A1 EP 3110889A1 EP 15706231 A EP15706231 A EP 15706231A EP 3110889 A1 EP3110889 A1 EP 3110889A1
Authority
EP
European Patent Office
Prior art keywords
silicone composition
addition
radicals
silicone
absorption capacity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP15706231.6A
Other languages
German (de)
French (fr)
Inventor
Enno Funk
Torsten Gottschalk-Gaudig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP3110889A1 publication Critical patent/EP3110889A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • 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
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C08K2003/3063—Magnesium sulfate

Definitions

  • the present invention relates to an addition-crosslinkable silicone composition which, after crosslinking, exhibits a high, reversible water absorption capacity, the production and use thereof.
  • silicone rubber be hydrophilic and have a high ability to reversibly pick up water.
  • the silicone rubber be hydrophilic and have a high ability to reversibly pick up water.
  • the water vapor of the breath or perspiration has no opportunity to escape and condensation and filming between skin and hardened silicone gum rapidly occurs. This leads to a very bad wearing comfort especially over a longer period.
  • the alkenyl group-containing polyorganosiloxane (A) preferably has a composition of the average general formula (1) R 1 x R 2 y SiO (4 _ x _ y) / 2 (1), wherein is a monovalent, optionally-substituted halo- or cyanosubsti-, optionally via an organic divalent group to silicon-bonded C] _-CIO hydrocarbon radical containing aliphatic carbon-carbon multiple bonds,
  • alkenyl groups R 1 are accessible to an addition reaction with a SiH-functional crosslinking agent (B).
  • a SiH-functional crosslinking agent B.
  • alkenyl groups having 2 to 6 carbon atoms such as vinyl, allyl, methailyl, 1-propenyl, 5-hexenyl, ethynyl, butadienyl, hexadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, preferably vinyl and allyl, are used.
  • Organic divalent groups, via which the alkenyl groups R 1 may be bonded to silicon of the polymer chain consist for example of oxyalkylene units, such as those of the general formula (2)
  • n values from 1 to 4, in particular 1 or 2 and
  • o mean values of 1 to 20, in particular from 1 to 5.
  • the oxyalkylene units of the general formula (2) are bonded to the left of a silicon atom.
  • radicals can be bonded in any position of the polymer chain, in particular on the terminal silicon atoms.
  • unsubstituted radicals R 2 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, such as the n-hexyl, heptyl, such as the n-heptyl, octyl, such as the n-octyl and iso-octyl, such as the 2, 2, 4-trimethylpentyl, nonyl, such as the n-nonyl, decyl such as the n-decyl radical;
  • Alkenyl radicals such as the vinyl, allyl, ⁇ 5-hexenyl, 4-vinylcyclohexyl and 3-norbornenyl radicals; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, 4-ethylcyclohexyl, cycloheptyl radicals, norbornyl radicals and methylcyclohexyl radicals;
  • Aryl radicals such as the phenyl, biphenylyl, naphthyl radical; Alkaryl
  • R 2 preferably has 1 to 6 carbon atoms. Particularly preferred are methyl and phenyl.
  • Component (A) may also be a mixture of different alkenyl-containing polyorganosiloxanes which differ, for example, in the alkenyl group content, the nature of the alkenyl group or structurally.
  • the structure of the alkenyl-containing polyorganosiloxanes (A) may be linear, cyclic or branched.
  • the content of tri- and / or tetrafunctional units leading to branched polyorganosiloxanes is typically very low, preferably at most 20 mol%, in particular at most 0.1 mol%.
  • the viscosity of the polyorganosiloxane (A) at 25 ° C is preferably 0.5 to 500 Pa-s, in particular 1 to 200 Pa-s, most preferably 1 to 100 Pa-s.
  • the at least two SiH functions per molecule containing organosilicon compound (B) preferably has a composition of the average general formula (4) H a R3 b siO (4 _ a _ b) / 2 (4), in which
  • R3 is a monovalent, optionally halogen or cyano-substituted, SiC-bonded C ⁇ -CIQ hydrocarbon radical which is free of aliphatic carbon-carbon multiple bonds and
  • a and b are nonnegative integers
  • R 1 preferably has 1 to 6 carbon atoms. Particularly preferred are methyl and phenyl.
  • organosilicon compound (B) containing three or more SiH bonds per molecule.
  • organosilicon compound (B) having only two SiH bonds per molecule, it is advisable to use a polyorganosiloxane (A) which has at least three alkenyl groups per molecule.
  • the organosilicon compound (B) preferably contains at least three and at most 600 silicon atoms per molecule. Preferred is the use of organosilicon compound (B) containing 4 to 200 silicon atoms per molecule.
  • the structure of the organosilicon compound (B) may be linear, branched, cyclic or network-like.
  • organosilicon compounds (B) are linear polyorganosiloxanes of the general formula (5)
  • the SiH-functional organosilicon compound (B) is preferably contained in the crosslinkable silicone composition in an amount such that the molar ratio of SiH groups to alkenyl groups is 0.5 to 5, especially 1.0 to 3.0.
  • hydrosilylation catalyst (C) it is possible to use all known catalysts which catalyze the hydrosilylation reactions taking place in the crosslinking of addition-crosslinking silicone mixtures.
  • the hydrosilylation catalysts (C) used are in particular metals and their compounds from the group consisting of platinum, rhodium, palladium, ruthenium and iridium.
  • platinum and platinum compounds are used. Particularly preferred are those platinum compounds which are soluble in polyorganosiloxanes.
  • soluble platinum compounds which can be used are the platinum-olefin complexes of the formulas (PtCl.sub.2.alphine) .sub.2 and H (PtCl.sub.3.alfin), preferably alkenes having from 2 to 8 carbon atoms, such as ethylene, propylene and isomers of butene and octene, or cycloalkenes having from 5 to 7 carbon atoms, such as cyclopentene, cyclohexene and cycloheptene.
  • platinum-cyclopropane complex of the formula (PtCl 2 C 3 H 6 ) 2 / the reaction products of hexachloroplatinic acid with alcohols, ethers and aldehydes or mixtures thereof or the reaction product of hexachloroplatinic acid with methylvinylcyclotetrasiloxane in the presence of sodium bicarbonate in ethanolic solution ,
  • platinum-cyclopropane complex of the formula (PtCl 2 C 3 H 6 ) 2 / the reaction products of hexachloroplatinic acid with alcohols, ethers and aldehydes or mixtures thereof or the reaction product of hexachloroplatinic acid with methylvinylcyclotetrasiloxane in the presence of sodium bicarbonate in ethanolic solution .
  • platinum-cyclopropane complex of the formula (PtCl 2 C 3 H 6 ) 2 / the reaction products of hexachloroplatinic acid with alcohols, ether
  • Divinyltetramethyldisiloxane is very suitable.
  • platinum compounds described in EP 1 077 226 A1 and EP 0 994 159 A1 the disclosure of which in this respect should also be the subject of this application.
  • the hydrosilylation catalyst (C) can be used in any desired form, for example also in the form of hydrosilylation catalyst-containing microcapsules, or Polyor- ganosiloxanpumblen, as described in EP 1 006 147 AI, the related disclosure should also be the subject of this application.
  • the content of hydrosilylation catalysts (C) is preferably selected so that the addition-crosslinkable silicone mixture (S) has a Pt content of 0.1 to 200 ppm by weight, in particular from 0.5 to 40 ppm by weight.
  • hydratable salt (D) means that the salt is in a state where it can additionally absorb water by hydration, that is, the salt is used either in its anhydrous form or in a partially hydrated form.
  • the hydrated salt is preferably particulate or powdery in nature and may be, for example, alkali metal / alkaline earth metal carbonate, bicarbonate, (poly) phosphate, citrate (anhydrous) or sulfate (anhydrous). Mixtures of two or more hydratable compounds may also be used.
  • (D) is preferably anhydrous sodium sulfate or anhydrous magnesium sulfate or a mixture thereof. Preference is given to using from 1 to 30% by weight of (D). Particularly preferably 5 to 25 wt .-%, most preferably 10 to 20 wt -.%.
  • the addition-crosslinkable silicone compositions according to the invention also contain, as further constituent, at least one filler (E).
  • Non-reinforcing fillers (E) with a BET surface area of up to 50 m 2 / g are, for example, quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, metal oxide powders such as aluminum, titanium, iron or zinc oxides or their mixed oxides, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic ulver.
  • Reinforcing fillers ie fillers having a BET surface area of at least 50 m 2 / g, in particular 100 to 400 m 2 / g, are, for example, fumed silica, precipitated silica, aluminum hydroxide, carbon black, such as furnace and acetylene black and silicon aluminum Mixed oxides of large BET surface area.
  • the stated fillers (E) may be rendered hydrophobic, for example by treatment with organosilanes, organosilazanes or siloxanes or by etherification of hydroxyl groups to alkoxy groups. It may be one kind of filler (E), it may also be a mixture of at least two fillers (E) are used.
  • the silicone compositions of the invention contain at least 3 wt .-%, more preferably at least 5 wt .-%, in particular at least 10 wt .-% and at most 50 wt .-% filler content (E).
  • the silicone compositions according to the invention may optionally contain, as further constituent (F), possible additives in a proportion of 0 to 70% by weight, preferably 0.0001 to 40% by weight.
  • additives may be, for example, resinous polyorganosiloxanes other than the polyorganosiloxanes (A) and (B), dispersing aids, solvents, adhesion promoters, pigments, dyes, plasticizers, organic polymers, heat stabilizers and inhibitors. These include additives such as dyes and pigments.
  • thixotropic constituents such as finely divided silica or other commercially available thixotropic additives, can be contained as constituents.
  • a further constituent (F) for better crosslinking preferably at most 0.5% by weight, particularly preferably at most 0.3% by weight, in particular ⁇ 0.1% by weight, of peroxide may be present.
  • additives can be included, which serve to specifically adjust the processing time, light-off temperature and crosslinking rate of the crosslinking compounds.
  • These inhibitors and stabilizers are well known in the field of crosslinking compositions.
  • a further subject of the present invention is a process for the preparation of the addition-crosslinkable silicone composition according to the invention, a process for the preparation of the crosslinked silicone rubber from the silicone compositions according to the invention and the silicone rubber moldings or silicone rubber coatings obtainable in this way.
  • the preparation or compounding of the silicone composition according to the invention is preferably carried out by mixing the components (A) and (D) and (E) and optionally (F).
  • the composition of the invention may be prepared as a 1-, 2- or multi-component composition.
  • crosslinking after addition of crosslinker (B) and hydrosilylation catalyst (C) is preferably carried out by heating, preferably at 30 to 250 ° C, preferably at least 50 ° C, in particular at least 100 ° C, preferably at 150-210 ° C. ,
  • the silicone gums according to the invention thus obtained have the advantage that they have a surprisingly high water absorption and a good permanence of the component (D) in the crosslinked silicone rubber
  • silicone gum according to the invention can be used as shaped articles, for example for respiratory masks, clothing, upholstery or furniture.
  • Silicone rubber coatings of the invention obtained in this way are used, for example, on fibers or fabrics.
  • Another possible use of the cured silicone rubber according to the invention is its use as a reusable desiccant, for example in the form of granules or platelets.
  • the viscosities are determined at 25 ° C and atmospheric pressure of 1013 hPa.
  • a suitable method is the rotational viscometric measurement according to DIN EN ISO 3219.
  • ELASTOSIL ® are commercially available addition-2-component (2K) silicone compositions of Wacker Chemie AG, Kunststoff. Anhydrous sodium sulfate and anhydrous magnesium sulfate were purchased from Merck KGaA, Darmstadt. example 1
  • This program is used in succession 5 times to optimally homogenize the sample - in each case you use a spatula to dissolve the mixture from the sides and the bottom of the mixing container.
  • Vulcanization is carried out in a laboratory press P300 P / M from Collin at 165 ° C. for 5 min and a pressure of 380 N / cm 2.
  • a vulcanizate sample is stored a) for 8 hours and b) for 700 hours in demineralised water.
  • the weight increase after drying with absorbent paper a) 4.1% and b) 39.2 o,
  • Example 1 The procedure of Example 1 is repeated with the modification that 18 g (10 wt .-%) of anhydrous sodium sulfate with each 81 g Elastosil ® 3003/40 A and B component are homogenized.
  • Example 2 The vulcanization is then carried out as described in Example 1 and a vulcanizate sample a) is stored for 8 hours and b) for 700 hours in demineralized water.
  • the weight gain after drying is a) 4.5% and b) 78.4%.
  • Example 1 The procedure of Example 1 is repeated with the modification that 27 g (15 wt .-%) of anhydrous sodium sulfate are homogenized with 76.5 g Elastosil ® 3003/40 A and B component.
  • the vulcanization is then carried out as described in Example 1 and a vulcanizate sample a) is stored for 8 hours and b) for 700 hours in demineralized water.
  • the weight gain after drying is a) 5.3% and b) 171.4%.
  • Example 1 The procedure of Example 1 is repeated with the modification that 9 g (5 wt .-%) of anhydrous magnesium sulfate with each 85.5 g Elastosil ® 3003/40 A and B component homogenized Siert.
  • Example 5 The vulcanization is then carried out as described in Example 1 and a vulcanizate sample a) is stored for 8 hours and b) for 700 hours in demineralized water. The weight gain after drying is a) 4.0% and b) 43.8%.
  • Example 5 The weight gain after drying is a) 4.0% and b) 43.8%.
  • Example 1 The procedure of Example 1 is repeated with the modification that 18 g (10 wt .-%) of anhydrous magnesium sulfate with each 81 g of Elastosil ® 3003/40 A and B component homogenized Siert.
  • Example 2 The vulcanization is then carried out as described in Example 1 and a vulcanizate sample a) is stored for 8 hours and b) for 700 hours in demineralized water.
  • the weight gain after drying is a) 4.6% and b) 54.7%.
  • Example 1 The procedure of Example 1 is repeated with the modification that 18 g (10 wt .-%) corn starch are homogenized with 81 g Elastosil ® 3003/40 A and B component.
  • Example 2 The vulcanization is then carried out as described in Example 1 and a vulcanizate sample a) is stored for 8 hours and b) for 700 hours in demineralized water.
  • the weight gain after drying is a) 0.8% and b) 2.8%.
  • Example 1 The procedure of Example 1 is repeated with the modification that 18 g (10 wt .-%) of gelatin are homogenized with 81 g each Elastosil ® 3003/40 A and B component.
  • Example 2 The vulcanization is then carried out as described in Example 1 and a vulcanizate sample a) is stored for 8 hours and b) for 700 hours in demineralized water.
  • the weight gain after drying is a) 2.9% and b) 16.6%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to an addition cross-linking silicone composition containing: (A) at least one polyorganosiloxane having at least two alkenyl groups per molecule and a viscosity of between 0.2 and 1000 Pa⋅s at 25°C; (B) at least one SiH-functional cross-linking agent; (C) at least one hydrosilylation catalyst; (D) at least one hydratable salt; and (E) at least one filler.

Description

Additionsvernetzende Siliconzusammensetzung mit hohem  Addition-crosslinking silicone composition with high
Wasseraufnahmevermögen Water absorption capacity
Die vorliegende Erfindung betrifft eine additionsvernetzbare Siliconzusammensetzung, die nach Vernetzung ein hohes, rever- sibles Wasseraufnahmevermögen zeigen, deren Herstellung und Verwendung . The present invention relates to an addition-crosslinkable silicone composition which, after crosslinking, exhibits a high, reversible water absorption capacity, the production and use thereof.
Bei bestimmten Anwendungen von Formkörpern oder Beschichtungen aus gehärtetem Silicongummi ist es wichtig, dass der Silicongummi hydrophil ist und eine hohe Fähigkeit zeigt Wasser reversibel aufzunehmen. Beispielsweise hat beim Tragen von Atemmasken oder Kleidungsstücken aus gehärtetem Silicongummi der Wasserdampf der Atemluft oder der Schweißabsonderung keine Möglichkeit zu entweichen und es kommt schnell zur Kondensation und Filmbildung zwischen Haut und gehärtetem Silicongummi. Dies führt zu einem sehr schlechten Tragekomfort besonders über einen längeren Zeitraum. In certain applications of molded or hardened silicone rubber coatings, it is important that the silicone rubber be hydrophilic and have a high ability to reversibly pick up water. For example, when wearing breathing masks or garments of cured silicone rubber, the water vapor of the breath or perspiration has no opportunity to escape and condensation and filming between skin and hardened silicone gum rapidly occurs. This leads to a very bad wearing comfort especially over a longer period.
Daher besteht seit langem der Bedarf Siliconzusammensetzungen zur Verfügung zu stellen, die zu Silicongummi aushärtbar sind, deren Oberflächen hydrophil sind und die eine hohes Vermögen zur reversiblen Feuchtigkeitsaufnahme aufweisen, also die Abgabe der aufgenommenen Feuchtigkeit an die umgebende Luft ermöglichen . Therefore, there has long been a need to provide silicone compositions which are curable into silicone rubber whose surfaces are hydrophilic and which have a high ability to reversibly absorb moisture, thus allowing the absorption of absorbed moisture into the surrounding air.
Als eine Lösung schlägt der Fachartikel „Effect of Different Water-Soluble Additives on Water Sorption into Silicone Rub- ber"; Carelli und G. Di Colo, Journal of Pharmaceutical Sciences, Vol. 72, No. 3, March 1983 vor, Siliconzusammensetzungen mit den Additiven Ethylenglycol , Glycerin, Polyethylenglycole 200, 400 und 6000, Polysorbat 80 und Lactose auszurüsten. Nachteilig ist jedoch, dass diese Additive beispielsweise leicht ausgewaschen werden oder aus dem gehärten Silicongummi ausbluten. So dass eine langfristige Verwendung des gehärteten Si- licongummis nicht gewährleistet wird. As a solution, the paper "Effect of Different Water-Soluble Additives on Water Sorption Into Silicone Rubbers"; Carelli and G. Di Colo, Journal of Pharmaceutical Sciences, Vol. 72, No. 3, March 1983 suggests silicone compositions the additives ethylene glycol, glycerol, polyethylene glycols 200, 400 and 6000, polysorbate 80 and lactose equip. The disadvantage, however, is that these additives are easily washed out, for example, or bleed out of the cured silicone rubber. So that a long-term use of the hardened silicon rubber is not guaranteed.
Aufgabe war daher die Bereitstellung von Siliconzusammensetzungen die nach dem Aushärten eine hydrophile Oberfläche aufweisen und eine gute oder verbesserte, reversible Feuchtigkeitsaufnahme ermöglichen, ohne auszuwaschen oder auszubluten und weiter- hin gute mechanische und gummielastische Eigenschafen zeigen. It was therefore an object to provide silicone compositions which have a hydrophilic surface after curing and allow a good or improved, reversible moisture absorption, without washing out or bleeding out and continue to show good mechanical and rubber-elastic properties.
Überraschenderweise wird diese Aufgabe gelöst von erfindungsgemäßen additionsvernetzbaren Siliconzusammensetzungen enthalten Surprisingly, this object is achieved by addition-crosslinkable silicone compositions according to the invention
(A) mindestens ein Polyorganosiloxan mit mindestens zwei Alke- nylgruppen pro Molekül und einer Viskosität bei 25°C von 0,2 bis 1000 Pa-s, (A) at least one polyorganosiloxane having at least two alkenyl groups per molecule and a viscosity at 25 ° C. of from 0.2 to 1000 Pa.s,
(B) mindestens ein SiH- funktionelles Vernetzungsmittel,  (B) at least one SiH-functional crosslinking agent,
(C) mindestens einen Hydrosilylierungskatalysator,  (C) at least one hydrosilylation catalyst,
(D) mindestens ein hydratisierbares Salz,  (D) at least one hydratable salt,
(E) mindestens einen Füllstoff.  (E) at least one filler.
Das Alkenylgruppen enthaltende Polyorganosiloxan (A) besitzt vorzugsweise eine Zusammensetzung der durchschnittlichen allgemeinen Formel (1) RlxR2ySiO(4_x_y)/2 (1), auf , in der einen einwertigen, gegebenenfalls halogen- oder cyanosubsti- tuierten, gegebenenfalls über eine organische zweiwertige Gruppe an Silicium gebundenen C]_-Cio- Kohlenwasserstoffrest , der aliphatische Kohlenstoff-Kohlenstoff Mehrfachbindungen enthält , The alkenyl group-containing polyorganosiloxane (A) preferably has a composition of the average general formula (1) R 1 x R 2 y SiO (4 _ x _ y) / 2 (1), wherein is a monovalent, optionally-substituted halo- or cyanosubsti-, optionally via an organic divalent group to silicon-bonded C] _-CIO hydrocarbon radical containing aliphatic carbon-carbon multiple bonds,
einen einwertigen, gegebenenfalls halogen- oder cyanosubsti- tuierten, über Sic-gebundenen C^-Cio- Kohlenwasserstoffrest , der frei ist von aliphatischen Kohlenstoff-Kohlenstoff Mehrfachbindungen  a monovalent, optionally halogen or cyanosubstituted, over Sic-bonded C ^ -Cio hydrocarbon radical which is free of aliphatic carbon-carbon multiple bonds
eine solche nichtnegative Zahl, dass mindestens zwei Reste in jedem Molekül vorhanden sind, und  such a nonnegative number that at least two residues are present in each molecule, and
eine nicht negative Zahl, so dass (x+y) im Bereich von 1,8 bis 2,5 liegt, bedeuten. Die Alkenylgruppen R1 sind einer Anlagerungsreaktion mit einem SiH-funktionellen Vernetzungsmittel (B) zugänglich. Üblicherweise werden Alkenylgruppen mit 2 bis 6 Kohlenstoffatomen, wie Vinyl, Allyl, Methailyl, 1-Propenyl, 5-Hexenyl, Ethinyl , Buta- dienyl, Hexadienyl, Cyclopentenyl , Cyclopentadienyl , Cyclohexe- nyl, vorzugsweise Vinyl und Allyl, verwendet. a non-negative number such that (x + y) is in the range of 1.8 to 2.5. The alkenyl groups R 1 are accessible to an addition reaction with a SiH-functional crosslinking agent (B). Usually, alkenyl groups having 2 to 6 carbon atoms, such as vinyl, allyl, methailyl, 1-propenyl, 5-hexenyl, ethynyl, butadienyl, hexadienyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, preferably vinyl and allyl, are used.
Organische zweiwertige Gruppen, über die die Alkenylgruppen R1 an Silicium der Polymerkette gebunden sein können, bestehen beispielsweise aus Oxyalkyleneinheiten, wie solche der allgemeinen Formel (2) Organic divalent groups, via which the alkenyl groups R 1 may be bonded to silicon of the polymer chain, consist for example of oxyalkylene units, such as those of the general formula (2)
-(0)m[(CH2)n0]o- in der m die Werte 0 oder 1, insbesondere 0, - (0) m [(CH 2 ) n 0] o - in the m the values 0 or 1, in particular 0,
n Werte von 1 bis 4, insbesondere 1 oder 2 und n values from 1 to 4, in particular 1 or 2 and
o Werte von 1 bis 20, insbesondere von 1 bis 5 bedeuten. o mean values of 1 to 20, in particular from 1 to 5.
Die Oxyalkyleneinheiten der allgemeinen Formel (2) sind links an ein Siliciumatom gebunden. The oxyalkylene units of the general formula (2) are bonded to the left of a silicon atom.
Die Reste können in jeder Position der Polymerkette, insbesondere an den endständigen Siliciumatomen, gebunden sein. Beispiele für unsubstituierte Reste R2 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; Alkenylreste , wie der Vinyl-, Allyl-, η-5-Hexenyl- , 4 -Vinylcyclohexyl- und der 3 -Norbornenylrest ; Cycloalkylreste, wie Cyclopentyl- , Cyc- lohexyl-, 4 -Ethylcyclohexyl- , Cycloheptylreste , Norbornylreste und Methylcyclohexylreste ; Arylreste, wie der Phenyl-, Biphe- nylyl-, Naphthylrest ; Alkarylreste , wie o- , m- , p-Tolylreste und Ethylphenylreste ; Aralkylreste , wie der Benzylrest, der alpha- und der ß-Phenylethylrest . Beispiele für substituierte Kohlenwasserstoffreste als Reste R2 sind halogenierte Kohlenwasserstoffe, wie der Chlormethyl-, 3- Chlorpropyl- , 3 -Brompropyl , 3 , 3 , 3 -Trifluorpropyl undThe radicals can be bonded in any position of the polymer chain, in particular on the terminal silicon atoms. Examples of unsubstituted radicals R 2 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, such as the n-hexyl, heptyl, such as the n-heptyl, octyl, such as the n-octyl and iso-octyl, such as the 2, 2, 4-trimethylpentyl, nonyl, such as the n-nonyl, decyl such as the n-decyl radical; Alkenyl radicals such as the vinyl, allyl, η 5-hexenyl, 4-vinylcyclohexyl and 3-norbornenyl radicals; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, 4-ethylcyclohexyl, cycloheptyl radicals, norbornyl radicals and methylcyclohexyl radicals; Aryl radicals, such as the phenyl, biphenylyl, naphthyl radical; Alkaryl radicals, such as o-, m-, p-tolyl radicals and ethylphenyl radicals; Aralkyl radicals, such as the benzyl radical, the alpha- and the ß-phenylethyl radical. Examples of substituted hydrocarbon radicals as radicals R 2 are halogenated hydrocarbons, such as chloromethyl, 3-chloropropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl and
5 , 5 , 5 , 4 , 4 , 3 , 3 -Heptafluorpentylrest sowie der Chlorphenyl- , Dichlorphenyl- und Trifluortolylrest . R2 weist vorzugsweise 1 bis 6 Kohlenstoffatome auf. Insbesondere bevorzugt sind Methyl und Phenyl . 5, 5, 5, 4, 4, 3, 3 -heptafluoropentyl radical and the chlorophenyl, dichlorophenyl and Trifluortolylrest. R 2 preferably has 1 to 6 carbon atoms. Particularly preferred are methyl and phenyl.
Bestandteil (A) kann auch eine Mischung verschiedener Alke- nylgruppen enthaltender Polyorganosiloxane sein, die sich beispielsweise im Alkenylgruppengehalt , der Art der Alkenylgruppe oder strukturell unterscheiden. Component (A) may also be a mixture of different alkenyl-containing polyorganosiloxanes which differ, for example, in the alkenyl group content, the nature of the alkenyl group or structurally.
Die Struktur der Alkenylgruppen enthaltenden Polyorganosiloxane (A) kann linear, cyclisch oder auch verzweigt sein. Der Gehalt an zu verzweigten Polyorganosiloxanen führenden tri- und/oder tetrafunktionellen Einheiten ist typischerweise sehr gering, vorzugsweise höchstens 20 Mol-%, insbesondere höchstens 0,1 Mol-% . The structure of the alkenyl-containing polyorganosiloxanes (A) may be linear, cyclic or branched. The content of tri- and / or tetrafunctional units leading to branched polyorganosiloxanes is typically very low, preferably at most 20 mol%, in particular at most 0.1 mol%.
Besonders bevorzugt ist die Verwendung Vinylgruppen enthaltender Polydimethylsiloxane , deren Moleküle der allgemeinen Formel (3) (ViMe2Si01/2) 2 (ViMeSiO) p (Me2SiO) q (3), entsprechen, wobei die nichtnegativen ganzen Zahlen p und q folgende Relationen erfüllen: p>0 , 50< (p+q) <20000 , vorzugsweise 200< (p+q) <1000, und 0< (p+1 ) / (p+q) < 0.2. Insbesondere ist p = 0. Particularly preferred is the use of vinyl group-containing polydimethylsiloxanes whose molecules of the general formula (3) (ViMe 2 Si0 1/2) 2 (ViMeSiO) p (Me 2 SiO) q (3) corresponding to the non-negative integers p and q satisfy the following relations: p> 0, 50 <(p + q) <20000, preferably 200 <(p + q) <1000, and 0 <(p + 1) / (p + q) <0.2. In particular, p = 0.
Die Viskosität des Polyorganosiloxans (A) beträgt bei 25°C vorzugsweise 0,5 bis 500 Pa-s, insbesondere 1 bis 200 Pa-s, ganz besonders bevorzugt 1 bis 100 Pa-s. Die mindestens zwei SiH-Funktionen pro Molekül enthaltende Organosiliciumverbindung (B) besitzt vorzugsweise eine Zusammensetzung der durchschnittlichen allgemeinen Formel (4) HaR3bsiO(4_a_b)/2 (4), in der The viscosity of the polyorganosiloxane (A) at 25 ° C is preferably 0.5 to 500 Pa-s, in particular 1 to 200 Pa-s, most preferably 1 to 100 Pa-s. The at least two SiH functions per molecule containing organosilicon compound (B) preferably has a composition of the average general formula (4) H a R3 b siO (4 _ a _ b) / 2 (4), in which
R3 einen einwertigen, gegebenenfalls halogen- oder cyanosubsti- tuierten, über SiC-gebundenen C^-CIQ- Kohlenwasserstoffrest , der frei ist von aliphatischen Kohlenstoff-Kohlenstoff Mehrfachbindungen und  R3 is a monovalent, optionally halogen or cyano-substituted, SiC-bonded C ^ -CIQ hydrocarbon radical which is free of aliphatic carbon-carbon multiple bonds and
a und b nichtnegative ganze Zahlen sind, a and b are nonnegative integers,
mit der Maßgabe, dass 0.5< (a+b) <3 , 0 und 0<a<2, und dass mindestens zwei siliciumgebundene Wasserstoffatome pro Molekül vor- handen sind. with the proviso that 0.5 <(a + b) <3, 0 and 0 <a <2, and that at least two silicon-bonded hydrogen atoms are present per molecule.
Beispiele für sind die für angegebenen Reste. R^ weist vorzugsweise 1 bis 6 Kohlenstoffatome auf. Insbesondere bevorzugt sind Methyl und Phenyl . Examples are the radicals specified for. R 1 preferably has 1 to 6 carbon atoms. Particularly preferred are methyl and phenyl.
Bevorzugt ist die Verwendung einer drei oder mehr SiH-Bindungen pro Molekül enthaltenden Organosiliciumverbindung (B) . Bei Verwendung einer nur zwei SiH-Bindungen pro Molekül aufweisenden Organosiliciumverbindung (B) empfiehlt sich die Verwendung ei- nes Polyorganosiloxans (A) , das über mindestens drei Alke- nylgruppen pro Molekül verfügt. Preferred is the use of an organosilicon compound (B) containing three or more SiH bonds per molecule. When using an organosilicon compound (B) having only two SiH bonds per molecule, it is advisable to use a polyorganosiloxane (A) which has at least three alkenyl groups per molecule.
Der Wasserstoffgehalt der Organosiliciumverbindung (B) , welcher sich ausschließlich auf die direkt an Siliciumatome gebundenen Wasserstoffatome bezieht, liegt vorzugsweise im Bereich von 0,002 bis 1,7 Gew.-% Wasserstoff, vorzugsweise von 0,1 bis 1,7 Gew.-% Wasserstoff. Die Organosiliciumverbindung (B) enthält vorzugsweise mindestens drei und höchstens 600 Siliciumatome pro Molekül. Bevorzugt ist die Verwendung von Organosiliciumverbindung (B) , die 4 bis 200 Siliciumatome pro Molekül enthält. Die Struktur der Organosiliciumverbindung (B) kann linear, verzweigt, cyclisch oder netzwerkartig sein. The hydrogen content of the organosilicon compound (B), which refers exclusively to the hydrogen atoms bonded directly to silicon atoms, is preferably in the range of 0.002 to 1.7% by weight of hydrogen, preferably from 0.1 to 1.7% by weight of hydrogen. The organosilicon compound (B) preferably contains at least three and at most 600 silicon atoms per molecule. Preferred is the use of organosilicon compound (B) containing 4 to 200 silicon atoms per molecule. The structure of the organosilicon compound (B) may be linear, branched, cyclic or network-like.
Besonders bevorzugte Organosiliciumverbindungen (B) sind lineare Polyorganosiloxane der allgemeinen Formel (5) Particularly preferred organosilicon compounds (B) are linear polyorganosiloxanes of the general formula (5)
(HR42SiOl 2) c (R4 3SiOl/2) d(HR4Si02/2) e (R42Si02/2) f (5) , wobei (HR4 2 SiO l 2) c (R 4 3 SiO l / 2) d (HR 4 Si0 2/2) e (R 4 2Si0 2/2) f (5), wherein
die Bedeutungen von hat und  has the meanings of and
die nichtnegativen ganzen Zahlen c, d, e und f folgende Relationen erfüllen: (c+d)=2, (c+e)>2, 5<(e+f)<200 und l<e/ (e +f) <0, 1. the nonnegative integers c, d, e and f satisfy the following relations: (c + d) = 2, (c + e)> 2, 5 <(e + f) <200 and l <e / (e + f) <0, 1.
Die SiH-funktionelle Organosiliciumverbindung (B) ist vorzugs- weise in einer solchen Menge in der vernetzbaren Siliconzusammensetzung enthalten, dass das Molverhältnis von SiH-Gruppen zu Alkenylgruppen bei 0,5 bis 5, insbesondere bei 1,0 bis 3,0 liegt . Als Hydrosilylierungskatalysator (C) können alle bekannten Katalysatoren eingesetzt werden, welche die bei der Vernetzung von additionsvernetzenden Siliconmischungen ablaufenden Hydro- silylierungsreaktionen katalysieren. The SiH-functional organosilicon compound (B) is preferably contained in the crosslinkable silicone composition in an amount such that the molar ratio of SiH groups to alkenyl groups is 0.5 to 5, especially 1.0 to 3.0. As hydrosilylation catalyst (C) it is possible to use all known catalysts which catalyze the hydrosilylation reactions taking place in the crosslinking of addition-crosslinking silicone mixtures.
Als Hydrosilylierungskatalysatoren (C) werden insbesondere Metalle und deren Verbindungen aus der Gruppe Platin, Rhodium, Palladium, Ruthenium und Iridium eingesetzt. The hydrosilylation catalysts (C) used are in particular metals and their compounds from the group consisting of platinum, rhodium, palladium, ruthenium and iridium.
Vorzugsweise werden Platin und Platinverbindungen verwendet. Besonders bevorzugt werden solche Platinverbindungen, die in Polyorganosiloxanen löslich sind. Als lösliche Platinverbindungen können beispielsweise die Platin-Olefin-Komplexe der Formeln (PtCl2 · Olefin) 2 und H (PtCl3 · Olefin) verwendet werden, wo- bei bevorzugt Alkene mit 2 bis 8 Kohlenstoffatomen, wie Ethyl- en, Propylen, Isomere des Butens und Octens, oder Cycloalkene mit 5 bis 7 Kohlenstoffatomen, wie Cyclopenten, Cyclohexen und Cyclohepten, eingesetzt werden. Weitere lösliche Platin- Katalysatoren sind der Platin- Cyclopropan- Komplex der Formel (PtCl2C3H6) 2 / die Umsetzungsprodukte von Hexachloroplatinsäure mit Alkoholen, Ethern und Aldehyden bzw. Mischungen derselben oder das Umsetzungsprodukt von Hexachloroplatinsäure mit Me- thylvinylcyclotetrasiloxan in Gegenwart von Natriumbicarbonat in ethanolischer Lösung. Besonders bevorzugt sind Komplexe des Platins mit Vinylsiloxanen, wie sym-Preferably, platinum and platinum compounds are used. Particularly preferred are those platinum compounds which are soluble in polyorganosiloxanes. Examples of soluble platinum compounds which can be used are the platinum-olefin complexes of the formulas (PtCl.sub.2.alphine) .sub.2 and H (PtCl.sub.3.alfin), preferably alkenes having from 2 to 8 carbon atoms, such as ethylene, propylene and isomers of butene and octene, or cycloalkenes having from 5 to 7 carbon atoms, such as cyclopentene, cyclohexene and cycloheptene. Further soluble platinum catalysts are the platinum-cyclopropane complex of the formula (PtCl 2 C 3 H 6 ) 2 / the reaction products of hexachloroplatinic acid with alcohols, ethers and aldehydes or mixtures thereof or the reaction product of hexachloroplatinic acid with methylvinylcyclotetrasiloxane in the presence of sodium bicarbonate in ethanolic solution , Particular preference is given to complexes of platinum with vinylsiloxanes, such as
Divinyltetramethyldisiloxan . Ebenfalls sehr geeignet sind die in EP 1 077 226 AI und EP 0 994 159 AI beschriebenen Platinverbindungen, deren diesbezügliche Offenbarung auch Gegenstand dieser Anmeldung sein soll. Der Hydrosilylierungskatalysator (C) kann in jeder beliebigen Form eingesetzt werden, beispielsweise auch in Form von Hydrosilylierungskatalysator enthaltenden Mikrokapseln, oder Polyor- ganosiloxanpartikeln, wie beschrieben in EP 1 006 147 AI, deren diesbezügliche Offenbarung auch Gegenstand dieser Anmeldung sein soll. Divinyltetramethyldisiloxane. Likewise very suitable are the platinum compounds described in EP 1 077 226 A1 and EP 0 994 159 A1, the disclosure of which in this respect should also be the subject of this application. The hydrosilylation catalyst (C) can be used in any desired form, for example also in the form of hydrosilylation catalyst-containing microcapsules, or Polyor- ganosiloxanpartikeln, as described in EP 1 006 147 AI, the related disclosure should also be the subject of this application.
Der Gehalt an Hydrosilylierungskatalysatoren (C) wird vorzugsweise so gewählt, dass die additionsvernetzbare Siliconmischung (S) einen Pt-Gehalt von 0,1 bis 200 Gew.-ppm, insbesondere von 0,5 bis 40 Gew.-ppm besitzt. The content of hydrosilylation catalysts (C) is preferably selected so that the addition-crosslinkable silicone mixture (S) has a Pt content of 0.1 to 200 ppm by weight, in particular from 0.5 to 40 ppm by weight.
Der Begriff „hydratisierbares Salz (D) " bedeutet, dass das Salz in einem Zustand ist, in dem es zusätzlich Wasser durch Hydratation absorbieren kann. Das heißt, dass das Salz entweder in seiner wasserfreien Form oder in einer teilweise hydratisierten Form eingesetzt wird. The term "hydratable salt (D)" means that the salt is in a state where it can additionally absorb water by hydration, that is, the salt is used either in its anhydrous form or in a partially hydrated form.
Das hydratisierte Salz ist vorzugsweise in der Beschaffenheit teilchen- oder pulverförmig und kann beispielsweise Alkalime- tall-/Erdalkalimetallcarbonat , -bicarbonat, - (Poly) phosphat , citrat (wasserfrei) oder -sulfat (wasserfrei) sein. Gemische von zwei oder mehreren hydratisierbaren Verbindungen können ebenfalls verwendet werden. Für den Einsatz mit direktem Kontakt zur menschlichen Haut sollten nur gesundheitlich unbedenkliche hydratisierbare Salze (D) eingesetzt werden. Bevorzugt handelt es sich daher bei (D) um wasserfreies Natriumsulfat o- der um wasserfreies Magnesiumsulfat oder deren Mischung. Bevorzugt werden von 1 bis 30 Gew.% (D) eingesetzt. Besonders bevorzugt 5 bis 25 Gew.-%, ganz besonders bevorzugt 10 bis 20 Gew. -% . The hydrated salt is preferably particulate or powdery in nature and may be, for example, alkali metal / alkaline earth metal carbonate, bicarbonate, (poly) phosphate, citrate (anhydrous) or sulfate (anhydrous). Mixtures of two or more hydratable compounds may also be used. For use with direct contact with human skin only health-safe hydratable salts (D) should be used. Therefore, (D) is preferably anhydrous sodium sulfate or anhydrous magnesium sulfate or a mixture thereof. Preference is given to using from 1 to 30% by weight of (D). Particularly preferably 5 to 25 wt .-%, most preferably 10 to 20 wt -.%.
Die erfindungsgemäßen additionsvernetzbaren Siliconzusammensetzungen enthalten zudem als weiteren Bestandteil mindestens einen Füllstoff (E) . The addition-crosslinkable silicone compositions according to the invention also contain, as further constituent, at least one filler (E).
Nicht verstärkende Füllstoffe (E) mit einer BET-Oberfläche von bis zu 50 m2/g, sind beispielsweise Quarz, Diatomeenerde, Cal- ciumsilikat, Zirkoniumsilikat, Zeolithe, Metalloxidpulver, wie Aluminium-, Titan-, Eisen-, oder Zinkoxide bzw. deren Mischoxide, Bariumsulfat, Calciumcarbonat, Gips, Siliciumnitrid, Sili- ciumcarbid, Bornitrid, Glas- und Kunststoff ulver . Verstärkende Füllstoffe, also Füllstoffe mit einer BET-Oberfläche von mindestens 50 m2/g, insbesondere 100 bis 400 m2/g sind beispielsweise pyrogen hergestellte Kieselsäure, gefällte Kieselsäure, Aluminiumhydroxid, Ruß, wie Furnace- und Acetylenruß und Sili- cium-Aluminium-Mischoxide großer BET-Oberfläche . Non-reinforcing fillers (E) with a BET surface area of up to 50 m 2 / g are, for example, quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, metal oxide powders such as aluminum, titanium, iron or zinc oxides or their mixed oxides, barium sulfate, calcium carbonate, gypsum, silicon nitride, silicon carbide, boron nitride, glass and plastic ulver. Reinforcing fillers, ie fillers having a BET surface area of at least 50 m 2 / g, in particular 100 to 400 m 2 / g, are, for example, fumed silica, precipitated silica, aluminum hydroxide, carbon black, such as furnace and acetylene black and silicon aluminum Mixed oxides of large BET surface area.
Die genannten Füllstoffe (E) können hydrophobiert sein, beispielsweise durch die Behandlung mit Organosilanen, Organosila- zanen bzw. -siloxanen oder durch Verätherung von Hydroxylgruppen zu Alkoxygruppen . Es kann eine Art von Füllstoff (E) , es kann auch ein Gemisch von mindestens zwei Füllstoffen (E) eingesetzt werden. Vorzugsweise enthalten die erfindungsgemäßen Siliconzusammensetzungen mindestens 3 Gew.-%, besonders bevorzugt mindestens 5 Gew.-%, insbesondere mindestens 10 Gew.-% und höchstens 50 Gew.-% Füllstoffanteil (E) . Die erfindungsgemäßen Siliconzusammensetzungen können wahlweise als weiteren Bestandteil (F) mögliche Zusätze zu einem Anteil von 0 bis 70 Gew.-%, vorzugsweise 0,0001 bis 40 Gew.-%, enthalten. Diese Zusätze können beispielsweise harzartige Polyorgano- siloxane, die von den Polyorganosiloxanen (A) und (B) verschieden sind, Dispergierhilfsmittel , Lösungsmittel, Haftvermittler, Pigmente, Farbstoffe, Weichmacher, organische Polymere, Hitzestabilisatoren und Inhibitoren sein. Hierzu zählen Zusätze, wie Farbstoffe und Pigmente. Des Weiteren können als Bestandteil thixotropierende Bestandteile, wie hochdisperse Kieselsäure oder andere handelsübliche Thixotropieadditive enthalten sein. Auch können als weiterer Bestandteil (F) zur besseren Vernet- zung vorzugsweise maximal 0,5 Gew, besonders bevorzugt maximal 0,3 Gew.-%, insbesondere <0,1% Gew.-% Peroxid vorhanden sein. The stated fillers (E) may be rendered hydrophobic, for example by treatment with organosilanes, organosilazanes or siloxanes or by etherification of hydroxyl groups to alkoxy groups. It may be one kind of filler (E), it may also be a mixture of at least two fillers (E) are used. Preferably, the silicone compositions of the invention contain at least 3 wt .-%, more preferably at least 5 wt .-%, in particular at least 10 wt .-% and at most 50 wt .-% filler content (E). The silicone compositions according to the invention may optionally contain, as further constituent (F), possible additives in a proportion of 0 to 70% by weight, preferably 0.0001 to 40% by weight. These additives may be, for example, resinous polyorganosiloxanes other than the polyorganosiloxanes (A) and (B), dispersing aids, solvents, adhesion promoters, pigments, dyes, plasticizers, organic polymers, heat stabilizers and inhibitors. These include additives such as dyes and pigments. Furthermore, thixotropic constituents, such as finely divided silica or other commercially available thixotropic additives, can be contained as constituents. Also, as a further constituent (F) for better crosslinking, preferably at most 0.5% by weight, particularly preferably at most 0.3% by weight, in particular <0.1% by weight, of peroxide may be present.
Enthalten sein können zudem weitere Zusätze, die der gezielten Einstellung der Verarbeitungszeit, Anspringtemperatur und Ver- netzungsgeschwindigkeit der vernetzenden Massen dienen. Diese Inhibitoren und Stabilisatoren sind auf dem Gebiet der vernetzenden Massen sehr gut bekannt. In addition, other additives can be included, which serve to specifically adjust the processing time, light-off temperature and crosslinking rate of the crosslinking compounds. These inhibitors and stabilizers are well known in the field of crosslinking compositions.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Ver- fahren zur Herstellung der erfindungsgemäßen additionsvernetz- baren Siliconzusammensetzung, ein Verfahren zur Herstellung der vernetzten Silicongummi aus den erfindungsgemäßen Siliconzusammensetzungen sowie die so erhältlichen Silicongummi-Formteile oder Silicongummi -Beschichtungen . Die Herstellung oder Compoundierung der erfindungsgemäßen Siliconzusammensetzung erfolgt bevorzugt durch Mischen der Komponenten (A) und (D) und (E) und gegebenenfalls (F) . Die erfindungsgemäße Zusammensetzung kann als 1-, 2- oder Mehr- Komponentenzusammensetzung hergestellt werden. Die Vernetzung nach Zugabe von Vernetzer (B) und Hydrosilylierungskatalysator (C) erfolgt vorzugsweise durch Erwärmen, vorzugsweise bei 30 bis 250°C, bevorzugt bei mindestens 50°C, insbesondere bei min- destens 100°C, bevorzugt bei 150-210°C. A further subject of the present invention is a process for the preparation of the addition-crosslinkable silicone composition according to the invention, a process for the preparation of the crosslinked silicone rubber from the silicone compositions according to the invention and the silicone rubber moldings or silicone rubber coatings obtainable in this way. The preparation or compounding of the silicone composition according to the invention is preferably carried out by mixing the components (A) and (D) and (E) and optionally (F). The composition of the invention may be prepared as a 1-, 2- or multi-component composition. The crosslinking after addition of crosslinker (B) and hydrosilylation catalyst (C) is preferably carried out by heating, preferably at 30 to 250 ° C, preferably at least 50 ° C, in particular at least 100 ° C, preferably at 150-210 ° C. ,
Die so erhaltenen erfindungsgemäßen Silicongummi haben den Vorteil, dass sie eine überraschend hohe Wasserauf ahme und eine gute Permanenz der Komponente (D) im vernetzten Silicongummi The silicone gums according to the invention thus obtained have the advantage that they have a surprisingly high water absorption and a good permanence of the component (D) in the crosslinked silicone rubber
(kaum oder kein Auswaschen oder Ausbluten) sowie eine sehr gute Reversibilität der Wasserauf ahme zeigen. (hardly or no washing out or bleeding) and a very good reversibility of the water imprints show.
So erhaltene erfindungsgemäße Silicongummi können als Formkör- per beispielsweise für Atemmasken, Kleidung, Polster oder Möbel verwendet werden. So erhaltene erfindungsgemäße Silicongummi - Beschichtungen finden Einsatz beispielsweise auf Fasern oder Stoffen. Eine weitere Verwendungsmöglichkeit der gehärteten erfindungsgemäßen Silicongummi ist ihr Einsatz als wiederverwend- bares Trocknungsmittel beispielsweise in Form von Granulat oder Plättchen . Thus obtained silicone gum according to the invention can be used as shaped articles, for example for respiratory masks, clothing, upholstery or furniture. Silicone rubber coatings of the invention obtained in this way are used, for example, on fibers or fabrics. Another possible use of the cured silicone rubber according to the invention is its use as a reusable desiccant, for example in the form of granules or platelets.
Alle vorstehenden Symbole der vorstehenden Formeln weisen ihre Bedeutungen jeweils unabhängig voneinander auf. In allen For- mein ist das Siliciumatom vierwertig. Die Summe aller Bestand- teile der erfindungsgemäßen Siliconzusammensetzung ergeben 100 Gew. -% . All the above symbols of the above formulas each have their meanings independently of each other. In all forms, the silicon atom is tetravalent. The sum of all inventory Parts of the silicone composition according to the invention give 100% by weight.
Die Viskositäten werden bei 25°C und Normaldruck von 1013 hPa bestimmt. Eine geeignete Methode ist die rotationsviskosimetri- sche Messung gemäß DIN EN ISO 3219. The viscosities are determined at 25 ° C and atmospheric pressure of 1013 hPa. A suitable method is the rotational viscometric measurement according to DIN EN ISO 3219.
Beispiele : Examples:
In den nachstehend beschriebenen Beispielen beziehen sich alle Angaben von Teilen und Prozentsätzen, falls nicht anders angegeben, auf das Gewicht. Sofern nicht anders angegeben, werden die nachstehenden Beispiele bei einem Druck der umgebenden Atmosphäre, also etwa bei 1013 hPa, und bei Raumtemperatur, also bei 25 °C, bzw. bei einer Temperatur, die sich beim Zusammengeben der Reaktanden bei Raumtemperatur ohne zusätzliche Heizung oder Kühlung einstellt, durchgeführt. Im Folgenden beziehen sich alle Viskositätsangaben auf eine Temperatur von 25 °C. Die nachfolgenden Beispiele erläutern die Erfindung, ohne dabei beschränkend zu wirken. In the examples below, all parts and percentages are by weight unless otherwise specified. Unless otherwise indicated, the following examples are at a pressure of the surrounding atmosphere, ie at about 1013 hPa, and at room temperature, ie at 25 ° C, or at a temperature resulting from combining the reactants at room temperature without additional heating or Cooling stops, carried out. In the following, all viscosity data refer to a temperature of 25 ° C. The following examples illustrate the invention without being limiting.
Es werden folgende Abkürzungen verwendet : The following abbreviations are used:
sec . Sekunde sec. second
min. Minute minute minute
U/min Umdrehungen/Minute  Revolutions / minute
ELASTOSIL® sind kommerziell erhältliche additionsvernetzende 2- Komponenten (2K) Siliconzusammensetzungen der Wacker Chemie AG, München. Wasserfreies Natriumsulfat und wasserfreies Magnesiumsulfat wurden von der Fa. Merck KGaA, Darmstadt, bezogen. Beispiel 1 ELASTOSIL ® are commercially available addition-2-component (2K) silicone compositions of Wacker Chemie AG, Munich. Anhydrous sodium sulfate and anhydrous magnesium sulfate were purchased from Merck KGaA, Darmstadt. example 1
9 g (5 Gew.-%) wasserfreies Natriumsulfat werden mit jeweils 85,5 g ELASTOSIL® 3003/40 A- und B-Komponente zusammen eingewogen und an einem SpeedmixerTM DAC 400 FVZ der Firma Hauschild mit dem in Tabelle 1 aufgezeigtem Programm homogenisiert: 9 g (5 wt .-%) of anhydrous sodium sulfate were weighed each 85.5g ELASTOSIL ® 3003/40 A- and B components together and homogenized on a SpeedmixerTM DAC 400 FVZ the Hauschild with the aufgezeigtem in Table 1 Program:
Tabelle 1 Table 1
Dieses Programm verwendet man hintereinander 5 Mal zum optima- len homogenisieren der Probe - zwischendurch löst man jedes Mal mit einem Spatel das Gemisch von den Seiten und dem Boden des Mischbehälters . Vulkanisiert wird in einer Laborpresse P300 P/M der Fa. Collin bei 165°C für 5 min und einem Druck von 380 N/cm2. This program is used in succession 5 times to optimally homogenize the sample - in each case you use a spatula to dissolve the mixture from the sides and the bottom of the mixing container. Vulcanization is carried out in a laboratory press P300 P / M from Collin at 165 ° C. for 5 min and a pressure of 380 N / cm 2.
Eine Vulkanisatprobe wird a) 8 Stunden und b) 700 Stunden in demineralisiertem Wasser gelagert. Die Gewichtszunahme beträgt nach dem Abtrocknen mit saugfähigem Papier a) 4,1 % und b) 39,2 o, A vulcanizate sample is stored a) for 8 hours and b) for 700 hours in demineralised water. The weight increase after drying with absorbent paper a) 4.1% and b) 39.2 o,
"o ■ "o ■
Beispiel 2 Example 2
Die Vorgehensweise von Beispiel 1 wird wiederholt mit der Abän- derung, dass 18 g (10 Gew.-%) wasserfreies Natriumsulfat mit jeweils 81 g Elastosil® 3003/40 A- und B-Komponente homogenisiert werden. The procedure of Example 1 is repeated with the modification that 18 g (10 wt .-%) of anhydrous sodium sulfate with each 81 g Elastosil ® 3003/40 A and B component are homogenized.
Dann wird wie in Beispiel 1 beschrieben vulkanisiert und eine Vulkanisatprobe a) 8 Stunden und b) 700 Stunden in deminerali- siertem Wasser gelagert. Die Gewichtszunahme beträgt nach dem Abtrocknen a) 4,5 % und b) 78,4 %. The vulcanization is then carried out as described in Example 1 and a vulcanizate sample a) is stored for 8 hours and b) for 700 hours in demineralized water. The weight gain after drying is a) 4.5% and b) 78.4%.
Beispiel 3 Example 3
Die Vorgehensweise von Beispiel 1 wird wiederholt mit der Abänderung, dass 27 g (15 Gew.-%) wasserfreies Natriumsulfat mit jeweils 76,5 g Elastosil® 3003/40 A- und B-Komponente homogenisiert werden. Dann wird wie in Beispiel 1 beschrieben vulkanisiert und eine Vulkanisatprobe a) 8 Stunden und b) 700 Stunden in deminerali- siertem Wasser gelagert. Die Gewichtszunahme beträgt nach dem Abtrocknen a) 5,3 % und b) 171,4 %. The procedure of Example 1 is repeated with the modification that 27 g (15 wt .-%) of anhydrous sodium sulfate are homogenized with 76.5 g Elastosil ® 3003/40 A and B component. The vulcanization is then carried out as described in Example 1 and a vulcanizate sample a) is stored for 8 hours and b) for 700 hours in demineralized water. The weight gain after drying is a) 5.3% and b) 171.4%.
Beispiel 4 Example 4
Die Vorgehensweise von Beispiel 1 wird wiederholt mit der Abänderung, dass 9 g (5 Gew.-%) wasserfreies Magnesiumsulfat mit jeweils 85,5 g Elastosil® 3003/40 A- und B-Komponente homogeni- siert werden. The procedure of Example 1 is repeated with the modification that 9 g (5 wt .-%) of anhydrous magnesium sulfate with each 85.5 g Elastosil ® 3003/40 A and B component homogenized Siert.
Dann wird wie in Beispiel 1 beschrieben vulkanisiert und eine Vulkanisatprobe a) 8 Stunden und b) 700 Stunden in deminerali- siertem Wasser gelagert. Die Gewichtszunahme beträgt nach dem Abtrocknen a) 4,0 % und b) 43,8 %. Beispiel 5 The vulcanization is then carried out as described in Example 1 and a vulcanizate sample a) is stored for 8 hours and b) for 700 hours in demineralized water. The weight gain after drying is a) 4.0% and b) 43.8%. Example 5
Die Vorgehensweise von Beispiel 1 wird wiederholt mit der Abänderung, dass 18 g (10 Gew.-%) wasserfreies Magnesiumsulfat mit jeweils 81 g Elastosil® 3003/40 A- und B-Komponente homogeni- siert werden. The procedure of Example 1 is repeated with the modification that 18 g (10 wt .-%) of anhydrous magnesium sulfate with each 81 g of Elastosil ® 3003/40 A and B component homogenized Siert.
Dann wird wie in Beispiel 1 beschrieben vulkanisiert und eine Vulkanisatprobe a) 8 Stunden und b) 700 Stunden in deminerali- siertem Wasser gelagert. Die Gewichtszunahme beträgt nach dem Abtrocknen a) 4,6 % und b) 54,7 %. The vulcanization is then carried out as described in Example 1 and a vulcanizate sample a) is stored for 8 hours and b) for 700 hours in demineralized water. The weight gain after drying is a) 4.6% and b) 54.7%.
Vergleichsbeispiel 1 (nicht erfindungsgemäß) Comparative Example 1 (not according to the invention)
Die Vorgehensweise von Beispiel 1 wird wiederholt mit der Abänderung, dass 18 g (10 Gew.-%) Maisstärke mit jeweils 81 g Elastosil® 3003/40 A- und B-Komponente homogenisiert werden. The procedure of Example 1 is repeated with the modification that 18 g (10 wt .-%) corn starch are homogenized with 81 g Elastosil ® 3003/40 A and B component.
Dann wird wie in Beispiel 1 beschrieben vulkanisiert und eine Vulkanisatprobe a) 8 Stunden und b) 700 Stunden in deminerali- siertem Wasser gelagert. Die Gewichtszunahme beträgt nach dem Abtrocknen a)0,8 % und b) 2,8 %. The vulcanization is then carried out as described in Example 1 and a vulcanizate sample a) is stored for 8 hours and b) for 700 hours in demineralized water. The weight gain after drying is a) 0.8% and b) 2.8%.
Vergleichsbeispiel 2 (nicht erfindungsgemäß) Comparative Example 2 (not according to the invention)
Die Vorgehensweise von Beispiel 1 wird wiederholt mit der Abänderung, dass 18 g (10 Gew.-%) Gelatine mit jeweils 81 g Elasto- sil® 3003/40 A- und B-Komponente homogenisiert werden. The procedure of Example 1 is repeated with the modification that 18 g (10 wt .-%) of gelatin are homogenized with 81 g each Elastosil ® 3003/40 A and B component.
Dann wird wie in Beispiel 1 beschrieben vulkanisiert und eine Vulkanisatprobe a) 8 Stunden und b) 700 Stunden in deminerali- siertem Wasser gelagert. Die Gewichtszunahme beträgt nach dem Abtrocknen a) 2,9 % und b) 16,6 %. The vulcanization is then carried out as described in Example 1 and a vulcanizate sample a) is stored for 8 hours and b) for 700 hours in demineralized water. The weight gain after drying is a) 2.9% and b) 16.6%.

Claims

Patentansprüche claims
1. Additionsvernetzbare Siliconzusammensetzung enthalten 1. Addition-crosslinkable silicone composition
(A) mindestens ein Polyorganosiloxan mit mindestens zwei Al- kenylgruppen pro Molekül und einer Viskosität bei 25°C von 0,2 bis 1000 Pa-s, (A) at least one polyorganosiloxane having at least two alkylene groups per molecule and a viscosity at 25 ° C. of from 0.2 to 1000 Pa.s,
(B) mindestens ein SiH- funktionelles Vernetzungsmittel, (B) at least one SiH-functional crosslinking agent,
(C) mindestens einen Hydrosilylierungskatalysator , (C) at least one hydrosilylation catalyst,
(D) mindestens ein hydratisierbares Salz, und  (D) at least one hydratable salt, and
(E) mindestens einen Füllstoff.  (E) at least one filler.
2. Additionsvernetzbare Siliconzusammensetzung gemäß Anspruch 1, bei dem (D) ausgewählt wird aus der Gruppe wasserfreies Natriumsulfat, wasserfreies Magnesiumsulfat oder deren Mischung. 2. An addition-crosslinkable silicone composition according to claim 1, wherein (D) is selected from the group of anhydrous sodium sulfate, anhydrous magnesium sulfate or a mixture thereof.
3. Verfahren zur Herstellung von Silicongummi -Formteilen oder Silicongummi-Beschichtungen, durch Erwärmen auf 30 bis 250°C der additionsvernetzbaren Siliconzusammensetzung gemäß den Ansprüchen 1 oder 2. 3. A process for the preparation of silicone rubber moldings or silicone rubber coatings, by heating to 30 to 250 ° C of the addition-crosslinkable silicone composition according to claims 1 or 2.
EP15706231.6A 2014-02-27 2015-02-24 Addition cross-linking silicone composition with a high water-absorption capacity Withdrawn EP3110889A1 (en)

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DE19851764A1 (en) 1998-12-04 2000-06-08 Wacker Chemie Gmbh Heat-curable one-component addition-curing silicone materials
JP4000432B2 (en) * 1998-12-16 2007-10-31 富田製薬株式会社 Hygroscopic ink and moisture removal container
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