WO2024084490A1 - Emergency rescue & aid support system - erass - Google Patents

Emergency rescue & aid support system - erass Download PDF

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WO2024084490A1
WO2024084490A1 PCT/IN2023/000010 IN2023000010W WO2024084490A1 WO 2024084490 A1 WO2024084490 A1 WO 2024084490A1 IN 2023000010 W IN2023000010 W IN 2023000010W WO 2024084490 A1 WO2024084490 A1 WO 2024084490A1
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groups
component
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platinum
terminated
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PCT/IN2023/000010
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French (fr)
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Thandal Muraliraja RAM KISHORE
G Balaganesan
R Sundararajan
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Ram Kishore Thandal Muraliraja
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  • the present disclosure relates to hydrosilylation (addition) curable silicone rubber compositions, to silicone elastomeric materials with an improved high temperature (greater than or equal to ( ⁇ 190 o C)) compression set in accordance with ISO 815-1 method A which are produced by curing said hydrosilylation (addition) curable silicone rubber compositions and to a method for preparing said silicone elastomeric materials.
  • the present disclosure also extends to uses for such materials in or for the manufacture of silicone coatings for standard non-silicone insulators, as cable coatings e.g., for safety cables, in cable accessories such as electrical connectors, connector seals, terminations and wire seals, and for other electrical and electronic parts, particularly for the automotive industry and/or in or as hoses and gaskets for e.g., vehicle engines.
  • Hydrosilylation curable silicone rubber compositions containing: (i) organopolysiloxane polymers having unsaturated (alkenyl and/or alkynyl) groups; (ii) compounds containing silicon-bonded hydrogen atoms; and (iii) a hydrosilylation catalyst are known in the art and are used to prepare silicone elastomeric materials with a broad spectrum of physical properties including electrical insulation, resistance and stability to heat, freeze resistance, abrasion resistance, fire retardancy, and long-term flexibility.
  • Silicone elastomers both liquid silicone rubbers (LSRs) and high consistency rubbers (HCRs) have been broadly utilized as seals in or for electrical connectors due to their excellent balance of mechanical properties, chemical and thermal stabilities and ease of processing. They may be used to mate rigid thermoplastic housing components forming a tight connection that provides both electrical and environmental isolation to connector junctions.
  • LSRs liquid silicone rubbers
  • HCRs high consistency rubbers
  • Compression set is a thermally induced fatigue behavior of a silicone elastomeric material which may be defined as the loss in ability of said silicone elastomeric material to recover to its original thickness after compression for specific period of time at a set (elevated) temperature.
  • a compression set value may be measured, for example, following the industrial standard ISO 815-1:2019 methods A, B or C and is identified as a percentage, such that if there is complete recovery, i.e., if the thickness of a test specimen is identical before and after the application of a load, the compression set is 0%; if, in contrast, a 25% compression of a silicone elastomeric material applied during a test remains unchanged when the load is removed, the compression set is 100% because it has failed to return to its original shape at all.
  • hydrosilylation curable silicone compositions often, if not always, do not undergo complete cure during the standard curing process. This is thought to at least partially be because of incomplete hydrosilylation due to steric hindrance during interaction of vinyl containing silicone polymers, Si-H cross-linker(s) and hydrosilylation catalysts (most typically platinum based catalysts.
  • a hydrosilylation cured silicone elastomeric material when compressed at an elevated temperature, further cross-linking may occur within the body of the silicone elastomeric material specifically at previously unreacted Si-H positions.
  • inter-molecular bond formation can occur between polydimethylsiloxane (PDMS) chains, again particularly at previously unreacted Si-H excess positions (via hydrolysis, oxidative or thermally induced reaction pathways), and thermal, oxidative, and thermo-oxidative rearrangements may occur within or between individual PDMS chains of the silicone elastomeric material.
  • PDMS polydimethylsiloxane
  • silicone elastomeric materials have a substantial compression set e.g., of greater than 50% or even greater than 60% even after compression at temperatures of 125 o C and 150 o C for short periods of time e.g., 22 hours and can suffer from problems caused by a consequential change in shape and/or a significant increase in hardness during long-term service in high-temperature applications unless they undergo a post-cure heating process.
  • T1 is for the temperature class -40° C to +85°C
  • T2 is for the temperature range -40° C to +100°C
  • T3 is for the temperature range -40° C to +125°C
  • T4 is for the temperature range -40° C to +150°C
  • T5 is for the -40° C to 175 °C.
  • Current sealed connector assemblies are fulfilling the T3 temperature class.
  • US8080598B2 proposed a hydrosilylation cured silicone rubber having low compression set without post curing using a diacyl-hydrazide-based compound such as dodecanedioyl-di-(N′-salicyloyl)hydrazine, a synonym for which is 1-N',12-N'-bis(2-hydroxybenzoyl)dodecanedihydrazide, as well as several alternatives, in combination with a cure inhibitor selected from an acetylene-containing silane, a vinyl- containing low-molecular- weight organosiloxane compound, or an alcohol derivative having carbon- carbon triple bonds to reduce compression set.
  • a cure inhibitor selected from an acetylene-containing silane, a vinyl- containing low-molecular- weight organosiloxane compound, or an alcohol derivative having carbon- carbon triple bonds to reduce compression set.
  • hydrosilylation curable silicone rubber composition which comprises the following components: a) one or more polyorganosiloxanes containing at least two unsaturated groups, selected from alkenyl groups and alkynyl groups, per molecule and having a viscosity in a range of from 1000 mPa.s to 100,000 mPa.s at 25 o C; b) an organosilicon compound having at least two, alternatively at least three Si-H groups per molecule; c) a silica reinforcing filler which is optionally hydrophobically treated; d) a hydrosilylation catalyst comprising or consisting of a platinum group metal or a compound thereof; e) a phthalocyanine compound or a metal derivative of such a compound, where the metal is copper, nickel, cobalt, iron, manganese, chromium, zinc, platinum, palladium, and vanadium and which is present in an amount of from 0.02 wt.
  • % to 2.5 wt. % of the composition f) cyanuric acid, biuret or a mixture thereof in an amount of from 0.005 to 0.2 wt. % of the composition; and g) one or more of magnesium hydroxide, magnesium carbonate, magnesium hydroxy carbonate or manganese carbonate in an amount 0.25 to 2.0 wt. % of the composition; wherein the total wt. % of the composition is 100 wt. %.
  • silicone elastomeric material which is the cured product of the above hydrosilylation curable silicone rubber composition, which silicone elastomeric material has a compression set of no more than 15%, preferably no more than 10% when measured in accordance with industrial standard norm ISO 815-1 method A after compression at 175 o C for 22 hours and a compression set of no more than 20%, preferably no more than 15% when measured in accordance with industrial standard norm ISO 815-1 method A after compression at 200 o C for 22 hours; alternatively having a compression set of 30 % or less, preferably 25 % or less, when measured in accordance with industrial standard norm ISO 815-1 method A after compression at 175 o C for 168 hours and a compression set of 40 % or less, preferably 35 % or less, when measured in accordance with industrial standard norm ISO 815-1 method A after compression at 200 o C for 168 hours (one week).
  • a process for making a silicone elastomeric material comprising the steps of mixing: a) one or more polyorganosiloxanes containing at least two unsaturated groups, selected from alkenyl groups and alkynyl groups, per molecule and having a viscosity in a range of from 1000 mPa.s to 100,000 mPa.s at 25 o C; b) an organosilicon compound having at least two, alternatively at least three Si-H groups per molecule; c) a silica reinforcing filler which is optionally hydrophobically treated; d) a hydrosilylation catalyst comprising or consisting of a platinum group metal or a compound thereof; e) a phthalocyanine compound or a metal derivative of such a compound, where the metal is copper, nickel, cobalt, iron, manganese, chromium, zinc, platinum, palladium, and vanadium and which is present in an amount of from 0.02 wt.
  • composition % to 2.5 wt. % of the composition; f) cyanuric acid, biuret or a mixture thereof in an amount of from 0.005 to 0.2 wt. % of the composition; and g) one or more of magnesium hydroxide, magnesium carbonate, magnesium hydroxy carbonate or manganese carbonate in an amount 0.25 to 2.0 wt. % of the composition; and curing the composition at a temperature of from 80 o C to 200 o C.
  • a silicone elastomeric material obtained or obtainable from a process comprising the steps of mixing a: a) one or more polyorganosiloxanes containing at least two unsaturated groups, selected from alkenyl groups and alkynyl groups, per molecule and having a viscosity in a range of from 1000 mPa.s to 100,000 mPa.s at 25 o C; b) an organosilicon compound having at least two, alternatively at least three Si-H groups per molecule; c) a silica reinforcing filler which is optionally hydrophobically treated; d) a hydrosilylation catalyst comprising or consisting of a platinum group metal or a compound thereof; e) a phthalocyanine compound or a metal derivative of such a compound, where the metal is copper, nickel, cobalt, iron, manganese, chromium, zinc, platinum, palladium, and vanadium and which is present in an amount of from 0.02 w
  • % to 2.5 wt. % of the composition f) cyanuric acid, biuret or a mixture thereof in an amount of from 0.005 to 0.2 wt. % of the composition; and g) one or more of magnesium hydroxide, magnesium carbonate, magnesium hydroxy carbonate or manganese carbonate in an amount 0.25 to 2.0 wt. % of the composition; wherein the total wt. % of the composition is 100 wt.
  • composition at a temperature of from 80 o C to 200 o C; which silicone elastomeric material has a compression set of no more than 20% after 22 hours compression at temperatures up to 190 o C, alternatively up to 200 o C, when measured in accordance with industrial standard norm ISO 815-1:2019 method A.
  • component (a) has at least three unsaturated groups per molecule.
  • the unsaturated groups of component (a) may be terminal, pendent, or in both locations.

Abstract

The present invention "ERASS" provides an Unmanned Aerial Vehicle (UAV) based lifesaving vests/buoy and/or lifesaving kits dropping system. The UAV lifesaving kits dropping device comprises of a lifesaving kit which provides the connecting link from rescuer to victim. Wherein the connecting mechanism comprises the life buoy which is fixed to the body of the drone. The dropping mechanism enables the delivery of lifesaving equipment's/kits is installed in the critical lifesaving delivery mechanism and comprises a steering motor, guiding ropes and the control mechanism and other equipment's is installed on the system and also other surveillance and other rescue sensors, equipment's can be enables in the same system for an effective rescue operation. In the UAV based life buoy dropping device, the design of utilizing the baffles to block the life buoy is adopted, one or multiple life buoys can be accurately dropped multiple lifesaving kits for multiple times, and one unmanned aerial vehicle can rescue multiple targets during the operation. The core of this invention is to provide the interlinking mechanism between the victims and ground rescue team through a physical connect mechanism.

Description

LIQUID SILICONE RUBBER COMPOSITION The present disclosure relates to hydrosilylation (addition) curable silicone rubber compositions, to silicone elastomeric materials with an improved high temperature (greater than or equal to (≥190oC)) compression set in accordance with ISO 815-1 method A which are produced by curing said hydrosilylation (addition) curable silicone rubber compositions and to a method for preparing said silicone elastomeric materials. The present disclosure also extends to uses for such materials in or for the manufacture of silicone coatings for standard non-silicone insulators, as cable coatings e.g., for safety cables, in cable accessories such as electrical connectors, connector seals, terminations and wire seals, and for other electrical and electronic parts, particularly for the automotive industry and/or in or as hoses and gaskets for e.g., vehicle engines. Hydrosilylation curable silicone rubber compositions containing: (i) organopolysiloxane polymers having unsaturated (alkenyl and/or alkynyl) groups; (ii) compounds containing silicon-bonded hydrogen atoms; and (iii) a hydrosilylation catalyst are known in the art and are used to prepare silicone elastomeric materials with a broad spectrum of physical properties including electrical insulation, resistance and stability to heat, freeze resistance, abrasion resistance, fire retardancy, and long-term flexibility. This unique combination of properties renders elastomers made from liquid silicone rubber suitable for utilisation in a wide range of electrical and/or insulative applications, such as in or for electrical connectors, commonly used to create closed electrical circuits in automotive, residential, and infrastructural settings. For example, Silicone elastomers (both liquid silicone rubbers (LSRs) and high consistency rubbers (HCRs)) have been broadly utilized as seals in or for electrical connectors due to their excellent balance of mechanical properties, chemical and thermal stabilities and ease of processing. They may be used to mate rigid thermoplastic housing components forming a tight connection that provides both electrical and environmental isolation to connector junctions. These may be used in automotive vehicles which are becoming increasingly dependent on electrical and electronical systems for the full operation thereof, even more so since the introduction of electric and hybrid vehicles. Hence, electrical failures can lead to devices such as radio, light, ventilation etc. malfunctioning or breaking down. Many of the electrical connectors used for such devices rely on the aforementioned silicone rubber materials to prevent electrical failings and they need to be able to avoid failure in e.g., vehicles at increasing engine temperatures. Many of these applications require silicone elastomeric materials to have a low compression set in addition to their electrical insulation and/or heat stability etc applications. Compression set is a key property of silicone elastomeric materials utilized in any of the above applications. Compression set is a thermally induced fatigue behavior of a silicone elastomeric material which may be defined as the loss in ability of said silicone elastomeric material to recover to its original thickness after compression for specific period of time at a set (elevated) temperature. A compression set value may be measured, for example, following the industrial standard ISO 815-1:2019 methods A, B or C and is identified as a percentage, such that if there is complete recovery, i.e., if the thickness of a test specimen is identical before and after the application of a load, the compression set is 0%; if, in contrast, a 25% compression of a silicone elastomeric material applied during a test remains unchanged when the load is removed, the compression set is 100% because it has failed to return to its original shape at all. Without being tied to current theories, it is believed is believed that the root cause of the inability of a silicone-based elastomeric material to recover to its original thickness after compression over a specified period of time at a set (elevated) temperature is that hydrosilylation curable silicone compositions often, if not always, do not undergo complete cure during the standard curing process. This is thought to at least partially be because of incomplete hydrosilylation due to steric hindrance during interaction of vinyl containing silicone polymers, Si-H cross-linker(s) and hydrosilylation catalysts (most typically platinum based catalysts. Thus, when a hydrosilylation cured silicone elastomeric material is compressed at an elevated temperature, further cross-linking may occur within the body of the silicone elastomeric material specifically at previously unreacted Si-H positions. Additionally, inter-molecular bond formation can occur between polydimethylsiloxane (PDMS) chains, again particularly at previously unreacted Si-H excess positions (via hydrolysis, oxidative or thermally induced reaction pathways), and thermal, oxidative, and thermo-oxidative rearrangements may occur within or between individual PDMS chains of the silicone elastomeric material. The occurrence of one or more of the above will cause an increase in crosslink density within the silicone elastomeric material and consequently a more rigid structure which prevents the silicone elastomeric material to return to its original thickness after compression. Many silicone elastomeric materials have a substantial compression set e.g., of greater than 50% or even greater than 60% even after compression at temperatures of 125oC and 150oC for short periods of time e.g., 22 hours and can suffer from problems caused by a consequential change in shape and/or a significant increase in hardness during long-term service in high-temperature applications unless they undergo a post-cure heating process. “Post curing” is the most straightforward way to minimise compression set where hydrosilylation-cured silicone materials are subjected to a period of several hours e.g., four or more hours of post-cure heating at temperature of 150oC or greater. However, post-curing is not usually commercially desired or indeed viable given increasing energy consumption and delays in manufacture time. Many applications described above typically desire silicone elastomeric materials having a compression set value which is as low a s possible e.g., no greater than 40%, across a wide spectrum of temperatures. In the United States electrical connector systems have to meet the requirements of the SAE International USCAR-2 “Performance Specification for Automotive Electrical Connector Systems” testing regime. Sealed connector assemblies are graded for their suitability for use over specified temperature ranges fulfilling a class of relevant automotive specifications for given temperature ranges. Currently there are five ranges identified as T1 – T5: T1 is for the temperature class -40° C to +85°C; T2 is for the temperature range -40° C to +100°C; T3 is for the temperature range -40° C to +125°C; T4 is for the temperature range -40° C to +150°C; and currently the highest grade is T5 for the -40° C to 175 °C. Current sealed connector assemblies are fulfilling the T3 temperature class. However, vehicle manufacturers are developing vehicles necessitating the need to withstand increased temperatures in vehicle engines and their surrounds due to, for example, better encapsulation, higher engine efficiency and turbocharger use etc. Hence, increasingly electrical connectors made from silicone rubber need to function at higher temperatures in order to meet T4 and T5 requirements. Given it is not desirable to be forced to post cure every elastomer after cure, a variety of additives have been proposed for the reduction of compression set without the need for post-cuing. In US5153244 compression set values of hydrosilylation cured silicone were substantially reduced by the introduction into said compositions of a phthalocyanine compound or a metal derivative of such a compound, where the metal was copper, nickel, cobalt or iron. US8080598B2 proposed a hydrosilylation cured silicone rubber having low compression set without post curing using a diacyl-hydrazide-based compound such as dodecanedioyl-di-(N′-salicyloyl)hydrazine, a synonym for which is 1-N',12-N'-bis(2-hydroxybenzoyl)dodecanedihydrazide, as well as several alternatives, in combination with a cure inhibitor selected from an acetylene-containing silane, a vinyl- containing low-molecular- weight organosiloxane compound, or an alcohol derivative having carbon- carbon triple bonds to reduce compression set. The introduction of US8080598B2 stated that “articles molded from an organopolysiloxane rubber composition curable by an addition reaction and compounded with a phthalocyanine compound have limited practical application because of coloration caused by the phthalocyanine”. Despite the teaching in US8080598B2, US9289963B2, US9598575B2 and US10000680B2 reverted back to the use of a phthalocyanine compound as a compression set additive. However, most of the previous compression set additives utilised, such as the above are suited for improving compression set after compression for at least 22 hours at up to the upper limit of T5 (+175oC) and most current silicone elastomers made from LSRs mainly only fulfill Classes T3 (maximum 125°C) or T4 (maximum 150°C) requirements with compression set of less than or equal to (≤) 50% after compression over 1008h at the respective temperature. Hence, they are not able to act sufficiently well to reduce compression set for newer target performances with permanent test temperatures of 175°C (T5) which are increasingly being considered /proposed due to the ever- increasing demands of the automotive industry and others. There is provided herein a hydrosilylation curable silicone rubber composition, which comprises the following components: a) one or more polyorganosiloxanes containing at least two unsaturated groups, selected from alkenyl groups and alkynyl groups, per molecule and having a viscosity in a range of from 1000 mPa.s to 100,000 mPa.s at 25oC; b) an organosilicon compound having at least two, alternatively at least three Si-H groups per molecule; c) a silica reinforcing filler which is optionally hydrophobically treated; d) a hydrosilylation catalyst comprising or consisting of a platinum group metal or a compound thereof; e) a phthalocyanine compound or a metal derivative of such a compound, where the metal is copper, nickel, cobalt, iron, manganese, chromium, zinc, platinum, palladium, and vanadium and which is present in an amount of from 0.02 wt. % to 2.5 wt. % of the composition; f) cyanuric acid, biuret or a mixture thereof in an amount of from 0.005 to 0.2 wt. % of the composition; and g) one or more of magnesium hydroxide, magnesium carbonate, magnesium hydroxy carbonate or manganese carbonate in an amount 0.25 to 2.0 wt. % of the composition; wherein the total wt. % of the composition is 100 wt. %. There is also provided a silicone elastomeric material which is the cured product of the above hydrosilylation curable silicone rubber composition, which silicone elastomeric material has a compression set of no more than 15%, preferably no more than 10% when measured in accordance with industrial standard norm ISO 815-1 method A after compression at 175oC for 22 hours and a compression set of no more than 20%, preferably no more than 15% when measured in accordance with industrial standard norm ISO 815-1 method A after compression at 200oC for 22 hours; alternatively having a compression set of 30 % or less, preferably 25 % or less, when measured in accordance with industrial standard norm ISO 815-1 method A after compression at 175oC for 168 hours and a compression set of 40 % or less, preferably 35 % or less, when measured in accordance with industrial standard norm ISO 815-1 method A after compression at 200oC for 168 hours (one week). There is also provided a process for making a silicone elastomeric material comprising the steps of mixing: a) one or more polyorganosiloxanes containing at least two unsaturated groups, selected from alkenyl groups and alkynyl groups, per molecule and having a viscosity in a range of from 1000 mPa.s to 100,000 mPa.s at 25oC; b) an organosilicon compound having at least two, alternatively at least three Si-H groups per molecule; c) a silica reinforcing filler which is optionally hydrophobically treated; d) a hydrosilylation catalyst comprising or consisting of a platinum group metal or a compound thereof; e) a phthalocyanine compound or a metal derivative of such a compound, where the metal is copper, nickel, cobalt, iron, manganese, chromium, zinc, platinum, palladium, and vanadium and which is present in an amount of from 0.02 wt. % to 2.5 wt. % of the composition; f) cyanuric acid, biuret or a mixture thereof in an amount of from 0.005 to 0.2 wt. % of the composition; and g) one or more of magnesium hydroxide, magnesium carbonate, magnesium hydroxy carbonate or manganese carbonate in an amount 0.25 to 2.0 wt. % of the composition; and curing the composition at a temperature of from 80oC to 200oC. There is also provided a silicone elastomeric material obtained or obtainable from a process comprising the steps of mixing a: a) one or more polyorganosiloxanes containing at least two unsaturated groups, selected from alkenyl groups and alkynyl groups, per molecule and having a viscosity in a range of from 1000 mPa.s to 100,000 mPa.s at 25oC; b) an organosilicon compound having at least two, alternatively at least three Si-H groups per molecule; c) a silica reinforcing filler which is optionally hydrophobically treated; d) a hydrosilylation catalyst comprising or consisting of a platinum group metal or a compound thereof; e) a phthalocyanine compound or a metal derivative of such a compound, where the metal is copper, nickel, cobalt, iron, manganese, chromium, zinc, platinum, palladium, and vanadium and which is present in an amount of from 0.02 wt. % to 2.5 wt. % of the composition; f) cyanuric acid, biuret or a mixture thereof in an amount of from 0.005 to 0.2 wt. % of the composition; and g) one or more of magnesium hydroxide, magnesium carbonate, magnesium hydroxy carbonate or manganese carbonate in an amount 0.25 to 2.0 wt. % of the composition; wherein the total wt. % of the composition is 100 wt. %; and curing the composition at a temperature of from 80oC to 200oC; which silicone elastomeric material has a compression set of no more than 20% after 22 hours compression at temperatures up to 190oC, alternatively up to 200oC, when measured in accordance with industrial standard norm ISO 815-1:2019 method A. There is also provided the use of a combination of components (e) (f) and (g) wherein e) is a phthalocyanine compound or a metal derivative of such a compound, where the metal is copper, nickel, cobalt, iron, manganese, chromium, zinc, platinum, palladium, and vanadium; f) is cyanuric acid, biuret or a mixture thereof in an amount of from 0.005 to 0.2 wt. % of the composition; and g) is one or more of magnesium hydroxide, magnesium carbonate, magnesium hydroxy carbonate or nd a
Figure imgf000008_0001
groups. Alternatively, component (a) has at least three unsaturated groups per molecule. The unsaturated groups of component (a) may be terminal, pendent, or in both locations.

Claims

Alkenyl groups may have 2 to 30, alternatively 2 to 24, alternatively 2 to 20, alternatively 2 to 12, alternatively 2 to 10, and alternatively 2 to 6 carbon atoms. Possible alkenyl groups are exemplified by, but not limited to, vinyl, allyl, methallyl, propenyl, and hexenyl and cyclohexenyl groups. Alkynyl groups may have 2 to 30, alternatively 2 to 24, alternatively 2 to 20, alternatively 2 to 12, alternatively 2 to 10, and alternatively 2 to 6 carbon atoms. Alkynyl groups may be exemplified by, but not limited to, ethynyl, propynyl, and butynyl groups. Component (a) has multiple units of the formula (I): R’aSiO(4-a)/2 (I) in which each R’ is independently selected from an aliphatic hydrocarbyl, or aliphatic non- halogenated organyl group (that is any aliphatic organic substituent group, regardless of functional type, having one free valence at a carbon atom). Saturated aliphatic hydrocarbyls are exemplified by, but not limited to alkyl groups such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl and cycloalkyl groups such as cyclohexyl. Unsaturated aliphatic hydrocarbyls are exemplified by, but not limited to the alkenyl groups and alkynyl groups described above. The aliphatic non-halogenated organyl groups are exemplified by, but not limited to, suitable nitrogen containing groups such as amido groups, imido groups; oxygen containing groups such as polyoxyalkylene groups, carbonyl groups, alkoxy groups and hydroxyl groups. The subscript “a” is 0, 1, 2 or 3, typically in this instance a is mainly 2 but may contain some units where a is 1 or 3. Siloxy units may be described by a shorthand (abbreviated) nomenclature, namely - "M," "D," "T," and "Q", when R’ is as described above, alternatively an alkyl group, typically a methyl group The M unit corresponds to a siloxy unit where a = 3, that is R’3SiO1/2; the D unit corresponds to a siloxy unit where a = 2, namely R’2SiO2/2; the T unit corresponds to a siloxy unit where a = 1, namely R’1SiO3/2; the Q unit corresponds to a siloxy unit where a = 0, namely SiO4/2. The polyorganosiloxane, such as a polydiorganosiloxane of component (a), is substantially linear but may contain a proportion of branching due to the presence of T units (as previously described) within the molecule, hence the average value of subscript a in structure (I) is about 2. Examples of typical R’ groups on component (a) the one or more polyorganosiloxanes containing at least two unsaturated groups, selected from alkenyl groups and alkynyl groups, per molecule, include mainly alkyl groups, especially methyl and ethyl, alternatively methyl groups but may also include aryl groups and/or fluoroalkyl groups such as trifluoropropyl or perfluoroalkyl groups in addition to the required at least two unsaturated groups selected from alkenyl and/or alkynyl groups, typically alkenyl groups The groups may be in pendent position (on a D or T siloxy unit) or may be terminal (on an M siloxy unit). Hence, the polymer chain of component (a) may be selected from polydimethylsiloxanes, alkylmethylpolysiloxanes, alkylarylpolysiloxanes or copolymers thereof (where reference to alkyl means any suitable alkyl group, alternatively an alkyl group having two or more carbons) providing each component (a) polymer comprises at least two alkenyl and or alkynyl groups, typically at least two alkenyl groups. Such polymer chains may have any suitable terminal groups, for example, they may be trialkyl terminated, alkenyldialkyl terminated alkynyldialkyl terminated or may be terminated with any other suitable terminal group combination providing each polymer contains at least two unsaturated groups selected from alkenyl and alkynyl groups per molecule. In one embodiment the terminal groups of such a polymer don’t comprise any silanol terminal groups. Hence component (a) may, for the sake of example, be: a dialkylalkenyl terminated polydimethylsiloxane, e.g., dimethylvinyl terminated polydimethylsiloxane; a dialkylalkenyl terminated dimethylmethylphenylsiloxane, e.g., dimethylvinyl terminated dimethylmethylphenylsiloxane; a trialkyl terminated dimethylmethylvinyl polysiloxane; a dialkylvinyl terminated dimethylmethylvinyl polysiloxane copolymer; a dialkylvinyl terminated methylphenylpolysiloxane, a dialkylalkenyl terminated methylvinylmethylphenylsiloxane; a dialkylalkenyl terminated methylvinyldiphenylsiloxane; a dialkylalkenyl terminated methylvinyl methylphenyl dimethylsiloxane; a trimethyl terminated methylvinyl methylphenylsiloxane; a trimethyl terminated methylvinyl diphenylsiloxane; or a trimethyl terminated methylvinyl methylphenyl dimethylsiloxane. Component a) has a viscosity of from 1000 mPa.s to 100,000 mPa.s at 25oC, alternatively 5000 mPa.s to 75,000 mPa.s at 25oC, 10,000 mPa.s to 60,000 mPa.s at 25oC and is preferably present in an amount of from 25 to 60 wt. % of the composition, alternatively in an amount of from 30 to 60 wt. % of the composition, alternatively in an amount of from 35 to 55 wt. % of the composition. Viscosity may be measured at 25 °C using either a BrookfieldTM rotational viscometer with spindle LV-4 for viscosities over 15,000mPa.s (Spindle LV-4 designed for viscosities in the range between 1,000-2,000,000 mPa.s) at an appropriate rpm and using a BrookfieldTM rotational viscometer with a cone plate arrangement with cone CP-52 for viscosities up to 15, 000mPa.s at 25°C and an appropriate rpm. Component (b) Component (b) functions as a cross-linker and is provided in the form of an organosilicon compound having at least two, alternatively at least three Si-H groups per molecule. Component (b) normally contains three or more silicon-bonded hydrogen atoms so that the hydrogen atoms can react with the unsaturated alkenyl and/or alkynyl groups of component (a) to form a network structure therewith and thereby cure the composition. Some or all of Component (b) may alternatively have two silicon bonded hydrogen atoms per molecule when polymer (a) has greater than two unsaturated groups per molecule. The molecular configuration of the organosilicon compound having at least two, alternatively at least three Si-H groups per molecule (b) is not specifically restricted. It may be a polyorganosiloxane which can have a straight chain, be branched (a straight chain with some branching through the presence of T groups), cyclic or be a silicone resin based. While the molecular weight of component (b) is not specifically restricted, the viscosity is typically from 5 to 50,000 mPa.s at 25ºC using the test methodology as described for component (a). Silicon-bonded organic groups used in component (b) may be exemplified by alkyl groups such as methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, hexyl; aryl groups such as phenyl tolyl, xylyl, or similar aryl groups; 3-chloropropyl, 3,3,3-trifluoropropyl, or similar halogenated alkyl group, preferred alkyl groups having from 1 to 6 carbons, especially methyl ethyl or propyl groups or phenyl groups. Preferably the silicon-bonded organic groups used in component (b) are alkyl groups, alternatively methyl, ethyl or propyl groups. Examples of the organosilicon compound having at least two, alternatively at least three Si-H groups per molecule (b) include but are not limited to: (a’) trimethylsiloxy-terminated methylhydrogenpolysiloxane, (b’) trimethylsiloxy-terminated polydimethylsiloxane-methylhydrogensiloxane, (c’) dimethylhydrogensiloxy-terminated dimethylsiloxane-methylhydrogensiloxane copolymers, (d’) dimethylsiloxane-methylhydrogensiloxane cyclic copolymers, (e’) copolymers and/or silicon resins consisting of (CH3)2HSiO1/2 units, (CH3)3SiO1/2 units and SiO4/2 units, (f’) copolymers and/or silicone resins consisting of (CH3)2HSiO1/2 units and SiO4/2 units, (g’) Methylhydrogensiloxane cyclic homopolymers having between 3 and 10 silicon atoms per molecule; alternatively, component (b), the cross-linker, may be a filler, e.g., silica treated with one of the above, and mixtures thereof. In one embodiment the Component (b) is selected from a methylhydrogenpolysiloxane capped at both molecular terminals with trimethylsiloxy groups; a copolymer of a methylhydrogensiloxane and a dimethylsiloxane capped at both molecular terminals with trimethylsiloxy groups; dimethylsiloxane capped at both molecular terminals with dimethylhydrogensiloxy groups; a copolymer of a methylhydrogensiloxane and a dimethylsiloxane capped at both molecular terminals with dimethylhydrogensiloxy groups. The cross-linker (b) is generally present in the hydrosilylation curable silicone rubber composition such that the molar ratio of the total number of the silicon-bonded hydrogen atoms in component (b) to the total number of alkenyl and/or alkynyl groups in component (a) is from 0.5 : 1.0 to 10.0 : 1.0. When this ratio is less than 0.5:1, a well-cured composition will not be obtained. When the ratio exceeds 10:1, there is a tendency for the hardness of the cured composition to increase when heated. Preferably component (b) is in an amount such that the molar ratio of silicon-bonded hydrogen atoms of component (b) to alkenyl/alkynyl groups, alternatively alkenyl groups of component (a) ranges from 0.7 : 1.0 to 5.0 : 1.0, alternatively from 0.9 : 1.0 to 2.5 : 1.0, and further alternatively from 0.9 : 1.0 to 2.0 : 1.0. The silicon-bonded hydrogen (Si-H) content of component (b) is determined using quantitative infra-red analysis in accordance with ASTM E168. In the present instance the silicon-bonded hydrogen to alkenyl (vinyl) and/or alkynyl ratio is important when relying on a hydrosilylation cure process. Generally, this is determined by calculating the total weight % of alkenyl groups in the composition, e.g., vinyl [V] and the total weight % of silicon bonded hydrogen [H] in the composition and given the molecular weight of hydrogen is 1 and of vinyl is 27 the molar ratio of silicon bonded hydrogen to vinyl is 27[H]/[V]. Typically, dependent on the number of unsaturated groups in component (a) as well as the number of Si-H groups in component (b), component (b) will be present in an amount of from 0.1 to 10 wt. % of the hydrosilylation curable silicone rubber composition, alternatively 0.1 to 7.5wt. % of the hydrosilylation curable silicone rubber composition, alternatively 0.5 to 7.5wt. %, further alternatively from 0.5% to 5 wt. % of the hydrosilylation curable silicone rubber composition. Component (c) Component (c) is a silica reinforcing filler which is optionally hydrophobically treated; The reinforcing fillers of component (c) may be exemplified by fumed silica and/or a precipitated silica and/or a colloidal silica. In one alternative, the fumed silica, precipitated silica and/or colloidal silica are provided in a finely divided form. Precipitated silica, fumed silica and/or colloidal silicas are particularly preferred because of their relatively high surface area, especially when provided in a finely divided form, which is typically at least 50 m²/g (BET method in accordance with ISO 9277: 2010). Fillers having surface areas of from 50 to 450 m²/g (BET method in accordance with ISO 9277: 2010), alternatively of from 50 to 300 m²/g (BET method in accordance with ISO 9277: 2010), are typically used. All these types of silica are commercially available. When silica reinforcing filler (c) is naturally hydrophilic (e.g., untreated silica fillers), it is typically treated with a treating agent to render it hydrophobic. These surface modified silica reinforcing fillers (c) do not clump and can be homogeneously incorporated into polydiorganosiloxane polymer (a), described below, as the surface treatment makes the fillers easily wetted by component (a). Typically, silica reinforcing filler (c) may be surface treated with any low molecular weight organosilicon compounds disclosed in the art applicable to prevent creping of liquid silicone rubber (LSR) compositions during processing. For example, organosilanes, polydiorganosiloxanes, or organosilazanes e.g., hexaalkyl disilazane, short chain siloxane diols to render the silica reinforcing filler (c) (s) hydrophobic and therefore easier to handle and obtain a homogeneous mixture with the other ingredients. Specific examples include, but are not restricted to, silanol terminated trifluoropropylmethylsiloxane, silanol terminated vinyl methyl (ViMe) siloxane, silanol terminated methyl phenyl (MePh) siloxane, liquid hydroxyldimethyl-terminated polydiorganosiloxane containing an average from 2 to 20 repeating units of diorganosiloxane in each molecule, hydroxyldimethyl terminated Phenylmethyl Siloxane, hexaorganodisiloxanes, such as hexamethyldisiloxane, divinyltetramethyldisiloxane; hexaorganodisilazanes, such as hexamethyldisilazane (HMDZ), divinyltetramethyldisilazane and tetramethyldi(trifluoropropyl)disilazane; hydroxyldimethyl terminated polydimethylmethylvinyl siloxane, octamethyl cyclotetrasiloxane, and silanes including but not limited to methyltrimethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, chlorotrimethyl silane, dichlorodimethyl silane, trichloromethyl silane. In one embodiment, the treating agent may be selected from silanol terminated vinyl methyl (ViMe) siloxane, liquid hydroxyldimethyl-terminated polydiorganosiloxane containing an average from 2 to 20 repeating units of diorganosiloxane in each molecule, hexaorganodisiloxanes, such as hexamethyldisiloxane, divinyltetramethyldisiloxane; hexaorganodisilazanes, such as hexamethyldisilazane (HMDZ), divinyltetramethyldisilazane and; hydroxyldimethyl terminated polydimethylmethylvinyl siloxane, octamethyl cyclotetrasiloxane, and silanes including but not limited to methyltriethoxysilane, dimethyldiethoxysilane and/or vinyltriethoxysilane. A small amount of water can be added together with the silica treating agent(s) as processing aid. The surface treatment of untreated silica reinforcing filler (c) may be undertaken prior to introduction in the composition or in situ (i.e., in the presence of at least a portion of the other ingredients of the composition herein by blending these ingredients together at room temperature or above until the filler is completely treated. Typically, untreated silica reinforcing filler (c) is treated in situ with a treating agent in the presence of component (a) which results in the preparation of a silicone rubber base material which can subsequently be mixed with other ingredients. Silica reinforcing filler (c) is optionally present in an amount of up to 40 wt. % of the composition, alternatively from 1.0 to 40wt. % of the composition, alternatively of from 5.0 to 35wt. % of the composition, alternatively of from 10.0 to 35wt. % of the composition. Component (d) Component (d) of the composition is a hydrosilylation catalyst comprising or consisting of a platinum group metal or a compound thereof. These are usually selected from catalysts of the platinum group of metals (platinum, ruthenium, osmium, rhodium, iridium and palladium), or a compound of one or more of such metals. Alternatively, platinum and rhodium compounds are preferred due to the high activity level of these catalysts in hydrosilylation reactions, with platinum compounds most preferred. In a hydrosilylation (or addition) reaction a hydrosilylation catalyst such as component (d) herein catalyses the reaction between an unsaturated group, usually an alkenyl group e.g., vinyl with Si-H groups. The catalyst (d) can be a platinum group metal, a platinum group metal deposited on a carrier, such as activated carbon, metal oxides, such as aluminum oxide or silicon dioxide, silica gel or powdered charcoal, or a compound or complex of a platinum group metal. Preferably the platinum group metal is platinum. Examples of preferred hydrosilylation catalysts (d) are platinum based catalysts, for example, platinum black, platinum oxide (Adams catalyst), platinum on various solid supports, chloroplatinic acids, e.g., hexachloroplatinic acid (Pt oxidation state IV) (Speier catalyst), chloroplatinic acid in solutions of alcohols e.g., isooctanol or amyl alcohol (Lamoreaux catalyst), and complexes of chloroplatinic acid with ethylenically unsaturated compounds such as olefins and organosiloxanes containing ethylenically unsaturated silicon-bonded hydrocarbon groups, e.g., tetra-vinyl-tetramethylcyclotetrasiloxane- platinum complex (Ashby catalyst). Soluble platinum compounds that can be used include, for example, the platinum-olefin complexes of the formulae (PtCl2.(olefin)2 and H(PtCl3.olefin), preference being given in this context to the use of alkenes having 2 to 8 carbon atoms, such as ethylene, propylene, isomers of butene and of octene, or cycloalkanes having 5 to 7 carbon atoms, such as cyclopentene, cyclohexene, and cycloheptene. Other soluble platinum catalysts are, for the sake of example a platinum-cyclopropane complex of the formula (PtCl2C3H6)2, the reaction products of hexachloroplatinic acid with alcohols, ethers, and aldehydes or mixtures thereof, or the reaction product of hexachloroplatinic acid and/or its conversion products with vinyl-containing siloxanes such as methylvinylcyclotetrasiloxane in the presence of sodium bicarbonate in ethanolic solution –. Platinum catalysts with phosphorus and amine ligands can be used as well, e.g., (Ph3P)2PtCl2; and complexes of platinum with vinylsiloxanes, such as sym- divinyltetramethyldisiloxane. Hence, specific examples of suitable platinum-based catalysts include (i) complexes of chloroplatinic acid with organosiloxanes containing ethylenically unsaturated hydrocarbon groups are described in US 3,419,593; (ii) chloroplatinic acid, either in hexahydrate form or anhydrous form; (iii) a platinum-containing catalyst which is obtained by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound, such as divinyltetramethyldisiloxane; (iv) alkene-platinum-silyl complexes as described in US Pat. No.6,605,734 such as (COD)Pt(SiMeCl2)2 where “COD” is 1,5-cyclooctadiene; and/or (v) Karstedt's catalyst, a platinum divinyl tetramethyl disiloxane complex typically containing about 1 wt. % of platinum typically in a vinyl siloxane polymer with a viscosity of from about 200 to 750 mPa.s using the test methodology as described for component (a). Solvents such as toluene and the like organic solvents have been used historically as alternatives but the use of vinyl siloxane polymers by far the preferred choice. These are described in US3,715,334 and US3,814,730. In one preferred embodiment component (d) may be selected from co-ordination compounds of platinum. In one embodiment hexachloroplatinic acid and its conversion products with vinyl-containing siloxanes, Karstedt's catalysts and Speier catalysts are preferred. Component (d) is typically present in a quantity of platinum atom that provides from 0.1 to 500ppm (parts per million) with respect to the weight of the reactive ingredients, components (a) and (b). The catalyst may be added as a single species or as a mixture of two or more different species. Typically, dependent on the form/concentration in which the catalyst is provided the amount of catalyst present will be within the range of from 0.05–1.5 wt. % of the composition, alternatively from 0.05–1.0 wt. %, alternatively from 0.1–1.0 wt. %, alternatively 0.1 to 0.5 wt. %, of the composition, wherein the platinum catalyst is provided in a masterbatch of polymer such as (a) described above. Component (e) Component (e) of the hydrosilylation curable silicone rubber composition is a phthalocyanine compound or a metal derivative of such a compound, where the metal is copper, nickel, cobalt, iron, manganese, chromium, zinc, platinum, palladium or vanadium, for example the phthalocyanine compound may have the following structure: A metal phthalocyanine e.g., copper phthalocyanine is depicted below In one embodiment component (e) comprises or consists of copper phthalocyanine Any suitable form of copper phthalocyanine may be utilised e.g., the pigment 15:3 or 15:4 beta version of copper phthalocyanine , the 15.2 alpha form of copper phthalocyanine may also be used. The 15:1 alpha form of copper phthalocyanine is suitable when sufficiently stable. with the 15:3 or 15:4 beta version of copper phthalocyanine particularly preferred. Component (e) the phthalocyanine compound or a metal derivative of such a compound is present in an amount of from 0.02 wt. % to 2.5 wt. % of the composition, alternatively of from 0.1 wt. % to 2.5 wt. % of the composition, alternatively of from 0.2 wt. % to 2.0 wt. % of the composition.
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