Silicone rubber adhesion

Abstract

The present disclosure relates to a method for adhering silicone elastomers made from hydrosilylation-curable silicone rubber compositions to inorganic substrates using a suitable adhesion mediator, the use of the adhesion mediator for said method and in connection with composite materials.

Description

[Technical field]

[0001] The present disclosure relates to a method for adhering a silicone elastomer made from a hydrosilylation-curable silicone rubber composition to an inorganic substrate using a suitable adhesion mediator, the use of the adhesion mediator for said method and in relation to a composite material, said composite material comprising an inorganic substrate adhered to a silicone elastomer using the aforementioned adhesion mediator composition.

[0002] Hydrosilylation-curable silicone rubber compositions cure via a hydrosilylation (addition) cure process to provide a silicone elastomeric material (otherwise referred to as silicone rubber).

[0003] The silicone elastomers obtained by curing the hydrosilylation-curable silicone rubber compositions have reliable properties and can be used in a wide variety of applications, such as, for example, electrical supplies, e.g., high voltage electrical insulation, electronics, automotive applications, and consumer applications, including, for example, food contact applications.

[0004] In many such applications, it is becoming increasingly desirable to produce molded composite parts that comprise silicone elastomers and other materials, such as inorganic materials, such as metals, metal alloys, glass, and ceramics.However, the preparation of such composites has proven difficult, since there is no adhesion between silicone elastomers and many inorganic materials that will be used as substrates, especially when the inorganic materials are substantially unreactive with silicone elastomers or vice versa.As a result, the ability to provide composites of silicone elastomer materials and the inorganic substrates has been limited by the inability to form a sufficiently strong adhesive bond between the two.

[0005] To overcome this lack of adhesion, the first method utilized was the application of a primer onto the substrate surface, with or without prior activation of the substrate. A primer is a preliminary coating that is applied onto the substrate and then dried and / or cured to provide improved adhesion between the substrate and the hydrosilylation curable silicone rubber composition that is then applied thereon. A primer does not always build up adhesion to the inorganic substrate unless it is cleaned and / or activated using special treatments such as, for example, solvents, ultrasonic baths, and / or flame, corona, or plasma treatments. Typically, a primer is applied onto the substrate surface to a suitable thickness of less than 10 μm up to 1 mm depending on the nature of the primer. After application and evaporation of the solvent at room temperature or elevated temperature, many primers need to be pre-cured at temperatures of 60-130° C. for 20-120 minutes. However, the use of methods that require a primer has created several problems. The use of primers for composite parts / articles is generally not preferred because they may be unreliable, may have quality control and reliability issues, and traditionally contain high percentages of organic solvents that evaporate during the drying / curing process, often resulting in undesirable volatile organic compound (VOC) environmental issues.

[0006] The use of such primers has proven particularly problematic with respect to preparation of composite parts / articles for use in highly regulated applications, such as skin contact and food contact applications.

[0007] Composite parts / articles made of one or more inorganic substrates and one or more silicone elastomers are often prepared by injection molding processes, including overmolding (e.g., injection molding of a hydrosilylation-curable silicone rubber composition onto an inorganic substrate) or 2K injection molding processes, which refers to molding both the inorganic substrate and the hydrosilylation-curable silicone rubber composition into one composite silicone elastomer / inorganic substrate article or part by using a 2K injection molding machine. Historically, this has prevented the majority of primers from being utilized due to their raw materials, especially volatile organic solvents.

[0008] It is an object of the present disclosure to provide a method for adhering silicone elastomers to inorganic substrates using a suitable adhesion mediator composition.

[0009] The present disclosure provides a method for preparing a composite of a silicone elastomer and an inorganic substrate, comprising the steps of: (a) optionally cleaning and / or activating the inorganic substrate surface; (b) treating the optionally cleaned and / or activated inorganic substrate surface with an adhesion mediator composition; (c) applying a hydrosilylation-curable silicone rubber composition onto the treated surface resulting from step (b); (d) curing the hydrosilylation-curable silicone rubber composition; and Including, The adhesion mediator composition comprises: (i) Formula Si(OR)R 1 where each R may be the same or different and is an alkyl group having at least 2 carbons per group; 1 may be the same or different and are unsaturated groups selected from alkenyl or alkynyl groups, present in an amount of 20 to 45 weight percent of the adhesion mediator composition; (ii) a platinum group metal hydrosilylation catalyst, the platinum group metal being present in an amount of 0.1 to 1.5 weight percent of the adhesion mediator composition; (iii) an alkoxytitanium compound having 2 to 4 alkoxy groups in an amount of 1 to 10% by weight of the adhesion mediator composition; (iv) Formula Si(OR 2 )4(in the formula, each R 2 are alkyl groups having at least 2 carbons per group, which may be the same or different, and are present in an amount of 5 to 20 weight percent of the adhesion mediator composition; (v) (a') a polyorganosiloxane containing at least two unsaturated groups per molecule selected from alkenyl and alkynyl groups and having a viscosity in the range of 50 mPa·s to 9000 mPa·s at 20 rpm at 25°C using a Brookfield™ viscometer equipped with an RV-4 spindle; or (b') a mixture of two or more polyorganosiloxanes containing at least two unsaturated groups per molecule selected from alkenyl and alkynyl groups, the mixture having a viscosity in the range of 50 mPa·s to 9000 mPa·s at 20 rpm at 25°C using a Brookfield™ viscometer equipped with an RV-4 spindle; Either component (v) present in an amount of 25 to 60 weight percent of the adhesion mediator composition; The present invention relates to a method comprising the steps of:

[0010] The total weight percent (wt%) of the adhesion mediator composition used in this method in any combination is 100 wt%. There was no need to wait for the adhesion mediator layer to dry or cure. In fact, it is preferred to apply the hydrosilylation curable silicone rubber composition before the adhesion mediator layer cures or solidifies. Also provided is the use of the adhesion mediator composition as described above in the preparation of silicone elastomers and inorganic composites.

[0011] 1. A composite part or article resulting or obtainable from a process for preparing a composite of a silicone elastomer and an inorganic substrate, the process comprising: (a) optionally cleaning and / or activating the inorganic substrate surface; (b) treating the optionally cleaned and / or activated inorganic substrate surface with an adhesion mediator composition; (c) applying a hydrosilylation-curable silicone rubber composition onto the treated surface resulting from step (b); (d) curing the hydrosilylation-curable silicone rubber composition; and Including, The adhesion mediator composition comprises: (i) Formula Si(OR)R 1 where each R may be the same or different and is an alkyl group having at least 2 carbons per group; 1 may be the same or different and are unsaturated groups selected from alkenyl or alkynyl groups, present in an amount of 20 to 45 weight percent of the adhesion mediator composition; (ii) a platinum group metal hydrosilylation catalyst, the platinum group metal being present in an amount of 0.1 to 1.5 weight percent of the composition; and (iii) an alkoxytitanium compound having 2 to 4 alkoxy groups in an amount of 1 to 10% by weight of the adhesion mediator composition; (iv) Formula Si(OR 2 )4(in the formula, each R 2 are alkyl groups having at least 2 carbons per group, which may be the same or different, and are present in an amount of 5 to 20 weight percent of the adhesion mediator composition; (v) (a') a polyorganosiloxane containing at least two unsaturated groups per molecule selected from alkenyl and alkynyl groups and having a viscosity in the range of 50 mPa·s to 9000 mPa·s at 20 rpm at 25°C using a Brookfield™ viscometer equipped with an RV-4 spindle; or (b') a mixture of two or more polyorganosiloxanes containing at least two unsaturated groups per molecule selected from alkenyl and alkynyl groups, the mixture having a viscosity in the range of 50 mPa·s to 9000 mPa·s at 20 rpm at 25°C using a Brookfield™ viscometer equipped with an RV-4 spindle; Either component (v) present in an amount of 25 to 60 weight percent of the adhesion mediator composition; Also provided is a composite part or article comprising:

[0012] Advantageously, the method of bonding silicone elastomers to inorganic substrates using the above adhesion mediator compositions allows for instant overmolding and does not rely on primer pre-cure treatments or solvent evaporation, i.e., it is designed to be free of major volatile organic compounds (VOCs) such as organic solvents.

[0013] Any suitable inorganic substrate may be utilized. In one embodiment, the inorganic substrate is selected from metals, such as aluminum, steel, copper, zinc, and their alloys, such as brass, glass, ceramic materials, such as silicon oxide, aluminum oxide, zirconium dioxide, aluminum silicate, cerium oxide, and composites thereof. When the inorganic substrate is glass, the glass substrate to which the composition is applied may be virtually any glass substrate, such as borosilicate glass, soda-lime glass, silica glass, alkali barium glass, aluminosilicate glass, lead glass, phosphate glass, alkali borosilicate glass, xena glass, and / or fluorosilicate glass. Alternatively, the substrate may be pretreated glass, such as vacuum-deposited reflective metallized glazing, which may be used for commercial building and architectural spandrel applications.

[0014] The process described herein has four steps: (a) optionally cleaning and / or activating the inorganic substrate surface; (b) treating the optionally cleaned and / or activated inorganic substrate surface with an adhesion mediator composition; (c) applying a hydrosilylation-curable silicone rubber composition onto the treated surface resulting from step (b); (d) curing the hydrosilylation-curable silicone rubber composition.

[0015] Process (a) As indicated above, step (a) of the process described herein, i.e., cleaning and / or activation of the inorganic substrate surface, is optional. If desired, the cleaning and / or activation step can be carried out, for example, by plasma treatment, corona discharge treatment, UV-C / ozone or vacuum-UV irradiation, flame pyrolysis deposition of amorphous silicon dioxide, or flame treatment.

[0016] The term "plasma" encompasses a wide range of systems whose densities and temperatures vary by orders of magnitude. Some plasmas are very hot, all of whose microscopic species (ions, electrons, etc.) are in near thermal equilibrium, and the energy input to the system is distributed widely by atomic / electron level collisions. However, other plasmas, especially those utilized at room temperature and atmospheric pressure or vacuum, where collisions are relatively rare, have their constituent species at widely different temperatures and are referred to as "non-thermal equilibrium" plasmas, where the free electrons are very hot, at temperatures of several thousand Kelvin, while the neutral and ionic species remain cool. As the mass of the free electrons is negligible, the total heat content of the system is low, and plasmas, such as atmospheric pressure plasma discharges, such as atmospheric pressure dielectric barrier discharges and atmospheric pressure glow discharges, operate at temperatures close to room temperature, allowing the processing of temperature-sensitive materials, such as plastics or polymers, without subjecting the samples to thermal loads that would damage them. However, the hot electrons, through high energy collisions, generate a rich source of radicals and excited species with high chemical potential energies capable of intense chemical and physical reactivity and are therefore suitable for many technological applications, such as surface activation in this case.

[0017] Corona discharge is an electrical discharge caused by ionization of a fluid, such as air, surrounding a conductor carrying high voltage. It represents a localized region where the air (or other fluid) undergoes electrical breakdown and becomes conductive, allowing charge to continuously leak out of the conductor into the air, which can be useful for cleaning and / or activation purposes.

[0018] UV-C radiation is particularly advantageously provided at wavelengths of 100 nm to 280 nm, preferably 150 nm to 260 nm, particularly preferably 170 nm to 260 nm, and can be used to clean and / or activate the surface of suitable inorganic substrates and improve the adhesion of silicones thereon after application of a coating of an adhesion mediator composition as described herein above.

[0019] Flame pyrolysis deposition of amorphous silicon dioxide can be carried out by any suitable process, such as the "PYROSIL™ process" from Sura Instruments GmbH (Jena, Germany), in which a substrate is fed through a gas flame doped with a silicon-containing precursor material (PYROSIL™), which combusts in the flame and precipitates on the surface in a very thin, yet dense, tightly adherent silicon oxide coating (5-100 nm).

[0020] For each radiation-based cleaning / activation process used, the radiation is preferably generated by a suitable radiation source, which is moved over the surface of the inorganic substrate during irradiation, or the radiation source may be stationary and / or, for example, the substrate may be moved relative to the radiation source.

[0021] The irradiation of the surface of the inorganic substrate material with UV-C radiation is further advantageously carried out while forming ozone, which interacts with the surface during irradiation. It has been found that the irradiation of the inorganic material with UV-C radiation forms ozone by interaction with the air atmosphere, which then interacts with the surface of the inorganic material to substantially improve the activation of the surface. As a result, the formed ozone is additionally used to improve the adhesion of silicone on the surface of the inorganic material.

[0022] If the irradiation is carried out in a closed space, in particular in an irradiation chamber that is darker than the outside, the advantage is achieved in particular with ozone, that the ozone remains in the area of ​​the inorganic substrate near the surface and can participate in a corresponding interaction with the surface. Additionally, provisions can be made to amplify this effect, in order to correspondingly optimize the irradiation chamber to ensure the strongest possible interaction of ozone with the surface. For example, a small size irradiation chamber is selected so that the highest possible concentration of ozone is present on the surface of the inorganic material.

[0023] The duration of irradiation can be, for example, from 0.1 seconds up to 15 minutes, alternatively from 0.1 seconds up to 10 minutes, alternatively from 3 seconds up to 7 minutes, alternatively from 3 seconds up to 5 minutes, alternatively from 0.1 seconds up to 1 minute, alternatively from 0.4 seconds to 30 seconds.

[0024] With respect to this cleaning and / or activation step, UV-C or especially corona discharge are preferred methods for step (a) of the process, particularly with respect to metals, as they can oxidize the surface of substrates such as the metals described herein.

[0025] Process (b) Once the cleaning and / or activation step (a) is complete, a layer of the adhesion mediator composition as described above is applied onto the inorganic substrate surface, as required, according to step (b). Any suitable method may be used, i.e., spraying, brushing, rolling, flooding, and squeegeeing, application with a knife coater, or wiping or transfer printing with a sponge or stamping, etc., or in certain circumstances, depending on the size and shape of the substrate, the substrate may be dip-coated by immersion in a bath of the adhesion mediator composition. In the laboratory, it has been found that wiping the surface of the inorganic substrate once the adhesion mediator composition has been applied by a pipette or the like is entirely sufficient. The adhesion mediator composition coating after application onto the substrate is typically an area of ​​0.001 to 3 mm thick, alternatively 0.001 to 2 mm thick, alternatively 0.001 to 1 mm thick.

[0026] Step (b) of the process requires the use of the adhesion mediator composition described above, the components of which are discussed below. Component (i) Component (i) of the adhesion mediator composition has the formula Si(OR)R 1 wherein each R, which may be the same or different, is an alkyl group having at least 2 carbons per group, alternatively at least 2-20 carbons per group, alternatively at least 2-15 carbons per group, alternatively at least 2-10 carbons per group; alternatively, each R group may be selected from ethyl, propyl, n-butyl, t-butyl, pentyl, or hexyl, alternatively alkyl groups having 2-6 carbons per group, such as ethyl, propyl, n-butyl, isobutyl, or t-butyl, alternatively ethyl or propyl; Each R 1 may be the same or different and are unsaturated groups selected from alkenyl or alkynyl groups, or each R 1 may be the same or different and in each case are unsaturated groups selected from alkenyl or alkynyl groups having 2 to 20 carbons per group, alternatively 2 to 15 carbons per group, alternatively 2 to 10 carbons per group, or each R 1 are alkenyl groups which may be the same or different and are selected from vinyl, propenyl, n-butenyl, pentenyl, or hexenyl.

[0027] In one embodiment, component (i), the trialkoxysilane, is present in an amount from 20 to 40% by weight of the adhesion mediator composition, alternatively from 25% to 38% by weight of the adhesion mediator composition, alternatively from 25% to 35% by weight of the adhesion mediator composition.

[0028] In a preferred embodiment, the trialkoxysilane, component (i), has the formula Si(OR)R 1where each R is an alkyl group having 2 to 4 carbons per group, such as ethyl, propyl, n-butyl, isobutyl, or t-butyl, or ethyl or propyl, and 1 are the same or different and are alkenyl groups having 2 to 6 carbons per group, such as vinyl, propenyl, n-butenyl, pentenyl, or hexenyl, or each R 1 is a vinyl group).

[0029] Component (ii) Component (ii) of the adhesion mediator composition is a platinum group metal-based hydrosilylation curing catalyst. They are usually selected from catalysts of platinum group metals (platinum, ruthenium, osmium, rhodium, iridium, and palladium) or one or more compounds 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 being most preferred. In hydrosilylation (or addition) reactions, hydrosilylation catalysts such as component (ii) herein catalyze the reaction between unsaturated groups, usually alkenyl groups, such as vinyl, and Si-H groups.

[0030] The catalyst, component (ii), may be a platinum group metal, a platinum group metal deposited on a support, for example activated carbon, a metal oxide 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.

[0031] Examples of preferred hydrosilylation catalysts (ii) are platinum-based catalysts such as platinum black, platinum oxide (Adams' catalyst), platinum on various solid supports, chloroplatinic acid, such as hexachloroplatinic acid (Pt oxidation state IV) (Speier's catalyst), chloroplatinic acid in a solution of an alcohol, such as isooctanol or amyl alcohol (Lamoreaux's catalyst), and complexes of chloroplatinic acid with ethylenically unsaturated compounds, such as olefins, and organosiloxanes containing ethylenically unsaturated silicon-bonded hydrocarbon groups, such as tetra-vinyl-tetramethylcyclotetrasiloxane-platinum complex (Ashby's catalyst). Soluble platinum compounds that can be used include, for example, platinum-olefin complexes of the formula (PtCl2.(olefin)2 and H(PtCl3.olefin), in which the use of alkenes having 2 to 8 carbon atoms, such as ethylene, propylene, isomers of butene and isomers of octene, or cycloalkanes having 5 to 7 carbon atoms, such as cyclopentene, cyclohexene, and cycloheptene, is preferred. Other soluble platinum catalysts include, for example, platinum-cyclopropane complexes of the formula (PtCl2C3H6)2, hexacycloalkanes of the formula (PtCl2C3H6), and hexacycloalkanes of the formula (PtCl2C3H6). Reaction products of chloroplatinic acid with alcohols, ethers, and aldehydes, or mixtures thereof, or reaction products of hexachloroplatinic acid and / or its conversion products with vinyl-containing siloxanes such as methylvinylcyclotetrasiloxane in the presence of sodium bicarbonate in an ethanolic solution. Platinum catalysts with phosphorus, sulfur, and amine ligands can also be used, for example (Ph3P)2PtCl2, and complexes of platinum with vinyl siloxanes such as sym-divinyltetramethyldisiloxane.

[0032] Therefore, specific examples of suitable platinum-based catalysts include: (i') complexes of chloroplatinic acid with organosiloxanes containing ethylenically unsaturated hydrocarbon groups, as described in U.S. Pat. No. 3,419,593; (ii') Chloroplatinic acid, either in its hexahydrate or anhydrous form; (iii') platinum-containing catalysts obtained by a process comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound, such as divinyltetramethyldisiloxane; (iv) alkene-platinum-silyl complexes as described in U.S. Pat. No. 6,605,734, such as (COD)Pt(SiMeCl2)2, where "COD" is 1,5-cyclooctadiene, and / or (v') Karstedt's catalyst, which is a platinum divinyltetramethyldisiloxane complex, typically containing about 1% by weight of platinum in a vinylsiloxane polymer. Solvents such as organic solvents, such as toluene, have historically been used as alternatives, but the use of vinylsiloxane polymers is a much more preferred choice. These are described in U.S. Pat. Nos. 3,715,334 and 3,814,730. In a preferred embodiment, component (ii) may be selected from platinum coordination compounds. In one embodiment, hexachloroplatinic acid and its conversion products with vinyl-containing siloxanes, Karstedt's catalyst, and Speyer's catalyst are preferred.

[0033] The catalyst may be added as a single species or as a mixture of two or more different species. Typically, depending on the form / concentration in which the catalyst is provided, the amount of platinum group metal present, or the amount of platinum metal present, will be in the range of 0.1 to 1.5% by weight of the composition, alternatively 0.1 to 1.0% by weight, or alternatively 0.1 to 0.5% by weight of the composition.

[0034] Ingredient (iii) Component (iii) of the adhesion mediator composition is an alkoxytitanium compound having 2 to 4 alkoxy groups, such as Ti(OR 3 )4, Ti(OR 3 )3R 4 , Ti(OR 3 )2R 4 2, or chelated alkoxytitanium molecules, such as esters of titanic acid and enolates of acetoacetate, where R 3 R is a straight or branched alkyl group having 1 to 20 carbons, alternatively 1 to 15 carbons, alternatively 1 to 10 carbons, alternatively 1 to 6 carbons. 3Examples of R include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, branched secondary alkyl groups such as 2,4-dimethyl-3-pentyl. 4 is an organic group such as an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aromatic group having 6 to 20 carbon atoms, e.g., a phenyl group, or a mixture thereof. 4 R may be the same or different and are selected from alkyl, alkenyl, or alkynyl groups, or in each case alkyl, alkenyl, or alkynyl groups having up to 10 carbons, or up to 6 carbons, per group. 4 Examples of may include, but are not limited to, methyl, ethyl, propyl, butyl, vinyl, cyclohexyl, phenyl, tolyl groups.

[0035] Ti(OR 3 )4, Ti(OR 3 )3R 4 , or Ti(OR 3 )2R 4 When the component (iii) is Ti(OR 2), suitable examples of the component (iii) include, for example, tetramethyl titanate, tetraethyl titanate, tetra n-propyl titanate, tetra n-butyl titanate, tetra t-butyl titanate, tetraisobutyl titanate, and tetraisopropyl titanate. 3 )3R 4 When component (iii) is a chelated titanium, it can include esters of titanic acid and enolates of acetoacetate.

[0036] In one embodiment, component (iii) has the structure Ti(OR 3 )4, Ti(OR 3 )3R 4 , Ti(OR 3 )2R 4 2 (in the formula, each R 4 may be as above, and R 3 is an isobutyl or n-butyl group), or component (iii) is an enolate of an ester of titanic acid and an acetoacetate.

[0037] Component (iii) of the adhesion mediator composition, i.e., an alkoxytitanium compound having 2 to 4 alkoxy groups, may be present in an amount of from 1 to 10% by weight of the composition, alternatively from 2 to 8% by weight, alternatively from 2 to 7% by weight of the composition.

[0038] Component (iv) Component (iv) of the adhesion mediator composition is a compound represented by the formula Si(OR 2 ) 4 tetraalkoxysilanes, wherein each R 2 may be the same or different and are alkyl groups having at least 2 carbons per group, alternatively 2 to 20 carbons per group, alternatively 2 to 15 carbons per group, alternatively 2 to 10 carbons per group, alternatively ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, or hexyl, alternatively ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, and component (iv) is present in the adhesion mediator composition in an amount from 5 to 20% by weight of the composition, alternatively 5 to 15% by weight, alternatively 7 to 15% by weight.

[0039] Component(v) Component (v) of the adhesion mediator composition is (a') a polyorganosiloxane containing at least two unsaturated groups per molecule selected from alkenyl and alkynyl groups and having a viscosity in the range of 50 mPa·s to 9000 mPa·s at 20 rpm at 25°C using a Brookfield™ viscometer equipped with an RV-4 spindle; or (b') a mixture of two or more polyorganosiloxanes containing at least two unsaturated groups per molecule selected from alkenyl and alkynyl groups, the mixture having a viscosity in the range of 50 mPa·s to 9000 mPa·s at 20 rpm at 25°C using a Brookfield™ viscometer equipped with an RV-4 spindle; Either The component (v) is present in an amount of 25 to 60% by weight of the composition.

[0040] Both the polyorganosiloxane containing at least two unsaturated groups selected from alkenyl and alkynyl groups per molecule in (v)(a') and the mixture of two or more polyorganosiloxanes containing at least two unsaturated groups selected from alkenyl and alkynyl groups per molecule in (v)(b') have a viscosity in the range of 50 mPa·s to 9000 mPa·s at 20 rpm at 25°C using a Brookfield™ viscometer equipped with an RV-4 spindle, or a viscosity in the range of 100 mPa·s to 9000 mPa·s at 20 rpm at 25°C using a Brookfield™ viscometer equipped with an RV-4 spindle, or a viscosity in the range of 100 mPa·s to 9000 mPa·s at 20 rpm at 25°C using a Brookfield™ viscometer equipped with an RV-4 spindle, Alternatively, the viscosity ranges from 100 mPa·s to 8000 mPa·s at 20 rpm using a Brookfield™ viscometer equipped with an RV-4 spindle at 25° C.; or from 100 mPa·s to 7500 mPa·s at 20 rpm using a Brookfield™ viscometer equipped with an RV-4 spindle at 25° C.; or from 100 mPa·s to 7000 mPa·s at 20 rpm using a Brookfield™ viscometer equipped with an RV-4 spindle at 25° C.; or from 200 mPa·s to 7000 mPa·s at 20 rpm using a Brookfield™ viscometer equipped with an RV-4 spindle at 25° C.; or from 300 mPa·s to 5000 mPa·s at 20 rpm using a Brookfield™ viscometer equipped with an RV-4 spindle at 25° C.

[0041] (v) In the case of (b'), the mixture contains at least two unsaturated groups selected from alkenyl and alkynyl groups per molecule, and the viscosity of the resulting mixture is in the range of 50 mPa·s to 9000 mPa·s at 25°C at 20 rpm using a Brookfield™ viscometer equipped with an RV-4 spindle, or The composition may comprise a polyorganosiloxane having a viscosity in the range of 50 mPa·s to 25,000 mPa·s at 25° C., alternatively 100 mPa·s to 25,000 mPa·s at 25° C., alternatively 100 mPa·s to 15,000 mPa·s at 25° C., alternatively 100 mPa·s to 10,000 mPa·s at 25° C., in an amount of 25 to 60% by weight of the composition, alternatively 30 to 60% by weight of the composition, alternatively 35 to 55% by weight of the composition.

[0042] The viscosity of individual polymers in (v)(b') having a viscosity greater than 10,000 mPa·s measured at 25° C. may be measured using a Brookfield™ rotational viscometer equipped with spindle LV-4 (designed for viscosities in the range of 10,000 to 2,000,000 mPa·s) with the speed adapted according to the polymer viscosity, e.g., to 6 rpm.

[0043] Each polyorganosiloxane of component (v) is a polydiorganosiloxane having at least two unsaturated groups per molecule, the unsaturated groups being selected from alkenyl or alkynyl groups. Alternatively, each polyorganosiloxane of component (v) has at least three unsaturated groups per molecule.

[0044] The unsaturated groups of each polyorganosiloxane of component (v) may be at terminal, pendant, or both positions. The alkenyl groups may have 2 to 30, alternatively 2 to 24, alternatively 2 to 20, alternatively 2 to 12, alternatively 2 to 10, alternatively 2 to 6 carbon atoms. The alkenyls are exemplified by, but are not limited to, vinyl, allyl, methallyl, propenyl, and hexenyl groups, and cyclohexenyl groups. The alkynyls may be exemplified by, but are not limited to, ethynyl, propynyl, and butynyl groups. The alkynyl groups may have 2 to 30, alternatively 2 to 24, alternatively 2 to 20, alternatively 2 to 12, alternatively 2 to 10, alternatively 2 to 6 carbon atoms.

[0045] Each polyorganosiloxane of component (v) has the formula (I): R' a SiO (4-a) / 2 (I) In the formula, each R' is independently selected from an aliphatic hydrocarbyl group or an aliphatic non-halogenated organyl group (any aliphatic organic substituent having one free valence at a carbon atom, regardless of the type of functional group). 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 and alkynyl groups listed above. Aliphatic non-halogenated organyl groups are exemplified by, but not limited to, suitable nitrogen-containing groups such as amide groups, imide groups, polyoxyalkylene groups, oxygen-containing groups such as carbonyl groups, alkoxy groups, and hydroxyl groups. Further organyl groups may include sulfur-containing groups, phosphorus-containing groups, and boron-containing groups. The subscript "a" is 0, 1, 2, or 3.

[0046] The siloxy units may be described by the shorthand nomenclature "M", "D", "T" and "Q", where R' is as above or alternatively an alkyl group, typically a methyl group. M units are siloxy units where a=3, i.e., R'SiO 1 / 2 and D units are siloxy units where a=2, i.e., R'SiO 2 / 2 where T units are siloxy units where a=1, i.e., R'SiO 3 / 2 and Q units are siloxy units where a=0, i.e., SiO 4 / 2 Each polydiorganosiloxane of component (v) is substantially linear, but may contain a proportion of branching due to the presence of T units (as described above) within the molecule, such that the average value of a in structure (I) is about 2.

[0047] Typical examples of groups on each polyorganosiloxane of component (v) as described above include at least two unsaturated groups per molecule selected from alkenyl and alkynyl groups, typically alkenyl groups, with viscosities in the ranges as described above including predominantly alkenyl, alkynyl, and / or alkyl groups, or alkenyl and / or alkyl groups. The groups may be pendant (on D or T siloxy units) or terminal (on M siloxy units).

[0048] Each polyorganosiloxane of component (v) may be selected from, for example, polydimethylsiloxanes, alkylmethylpolysiloxanes, alkylarylpolysiloxanes, or copolymers thereof, containing alkenyl and / or alkynyl groups (reference to alkyl means any suitable alkyl group, or alternatively, alkyl groups having 2 or more carbons), and may have any suitable end groups, which may be, for example, trialkyl-terminated, alkenyldialkyl-terminated, alkynyldialkyl-terminated, or terminated with any other suitable combination of end groups, provided that each polymer contains at least two unsaturated groups selected from alkenyl and alkynyl groups per molecule. In one embodiment, the end groups of such polymers do not include any silanol end groups.

[0049] Thus, each polyorganosiloxane of component (v) can be, for example, The alkyl group may be a dialkylalkenyl-terminated polydimethylsiloxane, such as a dimethylvinyl-terminated polydimethylsiloxane, a dialkylalkenyl-terminated dimethylmethylphenylsiloxane, such as a dimethylvinyl-terminated dimethylmethylphenylsiloxane, a trialkyl-terminated dimethylmethylvinylpolysiloxane, a dialkylvinyl-terminated dimethylmethylvinylpolysiloxane copolymer, a dialkylvinyl-terminated methylphenylpolysiloxane, a dialkylalkenyl-terminated methylvinylmethylphenylsiloxane, a dialkylalkenyl-terminated methylvinyldiphenylsiloxane, a dialkylalkenyl-terminated methylvinylmethylphenyldimethylsiloxane, a trimethyl-terminated methylvinylmethylphenylsiloxane, a trimethyl-terminated methylvinyldiphenylsiloxane, or a trimethyl-terminated methylvinylmethylphenyldimethylsiloxane.

[0050] Thus, the adhesion mediator composition used in the process herein is (i) Formula Si(OR)R 1 where each R may be the same or different and is an alkyl group having at least 2 carbons per group; 1and wherein R, R and R are the same or different and are unsaturated groups selected from alkenyl or alkynyl groups, wherein the trialkoxysilane is present in an amount of 20-40% by weight of the composition, alternatively 25%-38% by weight of the adhesion mediator composition, alternatively 25%-35% by weight of the adhesion mediator composition; (ii) a platinum group metal hydrosilylation catalyst in an amount of 0.1 to 1.5% by weight of the composition, alternatively 0.1 to 1.0% by weight of the composition, alternatively 0.1 to 0.5% by weight of the composition; (iii) an alkoxytitanium compound having 2 to 4 alkoxy groups in an amount of 1 to 10%, alternatively 2 to 8%, alternatively 2 to 7% by weight of the composition; (iv) Formula Si(OR 2 )4(in the formula, each R 2 may be the same or different and have at least 2 carbons per group), present in an amount of 5 to 20%, alternatively 5 to 15%, alternatively 7 to 15% by weight of the composition; and (v) (a') polyorganosiloxanes containing at least two unsaturated groups per molecule selected from alkenyl and alkynyl groups, and having a viscosity in the range of 50 mPa·s to 9000 mPa·s, alternatively in the range of 100 mPa·s to 9000 mPa·s, alternatively in the range of 100 mPa·s to 8000 mPa·s, alternatively in the range of 100 mPa·s to 7500 mPa·s, alternatively in the range of 100 mPa·s to 7000 mPa·s, alternatively in the range of 200 mPa·s to 7000 mPa·s, alternatively in the range of 300 mPa·s to 5000 mPa·s, in each case using a Brookfield™ viscometer equipped with an RV-4 spindle at 25°C at 20 rpm; (b') a mixture of two or more polyorganosiloxanes containing at least two unsaturated groups per molecule selected from alkenyl and alkynyl groups, the mixture having a viscosity in the range of 50 mPa·s to 9000 mPa·s, alternatively in the range of 100 mPa·s to 9000 mPa·s, alternatively in the range of 100 mPa·s to 8000 mPa·s, alternatively in the range of 100 mPa·s to 7500 mPa·s, alternatively in the range of 100 mPa·s to 7000 mPa·s, alternatively in the range of 200 mPa·s to 7000 mPa·s, alternatively in the range of 300 mPa·s to 5000 mPa·s, at 20 rpm at 25°C, in each case using a Brookfield™ viscometer equipped with an RV-4 spindle; and component (v), which is either the polyorganosiloxane or the mixture, present in an amount from 25 to 60% by weight of the composition, alternatively in an amount from 30 to 60% by weight of the composition, alternatively in an amount from 35 to 55% by weight of the composition.

[0051] Any suitable combination of components (i)-(v) may be utilized with or without additives, however the total weight percent of the composition is 100 weight percent regardless of whether additives are included or not.

[0052] In one embodiment of the disclosure herein, the adhesion mediator composition used in the process herein comprises: (i) Formula Si(OR)R 1 where each R may be the same or different and is an alkyl group having at least 2 carbons per group; 1 and wherein R, R and R are the same or different and are unsaturated groups selected from alkenyl or alkynyl groups, wherein the trialkoxysilane is present in an amount of 20-40% by weight of the composition, alternatively 25%-38% by weight of the adhesion mediator composition, alternatively 25%-35% by weight of the adhesion mediator composition; (ii) a platinum group metal hydrosilylation catalyst selected from one or more coordination compounds of platinum in an amount of 0.1 to 1.5% by weight of the composition, alternatively 0.1 to 1.0% by weight of the composition, alternatively 0.1 to 0.5% by weight of the composition; (iii) Ti(OR 3 )4, Ti(OR 3 )3R 4 , Ti(OR 3 )2R 4 An alkoxytitanium compound having 2 to 4 alkoxy groups selected from the group consisting of R 4 may be the same or different and are selected from an alkyl group, an alkenyl group, or an alkynyl group; each R 3 is selected from an isobutyl or n-butyl group, or component (iii) is an ester of titanic acid and an enolate of an acetoacetate ester in an amount of 1 to 10% by weight of the composition, alternatively 2 to 8% by weight, alternatively 2 to 7% by weight, (iv) Formula Si(OR 2 )4(in the formula, each R 2 may be the same or different and are alkyl groups in an amount of 5 to 20%, alternatively 5 to 15%, alternatively 7 to 15% by weight of the composition; (v) (a') polyorganosiloxanes containing at least two unsaturated groups per molecule selected from alkenyl and alkynyl groups, and having a viscosity in the range of 50 mPa·s to 9000 mPa·s, alternatively 100 mPa·s to 9000 mPa·s, alternatively 100 mPa·s to 8000 mPa·s, alternatively 100 mPa·s to 7500 mPa·s, alternatively 100 mPa·s to 7000 mPa·s, alternatively 200 mPa·s to 7000 mPa·s, alternatively 300 mPa·s to 5000 mPa·s, in each case using a Brookfield™ viscometer with an RV-4 spindle at 25°C at 20 rpm; (b') a mixture of two or more polyorganosiloxanes containing at least two unsaturated groups per molecule, selected from alkenyl and alkynyl groups, wherein the mixture has a viscosity of from 50 mPa·s to 9000 mPa·s at 20 rpm at 25°C using a Brookfield™ viscometer equipped with an RV-4 spindle in each case. or a mixture having a viscosity in the range of 100 mPa·s to 9000 mPa·s, or a viscosity in the range of 100 mPa·s to 8000 mPa·s, or a viscosity in the range of 100 mPa·s to 7500 mPa·s, or a viscosity in the range of 100 mPa·s to 7000 mPa·s, or a viscosity in the range of 200 mPa·s to 7000 mPa·s, or a viscosity in the range of 300 mPa·s to 5000 mPa·s, and component (v), which is either the polyorganosiloxane or the mixture, present in an amount from 25 to 60% by weight of the composition, alternatively in an amount from 30 to 60% by weight of the composition, alternatively in an amount from 35 to 55% by weight of the composition.

[0053] Any suitable combination of components (i)-(v) may be utilized with or without additives, however the total weight percent of the composition is 100 weight percent regardless of whether additives are included or not.

[0054] The adhesion mediator compositions utilized in the processes herein can be mixed homogeneously using any suitable mixing means, and indeed for laboratory purposes, the compositions were mixed by hand in an appropriately sized container using a spoon or spatula or the like.

[0055] The adhesion mediator composition utilized in the method herein is not a primer in our opinion, since it works differently. A standard primer is a preliminary coating that is applied onto a substrate and then, in an essential step, dried and / or cured prior to the addition of the next layer. In this disclosure, the adhesion mediator composition does not undergo the essential drying / curing step to provide improved adhesion between the substrate and the silicone elastomer. Furthermore, there are no harmful or toxic solvents included in the composition that are designed to evaporate as part of the drying process. In the process herein, there is no need to wait for the adhesion mediator layer to dry or cure, and in fact, in one embodiment, the hydrosilylation curable silicone rubber composition is preferably applied before the adhesion mediator layer solidifies or cures. This significantly reduces environmental issues resulting from the emission of volatile organic compounds (VOCs) often associated with the use of primers, as well as regulatory issues such as skin contact and food contact applications. Instead, a reactive diluent (component (v)) is used that is non-volatile. The adhesion mediator reacts as a whole and is incorporated into the LSR / composite article.

[0056] Once the adhesion mediator composition has been applied onto the inorganic substrate, the hydrosilylation-curable silicone rubber composition may be immediately applied onto the adhesion mediator composition, and then the hydrosilylation-curable silicone rubber composition is cured at appropriate temperature and pressure to form a composite part / article. The fact that no drying step is required has the added benefit of shorter processing times and higher productivity compared to typical primer solutions.

[0057] Process (c) In step (c), a hydrosilylation-curable silicone rubber composition is applied onto the substrate treated with the adhesion mediator composition in step (b). Preferably, this may be performed immediately after applying the adhesion mediator composition onto the optionally activated substrate. By performing this step immediately, the adhesion mediator composition can soak into the hydrosilylation-curable silicone rubber composition surface at the inorganic substrate / hydrosilylation-curable silicone rubber composition interface, so that the adhesion mediator composition and the hydrosilylation-curable silicone rubber composition are effectively "cured" together on the surface of the inorganic substrate during step (d).

[0058] Any suitable hydrosilylation-curable silicone rubber composition may be applied onto the inorganic substrate coated with the adhesion mediator composition. Standard hydrosilylation-curable silicone rubber (or LSR) compositions used for application onto inorganic substrates treated with the adhesion mediator composition include: (I) one or more polyorganosiloxane polymers, e.g., one or more polydiorganosiloxane polymers having a chemical structure as described in component (v) of the adhesion mediator composition above and a viscosity of 1000 to 100,000 mPa·s at 25° C.; (II) optionally, one or more finely divided reinforcing fillers, or one or more finely divided reinforcing fillers in an amount of 5 to 40% by weight of the composition; (III) an organohydrogenpolysiloxane having at least two or at least three Si-H groups per molecule; (IV) a platinum group metal-based hydrosilylation reaction catalyst, as described under component (ii) of the adhesion mediator composition above, and, optionally, (V) a cure inhibitor.

[0059] Component (I) Component (I) of a typical hydrosilylation-curable silicone rubber (or LSR) composition is one or more polyorganosiloxane polymers, such as one or more polydiorganosiloxane polymers having the chemical structure described above for component (v) of the adhesion mediator composition, but which may have a viscosity of 1000 to 100,000 mPa·s at 25° C., measured as previously described. In the case of component (I), the polymer is present in the composition in an amount of 35 to 85% by weight of the composition.

[0060] Component (II) Component (II) of a typical hydrosilylation-curable silicone rubber (or LSR) composition is one or more reinforcing fillers, preferably provided in finely divided form.

[0061] The reinforcing fillers of component (II) may be exemplified by fumed silica and / or precipitated silica, in either case preferably micronized, and / or a suitable silicone resin.

[0062] Precipitated silica, fumed silica and / or colloidal silica are generally at least 50m 2 Particularly preferred due to their relatively high surface area of ​​50 to 450 m / g (BET method according to ISO 9277:2010). 2 / g (BET method according to ISO9277:2010), alternatively 50-300m 2 Use fillers with a surface area of ​​0.1 μm / g (BET method according to ISO 9277:2010). All these types of silica are commercially available.

[0063] If the reinforcing filler (II) is inherently hydrophilic (e.g., untreated silica filler), it is typically treated with a treating agent to render the filler hydrophobic. These surface-modified reinforcing fillers (II) do not agglomerate, and the surface treatment allows the filler to be easily wetted by the polydiorganosiloxane polymer (v), so that they can be homogeneously incorporated into the polydiorganosiloxane polymer (v) described below.

[0064] Typically, the reinforcing filler (II) can be surface treated with any low molecular weight organosilicon compound disclosed in the applicable art to prevent creping of the LSR composition during processing. For example, organosilanes, polydiorganosiloxanes, or organosilazanes, such as hexaalkyldisilazanes, short chain siloxanediols, which render the filler hydrophobic and therefore easier to handle and to obtain a homogeneous mixture with other ingredients. Specific examples include silanol-terminated trifluoropropylmethylsiloxane, silanol-terminated vinyl methyl (ViMe) siloxane, silanol-terminated methylphenyl (methylphenyl) silanol. phenyl, MePh) siloxanes, liquid hydroxyldimethyl terminated polydiorganosiloxanes containing an average of 2-20 diorganosiloxane repeat units in each molecule, hydroxyldimethyl terminated phenylmethylsiloxanes, hexaorganodisiloxanes such as hexamethyldisiloxane, divinyltetramethyldisiloxanes; hexamethyldisilazane (hexamethyldisilazane, HMDZ), divinyltetramethyldisilazane, and tetramethyldi(trifluoropropyl)disilazane; hydroxyldimethyl terminated polydimethylmethylvinylsiloxane, octamethylcyclotetrasiloxane, and silanes including, but not limited to, methyltrimethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, chlorotrimethylsilane, dichlorodimethylsilane, trichloromethylsilane.

[0065] In one embodiment, the treating agent may be selected from silanol terminated vinylmethyl (ViMe) siloxanes, liquid hydroxyldimethyl terminated polydiorganosiloxanes containing an average of 2-20 diorganosiloxane repeat units in each molecule, hexaorganodisiloxanes such as hexamethyldisiloxane, divinyltetramethyldisiloxane, hexaorganodisilazanes such as hexamethyldisilazane (HMDZ), divinyltetramethyldisilazane, and hydroxyldimethyl terminated polydimethylmethylvinylsiloxane, octamethylcyclotetrasiloxane, and methyltriethoxysilane, dimethyldiethoxysilane, and / or vinyltriethoxysilane. A small amount of water may be added with the silica treating agent as a processing aid.

[0066] The surface treatment of the untreated reinforcing filler (II) may be carried out prior to its introduction into the composition or in situ (i.e., in the presence of at least a portion of the other ingredients of the compositions herein by blending these ingredients together at room temperature or above until the filler is completely treated. Typically, the untreated reinforcing filler (II) is treated with a treating agent in situ in the presence of the polydiorganosiloxane polymer (I), thereby resulting in the preparation of a silicone rubber-based material which can then be mixed with other ingredients.

[0067] The reinforcing filler (II) is optionally present in an amount up to 40% by weight of the composition, alternatively from 1.0 to 40% by weight of the composition, alternatively from 5.0 to 35% by weight of the composition, alternatively from 10.0 to 35% by weight of the composition.

[0068] Ingredient (III) Component (III) of a standard hydrosilylation curable silicone rubber (or LSR) composition is a crosslinker in the form of a polyorganosiloxane containing at least two or three silicon-bonded hydrogen atoms per molecule. Typically, component (III) contains three or more silicon-bonded hydrogen atoms so that the hydrogen atoms can react with the unsaturated alkenyl or alkynyl groups of polymer (I) to form a network therewith, thereby curing the composition. Alternatively, when polymer (I) has more than two unsaturated groups per molecule, some or all of component (III) can have two silicon-bonded hydrogen atoms per molecule.

[0069] The molecular structure of the polyorganosiloxane containing at least 2 or 3 silicon-bonded hydrogen atoms per molecule (III) is not particularly limited and can be linear, partially branched linear, cyclic, or silicone resin-based.

[0070] The molecular weight of component (III) is not particularly limited, but the viscosity is typically 15-50,000 mPa·s at 25° C., and for viscosities below 1000 mPa·s, rely on either a Brookfield™ rotational viscometer with spindle LV-4 (designed for viscosities in the range of 1,000-2,000,000 mPa·s) or a Brookfield™ rotational viscometer with spindle LV-1 (designed for viscosities in the range of 15-20,000 mPa·s), adapting the speed according to the polymer viscosity to obtain good miscibility with polymer (I).

[0071] The silicon-bonded organic group used in component (III) may be exemplified by alkyl groups such as methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, hexyl, etc., aryl groups such as phenyl, tolyl, xylyl, etc., and halogenated alkyl groups such as 3-chloropropyl, 3,3,3-trifluoropropyl, etc., with methyl and phenyl groups being preferred. Preferably, the silicon-bonded organic group used in component (III) is an alkyl group, or a methyl group, an ethyl group, or a propyl group.

[0072] Examples of polyorganosiloxanes containing at least 2 or 3 silicon-bonded hydrogen atoms per molecule (III) include: (a'') trimethylsiloxy-terminated methylhydrogenpolysiloxane, (b'') trimethylsiloxy-terminated polydimethylsiloxane-methylhydrogensiloxane; (c'') dimethylhydrogensiloxy-terminated dimethylsiloxane-methylhydrogensiloxane copolymer; (d'') cyclic copolymer of dimethylsiloxane-methylhydrogensiloxane; (e'')(CH3)2HSiO 1 / 2 Unit: (CH3)3SiO 1 / 2 Units, and SiO 4 / 2 copolymers and / or silicone resins consisting of units; (f'')(CH3)2HSiO 1 / 2 Units, and SiO 4 / 2 copolymers and / or silicone resins consisting of units; (g'') methylhydrogensiloxane cyclic homopolymers having 3 to 10 silicon atoms per molecule, but are not limited thereto; Alternatively, the crosslinker, component B, can be a filler, such as silica that has been treated with one of the above, and mixtures thereof.

[0073] Component (III) can be exemplified by the following compounds: methylhydrogenpolysiloxanes terminally terminated with trimethylsiloxy groups; copolymers of methylhydrogensiloxane and dimethylsiloxane terminally terminated with trimethylsiloxy groups; dimethylsiloxane terminally terminated with dimethylhydrogensiloxy groups; copolymers of methylhydrogensiloxane and dimethylsiloxane terminally terminated with dimethylhydrogensiloxy groups; copolymers of methylhydrogensiloxane and methylphenylsiloxane terminally terminated with dimethylphenylsiloxy groups; cyclic methylhydrogenpolysiloxanes; (CH3)2HSiO 1 / 2Siloxane units and SiO 4 / 2 Copolymer consisting of units; (CH3)2HSiO 1 / 2 Siloxane unit, (CH3)3SiO 1 / 2 Siloxane units, and SiO 4 / 2 A copolymer consisting of units, in which some or all of the methyl groups of the above-mentioned polyorganosiloxane are substituted with alkyl groups such as ethyl groups and propyl groups; those substituted with aryl groups such as phenyl and tolyl; those substituted with halogenated alkyl groups such as 3,3,3-trifluoropropyl; or a mixture of two or more of the above-mentioned polyorganosiloxanes. In one embodiment, component (III) is selected from methylhydrogenpolysiloxanes whose molecular ends are capped with trimethylsiloxy groups; copolymers of methylhydrogensiloxane and dimethylsiloxane whose molecular ends are capped with trimethylsiloxy groups; dimethylsiloxanes whose molecular ends are capped with dimethylhydrogensiloxy groups; and copolymers of methylhydrogensiloxane and dimethylsiloxane whose molecular ends are capped with dimethylhydrogensiloxy groups.

[0074] The polyorganosiloxane crosslinker (III) is generally present in the curable silicone elastomer composition such that the molar ratio of the total number of silicon-bonded hydrogen atoms in component (III) to the total number of alkenyl and / or alkynyl groups in polymer (v) is 0.5:1 to 20:1. If this ratio is less than 0.5:1, a sufficiently cured composition is not obtained. If this ratio exceeds 20:1, the hardness of the cured composition tends to increase when heated. Preferably, it is present in an amount such that the ratio of the number of moles of silicon-bonded hydrogen atoms in component (III) to the number of moles of alkenyl groups in component (I) is in the range of 0.7:1.0 to 5.0:1.0, preferably 0.9:1.0 to 2.5:1.0, and most preferably 0.9:1.0 to 2.0:1.0.

[0075] The silicon-bonded hydrogen (Si-H) content of component (III) is determined using quantitative infrared analysis in accordance with ASTM E 168. In the present invention, the ratio of silicon-bonded hydrogen to alkenyl (vinyl) and / or alkynyl is important when relying on a hydrosilylation cure process.

[0076] Generally, this is determined by calculating the total weight percent of alkenyl groups, e.g., vinyl [V], in the composition and the total weight percent of silicon-bonded hydrogen [H] in the composition, where assuming a molecular weight of hydrogen of 1 and a molecular weight of vinyl of 27, the molar ratio of silicon-bonded hydrogen to vinyl is 27[H] / [V].

[0077] Typically, depending on the number of unsaturated groups in component (I) and the number of Si-H groups in component (III), component (III) is present in an amount from 0.1 to 25% by weight of the LSR composition, alternatively from 0.1 to 20% by weight of the LSR composition, alternatively from 0.1 to 15% by weight of the LSR composition, and further alternatively from 0.5% to 10% by weight of the LSR composition.

[0078] Component (IV) Component (IV) of a standard hydrosilylation curable silicone rubber (or LSR) composition is a platinum group metal-based hydrosilylation reaction catalyst, such as those described in component (ii) of the adhesion mediator composition above. Alternatively, component (IV) may be a UV-platinum catalyst system. Typically, it is present in an amount of platinum atoms providing 0.1 to 500 parts per million (ppm) based on the weight of the reactive raw materials, components (I) and (III). The catalyst may be added as a single species or as a mixture of two or more different species. Typically, depending on the form / concentration in which the catalyst is provided, the amount of catalyst present is in the range of 0.05 to 1.5% by weight of the composition, alternatively 0.05 to 1.0% by weight of the composition, alternatively 0.1 to 1.0% by weight of the composition, alternatively 0.1 to 0.5% by weight, where the platinum catalyst is provided in a masterbatch of a polymer, such as (I) and (v) above.

[0079] In one embodiment, the hydrosilylation catalyst is a coordination compound of platinum and the final composite contains up to 50 mg of platinum per kg, typically this being the cumulative sum of the platinum present in the adhesion mediator and the silicone rubber material applied onto the inorganic substrate, herein referred to as the adhesion mediator content.

[0080] Component (V) Component (V) of the standard hydrosilylation curable silicone rubber (or LSR) composition is one or more optional cure inhibitors. Cure inhibitors are used to prevent or slow the addition reaction cure process, if necessary, especially during storage. Optional addition reaction inhibitors for platinum-based catalysts are well known in the art and include hydrazines, triazoles, phosphines, mercaptans, organic nitrogen compounds, acetylene alcohols, silylated acetylene alcohols, maleates, fumarates, ethylenically or aromatically unsaturated amides, ethylenically unsaturated isocyanates, olefinic siloxanes, unsaturated hydrocarbon monoesters and diesters, conjugated ene-ynes, hydroperoxides, nitriles, and diaziridines. Alkenyl-substituted siloxanes, such as those described in U.S. Pat. No. 3,989,667, may also be used, of which cyclic methylvinyl siloxanes are preferred.

[0081] One class of known hydrosilylation reaction inhibitors are the acetylenic compounds disclosed in U.S. Patent No. 3,445,420. Acetylenic alcohols such as 2-methyl-3-butyn-2-ol constitute a preferred class of inhibitors which suppress the activity of platinum-containing catalysts at 25° C. Typically, compositions containing these inhibitors must be heated at temperatures above 70° C. in order to cure at a practical rate.

[0082] Examples of acetylenic alcohols and their derivatives include 1-ethynyl-1-cyclohexanol (ETCH), 2-methyl-3-butyn-2-ol, 3-butyn-1-ol, 3-butyn-2-ol, propargyl alcohol, 1-phenyl-2-propyn-1-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclopentanol, 3-methyl-1-penten-4-yn-3-ol, and mixtures thereof. Derivatives of acetylenic alcohols can include those compounds having at least one silicon atom.

[0083] In some cases, inhibitor concentrations as low as 1 mole of inhibitor per mole of catalyst metal, when present, will impart satisfactory storage stability and cure speed. In other cases, inhibitor concentrations of up to 500 moles of inhibitor per mole of catalyst metal are necessary. The optimum concentration for a given inhibitor in a given composition is readily determined by routine experimentation. Depending on the concentration and form in which the selected inhibitor is commercially provided / available, if present in the composition, the inhibitor is typically present in an amount of 0.0125-10% by weight of the composition.

[0084] In one embodiment, the inhibitor, if present, is selected from 1-ethynyl-1-cyclohexanol (ETCH) and / or 2-methyl-3-butyn-2-ol and is present in an amount of greater than 0 to 0.1% by weight of the composition.

[0085] Such compositions may also contain one or more optional additives depending on the intended use. Examples include mold release agents, non-reinforcing fillers, adhesion catalysts, peroxides, pigments, conductive fillers, thermally conductive fillers, pot life extension agents, flame retardants, lubricants, mold release agents, UV light stabilizers, germicides, wetting agents, heat stabilizers, compression set additives, and plasticizers. In one embodiment, the composition does not contain any optional additives other than component (V) above.

[0086] The hydrosilylation-curable silicone rubber compositions described above are typically stored prior to use in two or more parts. In the case of a two-part composition, the two parts are typically referred to as part (A) and part (B). Fluid (A) typically contains, in addition to polyorganosiloxane (I) and, if present, filler (II), a catalyst (IV); Fluid (B) typically comprises component (III) and, if present, component (V), the inhibitor, as well as any remaining polyorganosiloxane (I) and / or filler (II).

[0087] It is important that the catalyst (IV) is stored separately from the crosslinker (III) to prevent premature curing during storage.

[0088] Any optional additives may be present in either liquid (A) or liquid (B), or in both liquids, provided that they do not adversely affect the storage of any of the essential components present in each liquid.

[0089] A wide variety of hydrosilylation curable silicone compositions that can be used in the process herein are available on the market.These hydrosilylation curable silicone compositions include, for example, Silastic® RBL-9200-20(-70)LSR, Xiameter® RBL 2004-20(-75)LSR, Silastic® NPC 9300-40 / -50 / -70LSR, Silastic® LTC 9400-40 / -50LSR, and Silastic® 3D 3335LSR, all of which are available from Dow Silicones Corporation (Midland, Michigan). Other hydrosilylation-curable silicone compositions that may be utilized in the processes herein include moldable silicones such as those described in U.S. Pat. Nos. 8,691,910 (B2), 8,853,332 (B2), and 8,859,693 (B2).

[0090] The components of the hydrosilylation curable silicone rubber composition used herein can be mixed homogeneously using any suitable mixing means, such as a kneader mixer, a static mixer in a liquid injection molding machine, a Z-blade mixer, a two-roll mill (open mill), a three-roll mill, a Haake (trademark) Rheomix OS Lab mixer, a screw extruder, or a twin-screw extruder. Alternatively, a speed mixer, such as DC150.1FV, DAC400FVZ, or DAC600FVZ, sold by Hauschild, can be used.

[0091] The hydrosilylation-curable silicone rubber composition is applied on the surface of the inorganic substrate in step (c) after the inorganic substrate material is coated with the adhesion mediator composition in step (b). The hydrosilylation-curable silicone rubber composition can be applied by any suitable means, such as rolling, spreading, 3D printing, etc. Thus, the hydrosilylation-curable silicone rubber composition used in the process described herein can be applied and cured on the treated inorganic substrate by any suitable route, for example, by injection molding, press molding, extrusion molding, transfer molding, press vulcanization, or calendaring, for example, using a 2K injection mold. In one embodiment, the composite is prepared by injection molding using a two-part injection molding unit. The aforementioned hydrosilylation-curable silicone rubber composition can be applied on the surface of the inorganic substrate after the inorganic substrate material is coated with the adhesion mediator composition.

[0092] In the case of using a 3D printing method, a typical method of forming a three-dimensional (3-D) article may include multiple steps. For example, after the adhesion mediator composition is applied onto the inorganic substrate surface, the method may include (i) printing a first hydrosilylation-curable silicone rubber composition with a 3D printer to form a layer on the treated inorganic substrate. The method may further include (ii) heating the layer to form an at least partially cured layer. The method may also include (iii) printing a second heat-curable silicone composition with a 3D printer onto the at least partially cured layer to form a subsequent layer. The method may further include (iv) heating the subsequent layer to form an at least partially cured subsequent layer. Optionally, steps iii) and iv) may be repeated to form a 3D composite article using independently selected hydrosilylation-curable silicone rubber compositions for any additional layers. If desired, the inorganic substrate may be cleaned and / or activated or partially activated (e.g., a portion of the inorganic substrate surface is masked such that only the unmasked areas are activated) prior to step (i).

[0093] In one embodiment of the process defined above, step (c) of the process may be carried out by 3D printing the hydrosilylation curable silicone rubber composition onto an inorganic substrate surface, such as an inorganic substrate surface, that has been pretreated with the adhesion mediator composition described herein. In such a case, steps (c) and (d) may be as follows: printing the first hydrosilylation-curable silicone rubber composition described herein above with a 3D printer to form a layer on the inorganic material that has been treated with the adhesion mediator composition obtained from steps (a) and (b) and that has been optionally cleaned and / or activated; i. heating the layer to form an at least partially cured layer; ii. printing a second hydrosilylation-curable silicone rubber composition onto the at least partially cured layer with a 3D printer to form a subsequent layer; iii. heating the subsequent layer to form an at least partially cured subsequent layer; and iv. Optionally, steps iii) and iv) are repeated using independently selected thermosetting silicone compositions for any additional layers to form a 3-D article.

[0094] Process (d) Finally, in step (d), the hydrosilylation curable silicone rubber composition is cured at a temperature of from 80°C to 190°C, alternatively from 100°C to 180°C, alternatively from 100°C to 170°C, alternatively from 110°C to 170°C, alternatively from 110°C to 160°C.

[0095] The curing of the hydrosilylation-curable silicone rubber composition on the inorganic substrate can be carried out in any suitable manner, which may depend on the manner in which the hydrosilylation-curable silicone rubber composition is applied in step (c). For example, the curing can be carried out in a mold to form a molded composite part with the silicone elastomer resulting from the curing process adhering to the inorganic substrate. In the case of this inorganic substrate, the hydrosilylation-curable silicone rubber composition used herein can be, for example, injection molded to form an article adhering to the inorganic substrate after coating the inorganic substrate with the adhesion mediator composition, or the composition can be overmolded by injection molding around or onto such an inorganic substrate or article after coating the inorganic substrate with the adhesion mediator composition.

[0096] When cured in the presence of a heat-sensitive inorganic substrate, the hydrosilylation-curable silicone rubber compositions described herein above may be cured under conditions that allow for the development of mechanical adhesion with the heat-sensitive substrate, and more specifically, by using temperatures and cure times that do not distort, melt, or denature the heat-sensitive inorganic substrate.

[0097] Also provided is an article or composite part of an article obtained or obtainable from the above method.

[0098] In one embodiment herein, there is provided an article or composite part comprised of a silicone elastomer cured from a hydrosilylation-curable silicone rubber composition on a rigid or flexible inorganic substrate such as the types described above, provided that the rigid or flexible substrate has been coated with a layer of an adhesion mediator composition in step (b) of the process prior to application of the hydrosilylation-curable silicone rubber composition in step (c) of the process.

[0099] Examples of such articles or composite parts can be found in various industries, including, but not limited to, automotive applications, industrial applications, electronic applications, and consumer applications such as packaging, storage, processing, production, preparation, processing, consumption, and molding of food and beverage products for human consumption, provided that they meet the necessary regulations such as food contact, dishwasher compatibility, or beverage / fluid compliance (e.g., contact with hot water, coffee, tea in machines). In automotive applications, this can include housings with silicone seals or gaskets, plugs and connectors, components of various sensors, membranes, diaphragms, climate ventilation components, etc. Electronic applications can include cell phone cover seals, cell phone accessories, precision electronics, electrical switches and switch covers, watches and wristbands, wearable appliances such as face masks, wearable electronic devices, etc.

[0100] Composite parts may also be selected from parts of mobile phones, mobile communication devices, game consoles, watches, image receivers, DVD devices, MD (mini disc) devices, CD devices, and other precision electronic equipment, televisions, LCD televisions and plasma televisions flat screen displays, various home appliances, copiers, printers, facsimile machines, and other office equipment, connector seals, spark plug caps, components of various sensors, and other automotive components.

[0101] Composite articles and / or parts comprising or consisting of silicone rubber and inorganic materials used in the transport, packaging, storage, treatment, production, preparation, processing, consumption, and molding of household products and / or food and beverage products for human consumption may include parts of machines for producing, preparing, molding, and processing food, baking equipment such as baking molds, kitchen appliances, and / or food and beverage processing equipment such as drink makers, kettles, cutlery, pottery, ceramic ware, beverage containers including baby bottles, other types of containers, trays, food molds, and parts of ovens, including microwave ovens, refrigerators, bread makers, rice cookers, and / or dishwashers, as well as containers used in the transport and materials that come into contact with water intended for human consumption, etc. EXAMPLES

[0102] In the following examples, unless otherwise indicated, all viscosities were measured using a Brookfield™ rotational viscometer equipped with spindle RV-4 for viscosities below 10,000 mPa·s, at 25° C. and in each case at a speed of 20 rpm.

[0103] Each cleaned and / or activated substrate was coated with a layer of the adhesion mediator composition described herein above or the comparative coating composition shown in the respective table using a pipette to apply the adhesion mediator composition or the comparative coating composition shown in the respective table and then wipe the composition over the surface of the substrate to provide a continuous layer of the composition on the substrate. The adhesion mediator (composition of Example 1-1) coated substrate was then coated with a 2-3 mm layer of liquid silicone rubber (LSR) and cured at 120° C. for 15 minutes.

[0104] Several examples of adhesion mediators that can be utilized herein have been prepared and their compositions are disclosed below in Tables 1a and 1b.

[0105] [Table 1]

[0106] Polymer 1 was a vinyldimethyl-terminated polydimethylsiloxane with a viscosity of approximately 450 mPa·s at 25°C and a vinyl content of 0.46 wt % vinyl (Vi) content.

[0107] The Karstedt catalyst is provided in the Polymer 1 masterbatch.

[0108] [Table 2]

[0109] In Table 1b, in Examples 1-7 and 1-8, Polymer 2 was a 1:1 (by weight) mixture of two vinyldimethyl-terminated polydimethylsiloxanes having viscosities of approximately 450 and 2000 mPa s, respectively, at 25 °C, with an average vinyl content of 0.34 wt% vinyl (Vi). The viscosity of the mixture was 1190 mPa s. Polymer 3 was a 1:1 mixture of two vinyldimethyl-terminated polydimethylsiloxanes having viscosities of approximately 450 and 9000 mPa s, respectively, at 25 °C, with an average vinyl content of 0.28 wt% Vi. ​​The viscosity of the mixture was 2440 mPa s. When Polymer 2 replaced Polymer 1, the Karstedt catalyst was provided in the Polymer 2 masterbatch; similarly, when Polymer 3 replaced Polymer 1, the Karstedt catalyst was provided in the Polymer 3 masterbatch.

[0110] Working Example In the examples, the adhesion mediators described in Examples 1-9 in Table 1b were utilized to evaluate their ability to aid adhesion of LSR1 (Silastic™ 3D 3335 LSR) to a range of inorganic substrates. Silastic™ 3D 3335 LSR is commercially available from Dow Silicones Corporation (Midland, Michigan, USA).

[0111] The substrates used were several commercially available test panels purchased from Rocholl GmbH (Eschelbronn, Germany).

[0112] The test plate substrate used was glass (60 × 25 × 4 mm) including its dimensions. 3 );6061 T6 alloy aluminum (60×25×2mm 3 );SF-Cu F24 copper (60×25×1mm 3 );DX51 D+Z275 high temperature plated steel (60×25×1mm 3 ), and DC04 steel (60 x 25 x 1 mm 3 ) was.

[0113] First, various inorganic substrates were cleaned with isopropanol, which typically evaporated quickly, but the substrates were left at room temperature for approximately 10 minutes to dry before use.

[0114] Two test plates of each substrate were then utilized. The first of each test plate was coated with a layer of adhesion mediator composition (the composition of Example 2-1) using a pipette and then the composition was wiped onto the surface of the substrate to provide a continuous layer thereon. Each of the second test plates was not coated with adhesion mediator. Both the first and second test plates were then coated with a 2-3 mm layer of LSR, which was then cured at 120° C. for 15 minutes to form a test plate composite. The resulting test plate composite was stored for at least 24 hours before testing for adhesion. Each composite test plate was qualitatively tested by attempting to pull the LSR away from the test plate by hand.

[0115] [Table 3]

[0116] In all cases where an adhesion mediator was applied to the surface of the test plate, the silicone rubber layer did not separate from the test plate (referred to as "good" in Table 2), whereas in all cases where silicone rubber was applied to the surface of the test plate without pretreatment with an adhesion mediator, the adhesion was "poor," that is, the silicone rubber layer easily peeled off from the surface of the test plate.

Claims

1. A method for preparing a composite material of a silicone elastomer and an inorganic substrate, (a) Optionally, a step of cleaning and / or activating the surface of an inorganic substrate, (b) A step of treating the optionally cleaned and / or activated inorganic substrate surface with an adhesion mediating substance composition, (c) A step of applying the hydrosilylated curable silicone rubber composition onto the treated surface obtained in step (b), (d) A step of curing the hydrosilylated curable silicone rubber composition, Includes, The aforementioned adhesion mediating substance composition (i) Formula Si(OR) ３ R １ (In the formula, each R may be the same or different, and each R is an alkyl group having at least two carbon atoms per group, １ The trialkoxysilane is an unsaturated group selected from an alkenyl group or an alkynyl group, which may be the same or different, and is present in an amount of 20 to 45% by weight of the adhesion mediating material composition, (ii) A platinum group metal hydrosilylation reaction catalyst comprising a platinum group metal present in an amount of 0.1 to 1.5% by weight of the adhesion mediating material composition, (i) an amount of 1 to 10% by weight of the adhesion mediating material composition, an alkoxy titanium compound having 2 to 4 alkoxy groups, (ii) Formula Si(OR ２ ) ４ (In the formula, each R ２ A tetraalkoxysilane (which may be the same or different, and is an alkyl group having at least two carbon atoms per group), in an amount of 5 to 20% by weight of the adhesion mediating material composition, (iii) (a') A polyorganosiloxane containing at least two unsaturated groups selected from alkenyl groups and alkynyl groups per molecule, having a viscosity in the range of 50 mPa·s to 9000 mPa·s at 20 rpm at 25°C using a Brookfield™ viscometer equipped with an RV-4 spindle, or (b') A mixture of two or more polyorganosiloxanes, each containing at least two unsaturated groups selected from alkenyl groups and alkynyl groups, wherein the mixture has a viscosity in the range of 50 mPa·s to 9000 mPa·s at 20 rpm at 25°C, measured using a Brookfield™ viscometer equipped with an RV-4 spindle. One of the following: Component (v), which is either the polyorganosiloxane or the mixture thereof, present in an amount of 25 to 60% by weight of the adhesion mediating material composition, A method characterized by including

2. A method for preparing a composite material of a silicone elastomer and an inorganic substrate according to claim 1, wherein the surface of the inorganic substrate is cleaned and / or activated by one of the following: plasma treatment, corona discharge treatment, UV-C / ozone or vacuum-UV irradiation, flame thermal analysis of amorphous silicon dioxide, or flame treatment.

3. A method for preparing a composite material of a silicone elastomer and an inorganic substrate according to claim 1, wherein step (c) and / or (d) includes injection molding or 3D printing.

4. A method for preparing a composite material of a silicone elastomer and an inorganic substrate according to claim 1, 2, or 3, where the inorganic substrate is selected from metals, metal alloys, glass, or ceramic materials.

5. Component (i) of the adhesive medium composition is of the formula Si(OR) ３ R １ (wherein each R may be the same or different and is selected from ethyl, propyl, n-butyl, isobutyl, or t-butyl, and each R １ is an alkenyl group which may be the same or different and is selected from vinyl, propenyl, n-butenyl, pentenyl, or hexenyl), a method for preparing a composite material of a silicone elastomer and an inorganic substrate according to claim 1, 2, or 3.

6. A method for preparing a composite material of a silicone elastomer and an inorganic substrate according to claim 1, 2, or 3, wherein component (ii) of the adhesion mediating substance composition is one or more coordination compounds of platinum.

7. Component (iii) is given by formula Ti(OR ３ ) ４ , Ti(OR ３ ) ３ R ４ , Ti(OR ３ ) ２ R ４ ２ One or more alkoxytitanium compounds or chelated alkoxytitanium molecules, where R ３ is a linear or branched alkyl group having 1 to 20 carbon atoms, and if present, R ４ A method for preparing a composite material of a silicone elastomer and an inorganic substrate according to claim 1, wherein the organic group is, for example, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aromatic group having 6 to 20 carbon atoms, or a mixture thereof.

8. Component (iii) is structure Ti(OR ３ ) ４ , Ti(OR ３ ) ３ R ４ , Ti(OR ３ ) ２ R ４ ２ (In the formula, each R ３ A method for preparing a composite material of a silicone elastomer and an inorganic substrate according to claim 7, wherein component (iii) is selected from titanates of isobutyl groups, tertiary butyl groups, or n-butyl groups, or component (iii) is an enolate of a titanic acid ester and an acetoacetic acid ester.

9. Component (iv) is of formula Si(OR ２ ) ４ (In the formula, each R ２ A method for preparing a composite material of a silicone elastomer and an inorganic substrate according to claim 1, 2, or 3, wherein is a tetraalkoxysilane (selected from ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, or hexyl).

10. A method for preparing a composite material of a silicone elastomer and an inorganic substrate according to claim 1, 2, or 3, wherein the hydrosilylated curable silicone rubber composition is applied in step (c) before the layered adhesive mediating substance applied in step (b) hardens or solidifies.

11. A composite article or component obtained or obtainable from the method described in claim 1.

12. The composite article or component according to claim 11, which contains a maximum of 50 mg of platinum per kilogram.

13. The composite article or component according to claim 11 or 12, wherein the silicone elastomer and inorganic composite material are used in the transport, packaging, storage, processing, production, preparation, processing, and consumption applications of household products and / or food and beverage products for human consumption and / or in the molding thereof.

14. A method for preparing a composite material of a silicone elastomer and an inorganic substrate according to Claim 1, wherein the adhesive mediating material composition is: (i) Formula Si(OR) ３ R １ (In the formula, each R may be the same or different, and each R is an alkyl group having at least two carbon atoms per group, １ The trialkoxysilane is an unsaturated group selected from an alkenyl group or an alkynyl group, which may be the same or different, and is present in an amount of 20 to 45% by weight of the adhesion mediating material composition, (ii) A platinum group metal hydrosilylation reaction catalyst comprising a platinum group metal present in an amount of 0.1 to 1.5% by weight of the adhesion mediating material composition, (iii) an alkoxy titanium compound having 2 to 4 alkoxy groups in an amount of 1 to 10% by weight of the adhesion mediating material composition, (iv) Formula Si(OR ２ ) ４ (In the formula, each R ２ A tetraalkoxysilane (which may be the same or different, and is an alkyl group having at least two carbon atoms per group), in an amount of 5 to 20% by weight of the adhesion mediating material composition, (v) (a') A polyorganosiloxane containing at least two unsaturated groups selected from alkenyl groups and alkynyl groups per molecule, having a viscosity in the range of 50 mPa·s to 9000 mPa·s at 20 rpm at 25°C using a Brookfield™ viscometer equipped with an RV-4 spindle, or (b') A mixture of two or more polyorganosiloxanes, each containing at least two unsaturated groups selected from alkenyl groups and alkynyl groups, wherein the mixture has a viscosity in the range of 50 mPa·s to 9000 mPa·s at 20 rpm at 25°C, measured using a Brookfield™ viscometer equipped with an RV-4 spindle. One of the following: The use comprises component (v), which is either the polyorganosiloxane or the mixture thereof, present in an amount of 25 to 60% by weight of the adhesion mediating material composition.

15. The use according to claim 14, wherein the silicone elastomer and inorganic composite are used in the transport, packaging, storage, processing, production, preparation, modification, consumption, and molding of household products and / or food and beverage products for human consumption.