Inflatable safety device

Abstract

This disclosure describes inflatable articles, such as airbags for inflatable safety devices for vehicle occupant protection systems, processes for making the inflatable articles, hydrosilylation-curable silicone elastomer compositions, and their use in assembling the inflatable safety devices. The compositions used included organopolysiloxane additives containing at least one, or at least two, Si-H groups per molecule and at least one, or at least two, functional groups per molecule selected from anhydride and epoxy groups.

Description

[Technical Field]

[0001] The present disclosure describes inflatable articles such as airbags for inflatable safety devices in vehicle passenger protection systems, processes for manufacturing said inflatable articles, hydrosilylation-curable silicone elastomer compositions, and uses thereof in assembling said inflatable safety devices. [Background Art]

[0002] Inflatable safety device systems are used by the automotive industry to protect vehicle occupants by reducing damage in the event of an accident. Such inflatable safety device systems typically comprise a sensor, an inflator, and an inflatable article, for example an airbag that provides soft cushioning and restraint to vehicle occupants during a collision event. In the event of an accident, sensors are arranged to deploy a cushion between the occupant and potentially harmful surfaces within the vehicle, thereby activating the inflator to fill the airbag with gas.

[0003] All of these operations must occur within milliseconds after an accident to effectively protect the occupant. Airbags provide an energy-absorbing surface between the vehicle occupant and the steering wheel, instrument panel, body pillars, headliner, and windshield. Modern vehicles can contain up to ten airbag modules in various configurations, including driver, passenger, side curtain, seat-mounted, door-mounted, B and C pillar-mounted side impact, knee booster, inflatable seat belt, and pedestrian airbag modules.

[0004] In some applications of inflatable articles, such as airbags, pressurized gas needs to be retained within a fabric envelope for a relatively long period. This requirement exists, for example, with regard to side curtain airbags for the automotive industry. These side curtain airbags are intended to inflate upon impact, similar to conventional airbags. They expand to form a cushioned curtain, such as a window, between the passenger and a portion of the vehicle's side. This intention is not only to cushion the blow-on impact itself, as in the case of conventional driver and passenger airbags, but also to protect the passenger. For example, when a vehicle is rolling, it is important that the side curtain airbag is sufficiently pressurized during such a rolling process. While conventional driver and passenger airbags only need to maintain pressure for a brief moment, side curtain airbags need to maintain a suitable pressure for several seconds. Therefore, the latter are usually treated with a coating of elastomer to reduce or prevent airbag deflation. Similar applications exist where a pressurized fabric structure is desired to maintain a specific gas pressure for a relatively long period, for example, in an emergency chute for aerosols or inflatable rafts.

[0005] Other applications for inflatable articles do not necessarily require such coatings, and if they are simply designed to hold pressure for only a brief moment upon impact, for example, these may be referred to as untreated inflatable articles.

[0006] Historically, airbags are often made from two main fabric sheets, connected to each other at their periphery using airtight stitching, although an increasing number of alternatives are also used. The fabric sheets are often formed from woven or knitted fabrics made from synthetic fibers, such as polyamides like nylon 6,6 or polyester, and can be coated with an elastomer coating, depending on the intended use, to form the airbag. When the airbag inflates, one of the main fabric sheets is directed toward one or more of the passengers to be protected. The other sheet supports itself in the inflated state of the airbag device, for example, on one or more transverse windows and / or transverse vehicle structures. The fabric sheets of a typical airbag are sewn together to provide sufficient mechanical strength, for example, by joining the first and second panels together with silicone adhesive applied to the periphery of the panels, and then sewing the panels together with one or more seams of sewing thread or yarn. The seams are sewn through silicone adhesive to provide sufficient gas impermeability and / or pressure retention when the airbag is deployed. These characteristics result in a relatively time-consuming and expensive process for assembling airbags, requiring multiple steps to seal and sew the seams.

[0007] However, in airbags constructed using suture stitches to provide structural integrity of the seams, the suture stitches create holes or gaps in the fabric panels of the airbag cushion from the suture needles, reducing the localized strength of the airbag panels against the seams. Because stitching creates holes or gaps in the airbag panels for each passage of thread or yarn, the degradation of panel strength occurs locally against the seams when stitching is applied. Thus, each introduced needle hole creates a vulnerability in the airbag fabric, which may tear under the high temperature and high stress caused when the airbag is released from impact and storage, resulting in a failure to cushion the occupants as intended. This is a concern for airbags that are pre-coated and intended to be inflated for extended periods. [Overview of the initiative]

[0008] This specification refers to an inflatable article, A first cloth sheet and a second cloth sheet placed on top of it, A curing silicone adhesive comprising a curing silicone adhesive that forms a non-suture seam bond between a first fabric sheet and a second fabric sheet so as to create a bag-like structure, wherein the non-suture seam bond has a peak load / width of at least 3.5 kN / m, and the curing silicone adhesive is (A) One or more organopolysiloxanes containing at least two alkenyl groups and / or alkynyl groups per molecule and having a viscosity in the range of 1,000 mPa·s to 500,000 mPa·s at 25°C, (B) A hardening agent, (B)(i) Organic peroxide radical initiator, (B)(ii) Hydrosilylation curing catalyst package, a. Organosilicon compounds having at least two or at least three Si-H groups per molecule, and b. A curing agent comprising a hydrosilylation catalyst package containing a hydrosilylation catalyst, (C) at least one reinforcing filler and optionally one or more non-reinforcing fillers, (D) Provided is an expandable article which is an elastomer product of a curable silicone elastomer composition, comprising one or more organopolysiloxane additives, each containing at least one or at least two Si-H groups per molecule, and at least one or at least two functional groups per molecule selected from anhydride groups and epoxy groups.

[0009] Furthermore, a process for producing an expandable article, (i) Applying the first beads of the curable silicone elastomer composition described herein to the periphery of the first cloth sheet, (ii) Bringing the first beads of the curable silicone elastomer composition into contact with the surface of the second cloth sheet, (iii) A process is also provided which includes forming a non-suture seam comprising a curable silicone elastomer product of a curable silicone elastomer composition, thereby bonding a first fabric sheet to the fabric sheet through the non-suture seam, wherein the resulting non-suture seam bond has a peak load / width of at least 3.5 kN / m.

[0010] Furthermore, a process for producing an expandable article, (i) Applying the first beads of the curable silicone elastomer composition described herein to the periphery of the first cloth sheet, (ii) Applying the second beads of the curable silicone elastomer composition around the periphery of the second cloth sheet, as described above, (iii) To bring the first exposed surface of the first bead and the second exposed surface of the second bead into contact to form a single bead, (iv) A process is also provided which includes forming a non-suture seam comprising a curable silicone elastomer product of a curable silicone elastomer composition, thereby bonding a first fabric sheet to a second fabric sheet through the non-suture seam, wherein the resulting non-suture seam bond has a peak load / width of at least 3.5 kN / m.

[0011] Furthermore, the use of the above-described curable silicone elastomer composition as a seam sealant for expandable articles is also provided.

[0012] To avoid misunderstanding, the peak load / width values ​​described herein are determined by using the methods described in the examples herein.

[0013] Each fabric sheet is preferably a woven fabric, particularly a plain weave, but may be, for example, knitted or nonwoven. The fabric may be made from synthetic fibers or blends of natural and synthetic fibers, such as polyamide fibers such as nylon-6,6, polyester, polyimide, polyethylene, polypropylene, polyester cotton, or glass fibers. For use as an inflatable article, for example, airbag fabric can be folded into a relatively small volume, but is also strong enough to withstand high-speed deployment, for example, under the influence of explosive loading. As will be discussed below, the fabric may be treated with an elastomer coating to prevent or reduce shrinkage after inflation if inflation is required for a long period of time, or it may be left untreated in “impact” applications where the inflatable article is designed to inflate in the event of an impact of less than one second, for example.

[0014] This specification provides a detailed description of silicone adhesive compositions.

[0015] Each of the one or more organopolysiloxanes (A) contains at least two alkenyl groups and / or alkynyl groups, typically alkenyl groups bonded to a silicon atom per molecule, and has a viscosity of 1,000 mPa·s to 500,000 mPa·s at 25°C, or 1,000 mPa·s to 200,000 mPa·s at 25°C, or 1,000 mPa·s to 150,000 mPa·s at 25°C, or 1,000 mPa·s to 75,000 mPa·s at 25°C, using a Brookfield® rotational viscometer with a spindle (LV-4) and a rate (shear rate) adjusted according to the polymer viscosity. Unless otherwise specified, all viscosity measurements were taken at 25°C.

[0016] Examples of alkenyl groups include vinyl, allyl, butenyl, pentenyl, cyclohexenyl, and hexenyl groups. These groups may be in the pendant portion, the terminal portion, or both; that is, such groups may be present in any of the siloxy units of organopolysiloxane (A). Component (A) comprises linear and / or branched organopolysiloxanes containing multiple units of formula (1). R' a SiO 4-a / 2 (1) In the formula, each R' may be the same or different, and represents a hydrocarbon group having 1 to 18 carbon atoms, a substituted hydrocarbon group having 1 to 18 carbon atoms, or a hydrocarbon oxy group having up to 18 carbon atoms, and has an average a value of 1 to 3, preferably 1.8 to 2.2.

[0017] For the purposes of this application, "substitution" means that one or more hydrogen atoms in a hydrocarbon group are substituted by another substituent. Examples of such substituents include, but are not limited to, halogen atoms such as chlorine, fluorine, bromine, and iodine; halogen atom-containing groups such as chloromethyl, perfluorobutyl, trifluoroethyl, trifluoropropyl, and nonafluorohexyl groups; oxygen atoms; oxygen atom-containing groups such as (meth)acrylic and carboxyl groups; nitrogen atoms; nitrogen atom-containing groups such as amino, amide, and cyano functional groups; sulfur atoms; and sulfur atom-containing groups such as mercapto groups.

[0018] Unless otherwise specified, siloxy units may be written in abbreviation, i.e., "M", "D", "T", and "Q", when R is usually an alkyl group, such as a methyl group (further instruction on silicone nomenclature can be found in Walter Noll, Chemistry and Technology of Silicones, dated 1962, Chapter I, pages 1-9). The M unit is a siloxy unit in the formula where a=3, i.e., R3SiO 1 / 2This corresponds to the D unit, which is the siloxy unit where a=2 in the formula, i.e., R2SiO 2 / 2 This corresponds to the T unit, which is the siloxy unit where a=1 in the formula, i.e., R1SiO 3 / 2 This corresponds to the siloxy unit where a=0 in the formula, i.e., SiO 4 / 2 It corresponds to this.

[0019] An example of starting material (A) is a polydiorganosiloxane containing alkenyl or alkynyl groups at two terminal ends, but is typically an alkenyl group-containing polydiorganosiloxane, which can be represented by general formula (I): R'R''R'''SiO-(R''R'''SiO) m -SiOR'''R''R' (I)

[0020] In formula (I), each R' is an alkenyl group or alkynyl group, typically an alkenyl group containing 2 to 10 carbon atoms, such as vinyl, allyl, and 5-hexenyl.

[0021] R'' does not contain ethylenically unsaturated groups. Each R'' may be the same or different and is individually selected from monovalent saturated hydrocarbon groups generally containing 1 to 10 carbon atoms and monovalent aromatic hydrocarbon groups generally containing 6 to 12 carbon atoms. R'' may be unsubstituted or may be substituted with one or more groups (such as halogen atoms) that do not hinder the curing of the composition of the present invention. R'''' is R' or R', where m represents a suitable degree of polymerization for the raw material (A) and has a viscosity within the range discussed below.

[0022] Typically, all R'' and R''' groups in a compound according to formula (I) are methyl groups. Alternatively, at least one R'' and / or R''' group in a compound according to formula (I) is a methyl group, and the others are phenyl groups or 3,3,3-trifluoropropyl groups. This preference is based on the availability of reactants typically used to prepare polydiorganosiloxanes (starting material (A)) and the desired properties of cured elastomers prepared from compositions containing such polydiorganosiloxanes.

[0023] Particularly preferred examples of group R' include methyl, ethyl, propyl, butyl, cyclohexyl, phenyl, tolyl, chlorine, or fluorine-substituted propyl groups, such as 3,3,3-trifluoropropyl, chlorophenyl, β-(perfluorobutyl)ethyl, or chlorocyclohexyl. Preferably, at least some, more preferably substantially all, of the R'' groups are methyl. Some R' groups may be phenyl or fluoro groups. In one alternative example, the polydiorganosiloxane is primarily a polydialkylsiloxane and / or polydialkylalkylphenylsiloxane having at least two alkenyl groups in one molecule. In a further alternative example, the polydiorganosiloxane is primarily a polydimethylsiloxane having at least two alkenyl groups in one molecule. They are preferably of the formula R''3SiO 1 / 2 It is a substantially linear material with its ends sealed by siloxane groups.

[0024] In the formula, each R'' is either the same or different. It is understood that the curing rate and physical properties of the curable composition are influenced by the structure and degree of functionality of component (A). For example, in some embodiments, it may be advantageous to use branched, resinous, or cyclic-containing organopolysiloxanes having pendant alkenyl or alkynyl groups as part or all of component (A).

[0025] The viscosity of organopolysiloxane (A) at 25°C was typically obtained using a Brookfield® system with a spindle (LV-4) and the rate (shear rate) adjusted according to the polymer viscosity. All viscosity measurements were obtained at 25°C unless otherwise specified.

[0026] Examples of organopolysiloxanes (A) that may be used include vinyldimethylsiloxy-terminated dimethylsiloxane-vinylmethylsiloxane copolymer, vinyldimethylsiloxy-terminated polydimethylsiloxane, vinylmethylhydroxysiloxy-terminated dimethylsiloxane-vinylmethylsiloxane copolymer, and mixtures thereof.

[0027] The organopolysiloxane (A) may be a single polymer or a combination of two or more different polymers.

[0028] Organopolysiloxane (A) is present in the composition at a concentration of 10-85% by weight of the total weight of the composition, or 20-80% by weight of the total weight of the composition, or 20-75% by weight of the total weight of the composition, or 30-65% by weight of the total weight of the composition.

[0029] B) Hardener The compositions described herein may be cured with an organic peroxide radical initiator (B)(i) or a mixture of different types of peroxide catalysts.

[0030] The peroxide radical initiator (B)(i) may be any well-known commercial peroxide used to cure silicone and / or fluorosilicone elastomer compositions. The amount of organic peroxide used is determined by the nature of the curing process, the organic peroxide used, and the composition used. Typically, the amount of peroxide radical initiator (B)(i) used in the compositions described herein is in any case 0.2 to 3% by weight, or 0.2 to 2% by weight, based on the weight of the composition.

[0031] Suitable organic peroxides are substituted or unsubstituted dialkyl-, alkylaloyl-, and dialoyl-peroxides, such as benzoyl peroxide and 2,4-dichlorobenzoyl peroxide, ditert-butyl peroxide, dicumyl peroxide, lauroyl peroxide, t-butylcumyl peroxide, bis(t-butylperoxyisopropyl)benzene, cyclohexanone peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, bis(t-butylperoxy)-2,5-dimethylhexine, 2,4-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butyl peroxide, and 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane.

[0032] Alternatively, the composition is (B)(ii)(a)Organosilicon compounds having at least two or at least three Si-H groups per molecule, and (B)(ii)(b) Hydrosilylation catalyst can be cured using a hydrosilylation catalyst package (B)(ii) in the form of a hydrosilylation catalyst.

[0033] Component (B)(ii)(a) is a crosslinking agent in the form of an organosilicon compound containing at least two or three silicon-bonded hydrogen atoms per molecule. Typically, component (B)(ii)(a) contains three or more silicon-bonded hydrogen atoms, thereby curing the composition by reacting with unsaturated alkenyl or alkynyl groups in polymer (A) to form a network structure with them. Alternatively, if polymer (A) has more than two (>) alkenyl or alkynyl groups per molecule, some or all of component (B)(ii)(a) may have two silicon-bonded hydrogen atoms per molecule.

[0034] The structure of the organosilicon compound may be linear, branched, cyclic, or resinous. Cyclosilanes and cyclosiloxanes may have 3 to 12 silicon atoms, alternatively 3 to 10 silicon atoms, alternatively 3 to 4 silicon atoms. In acyclic polysilanes and polysiloxanes, silicon-bonded hydrogen atoms may be located at terminal positions, pendant positions, or both terminal and pendant positions.

[0035] Examples of suitable organosilanes include diphenylsilane, 2-chloroethylsilane, bis[(p-dimethylsilyl)phenyl] ether, 1,4-dimethyldisilylethane, 1,3,5-tris(dimethylsilyl)benzene, 1,3,5-trimethyl-1,3,5-trisilane, poly(methylsilylene)phenylene, and poly(methylsilylene)methylene. In some examples, the organohydrogensilane has the formula HR 1 2Si-R 2 -SiR 1 2H, wherein R 1 is C1~C 10 hydrocarbyl or C1~C 10 halogen-substituted hydrocarbyl, both of which do not contain aliphatic unsaturation, and R 2 is a hydrocarbylene group free of aliphatic unsaturation having a formula selected from 1,4- or 1,3-disubstituted phenyl, 4,4'- or 3,3'-disubstituted-1,1'-biphenyl, or para- or meta-disubstituted Ph(C g H 2g )Ph.

[0036] The molecular structure of organopolysiloxane (B)(ii)(a) containing at least 2 or 3 silicon-bonded hydrogen atoms per molecule is not particularly limited, and may be linear, linear with some branches, cyclic, or a silicone resin system. The molecular weight of this component is not particularly limited, but to obtain good miscibility with polymer (A), the viscosity is typically from 0.001 to 50 Pa·s at 25°C when measured using the cup / spindle method of ASTM D1084 Method B with a Brookfield® RV or LV spindle that is most appropriate for the viscosity range.

[0037] Examples of silicon-bonded organic groups used in component (B)(ii)(a) include alkyl groups such as methyl, ethyl, propyl, butenyl, pentenyl, and hexyl; aryl groups such as phenyl, tolyl, and xylyl; and halogenated alkyl groups such as 3-chloropropyl and 3,3,3-trifluoropropyl, with methyl and phenyl groups being preferred.

[0038] Organopolysiloxane (B)(ii)(a), containing at least two or three silicon-bonded hydrogen atoms per molecule, is typically added in an amount such that the molar ratio of the total number of silicon-bonded hydrogen atoms in component (B)(ii)(a) to the total number of alkenyl / alkynyl groups in polymer (A) is between 0.5:1 and 20:1. If this ratio is less than 0.5:1, a sufficiently cured composition cannot be obtained. If this ratio is greater than 20:1, the hardness of the cured composition tends to increase when heated.

[0039] Examples of organopolysiloxanes (B)(ii)(a) containing at least two or three silicon-bonded hydrogen atoms per molecule include, but are not limited to, the following: (a') Trimethylsiloxy-terminated methylhydrogenpolysiloxane, (b') Trimethylsiloxy-terminated polydimethylsiloxane-methylhydrogensiloxane, (c') Dimethylhydrogensiloxy-terminated dimethylsiloxane-methylhydrogensiloxane copolymer, (d') Dimethylsiloxane-methylhydrogensiloxane cyclic copolymer, (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')(CH3)2HSiO 1 / 2 Unit, SiO 4 / 2 Units and (C6H5)3SiO 1 / 2 Copolymers and / or silicone resins comprising units, and substitutes thereof in which methyl groups are substituted with phenyl groups or other alkyl groups.

[0040] Alternatively, the crosslinking agent of component (B)(ii)(a) may be a filler such as silica treated with one of the above.

[0041] Component (B)(ii)(a) can be exemplified by the following compounds: methylhydrogenpolysiloxane with trimethylsiloxy groups occupying both ends of the molecular chain; copolymer of methylhydrogensiloxane and dimethylsiloxane with trimethylsiloxy groups occupying both ends of the molecular chain; dimethylsiloxane with dimethylhydrogensiloxy groups occupying both ends of the molecular chain; copolymer of methylhydrogensiloxane and dimethylsiloxane with dimethylhydrogensiloxy groups occupying both ends of the molecular chain; copolymer of methylhydrogensiloxane and methylphenylsiloxane with dimethylphenylsiloxy groups occupying both ends of the molecular chain; cyclic methylhydrogenpolysiloxane; (CH3)2HSiO 1 / 2 Siloxane 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 Copolymers consisting of units; organopolysiloxanes in which some or all of the methyl groups are substituted with alkyl groups such as ethyl or propyl; organopolysiloxanes substituted with aryl groups such as phenyl or tolyl; organopolysiloxanes substituted with halogenated alkyl groups such as 3,3,3-trifluoropropyl; or mixtures of two or more of the above organopolysiloxanes.

[0042] The organopolysiloxane crosslinking agent (B)(ii)(a) is generally present in the curable silicone elastomer composition in an amount such that the ratio of the number of moles of silicon-bonded hydrogen atoms of component (B)(ii)(a) to the number of moles of alkenyl groups of component (A) 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).

[0043] The content of silicon-bonded hydrogen (Si-H) in component (B)(ii)(a) is determined using quantitative infrared analysis in accordance with ASTM E168. In the present invention, the ratio of silicon-bonded hydrogen to alkenyl (vinyl) and / or alkynyl is important when it depends on the hydrosilylation curing 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, where the molar ratio of silicon-bonded hydrogen to vinyl is 27 [H] / [V], with the molecular weight of hydrogen being 1 and the molecular weight of vinyl being 27.

[0044] Typically, depending on the number of unsaturated groups in component (A) and the number of Si-H groups in component (B)(ii)(a), component (B)(ii)(a) may be present in amounts of 0.1 to 40% by weight of the total composition, or 0.5 to 20% by weight of the total composition, or 0.5 to 10% by weight of the total composition, or alternatively, 1% to 5% by weight of the total composition.

[0045] Component (B)(ii)(b) is at least one hydrosilylation (addition) reaction catalyst. These are typically selected from one or more catalysts of the platinum metal group (platinum, ruthenium, osmium, rhodium, iridium, and palladium). Platinum and rhodium are preferred due to the high activity levels of these catalysts in the hydrosilylation reaction. Component (B)(ii)(b) catalyzes the reaction between the alkenyl group (e.g., vinyl group) of component (A) and the Si-H group of component (B)(ii)(a), resulting in a crosslinked network when the curable silicone elastomer composition hardens into an elastomer.

[0046] The catalyst (B)(ii)(b) may be a platinum group metal, a platinum group metal deposited on a support such as activated carbon, a metal oxide such as aluminum oxide or silicon dioxide, silica gel or powdered carbon, or a compound or complex of a platinum group metal.

[0047] Examples of preferred hydrosilylation catalysts (B)(ii)(b) include, but are not limited to, platinum-based catalysts such as platinum black, platinum on various solid supports, chloroplatinic acid, alcoholic solutions of chloroplatinic acid, and complexes of chloroplatinic acid with ethylenically unsaturated compounds such as olefins and organosiloxanes containing ethylenically unsaturated hydrocarbon groups bonded to silicon. Examples of soluble platinum compounds that can be used include platinum-olefin complexes of the formula (PtCl2·(olefin)2 and H(PtCl3·olefin)), and in this context, the use of alkenes having 2 to 8 carbon atoms, such as isomers of ethylene, propylene, butene, and octene, or cycloalkanes having 5 to 7 carbon atoms, such as cyclopentene, cyclohexene, and cycloheptene, is preferred. Other soluble platinum catalysts include, for example, the platinum-cyclopropane complex of formula (PtCl2C3H6)2, the reaction products of hexachloroplatinic acid with alcohols, ethers, and aldehydes or mixtures thereof, or the reaction products of hexachloroplatinic acid with methylvinylcyclotetrasiloxane in the presence of sodium bicarbonate in an ethanol solution. Platinum catalysts having phosphorus, sulfur, and amine ligands can also be used, for example, as platinum complexes with vinylsiloxanes such as (Ph)3P)2PtCl2 and sym-divinyltetramethyldisiloxane.

[0048] Therefore, suitable specific examples of platinum-based catalysts include: (i) Complexes of chloroplatinic acid with organosiloxanes containing ethylenically unsaturated hydrocarbon groups, as described in U.S. Patent No. 3,419,593; (ii) Platinum chloride in either hexahydrate or anhydrous form; (iii) A platinum-containing catalyst obtained by a method comprising reacting chloroplatinic acid with an aliphatic unsaturated organosilicon compound such as divinyltetramethyldisiloxane; (iv) Alkene-platinum-silyl complexes described in U.S. Patent No. 6,605,734, such as (COD)Pt(SiMeCl2)2 (wherein "COD" is 1,5-cyclooctadiene); and / or (v) Karstedt catalysts are typically complexes of platinum and divinyltetramethyldisiloxane, containing about 1% by weight of platinum, and may be used as a solvent, for example, toluene. These are described in US3,715,334 and US3,814,730.

[0049] The hydrosilylation catalyst (B)(ii)(b) of the hydrosilylated curable silicone elastomer composition used is present in the total composition in a catalytic amount, i.e., a sufficient amount or quantity to catalyze the addition / hydrosilylation reaction and cure the composition into an elastomer material under the desired conditions. The reaction rate and curing reaction rate can be adjusted by using various levels of hydrosilylation catalyst (B)(ii)(b). The catalytic amount of hydrosilylation catalyst (B)(ii)(b) is generally 0.01 ppm to 10,000 ppm, or 0.01 to 5,000 ppm, or 0.01 to 3,000 ppm, or 0.01 to 1,000 ppm, based on the combined weight of the polymer (A) and filler (C) of the composition, in parts by weight (ppm) of platinum metal per million parts. In certain embodiments, the catalytic amount of the catalyst may be in the range of 0.01 to 1,000 ppm, 0.01 to 750 ppm, 0.01 to 500 ppm, or 0.01 to 100 ppm of metal, based on the weight of the composition. The range may relate only to the metal content in the catalyst or to the catalyst as a whole (including its ligands), as specified, but typically these ranges relate only to the metal content in the catalyst. The catalyst may be added as a single species or as a mixture of two or more different species. Typically, the amount of catalyst present is in the range of 0.001 to 3.0% by weight of the composition, depending on the form / concentration in which the catalyst package is provided.

[0050] Component (C) is one or more pulverized reinforcing fillers, optionally combined with one or more reinforcing fillers and / or non-reinforcing fillers.

[0051] The reinforcing filler of component (C) may be exemplified by pulverized fumed silica and / or pulverized precipitated silica, colloidal silica and / or a suitable silicone resin.

[0052] Settling silica fumed silica and / or colloidal silica are generally at least 50 m 2 They are particularly preferred due to their relatively high surface area, measured per g (BET method according to ISO 9277:2010). Generally, 50-450 m². 2 / g (BET method according to ISO9277:2010), or 50-300m 2 Use a filler with a surface area of ​​ / g (BET method according to ISO9277:2010). All of these types of silica are commercially available.

[0053] If the reinforcing filler (C) is originally hydrophilic (for example, an untreated silica filler), it is typically treated with a treatment agent to make it hydrophobic. These surface-modified reinforcing fillers (C) do not aggregate, and the surface treatment allows the filler to be easily wetted by the polydiorganosiloxane polymer (A), so that it can be homogeneously incorporated into the polydiorganosiloxane polymer (A) described below.

[0054] Typically, the reinforcing filler (C) can be surface-treated with any low molecular weight organosilicon compound disclosed in the Art that is applicable to prevent creping of the organosiloxane composition during processing. For example, organosilanes, polydiorganosiloxanes, or organosilazanes, such as hexaalkyldisilazanes or short-chain siloxane diols, which make the filler hydrophobic, thereby making it easier to handle and obtaining a homogeneous mixture with other raw materials. Specific examples include silanol-terminated trifluoropropylmethylsiloxane, silanol-terminated vinylmethyl (ViMe)siloxane, silanol-terminated MePhsiloxane, liquid hydroxyl-terminated polydiorganosiloxanes containing 2 to 20 repeating units of diorganosiloxane in each molecule, hydroxyldimethyl-terminated phenylmethylsiloxane, hexamethyldisiloxane, divinyltetramethyldisiloxane, and other hexaorganodisiloxanes; hexamethyldisilazane (HMDZ), divinyltetramethyldi Silanes include, but are not limited to, silanes such as silazanes, hexaorganodisilazanes such as tetramethyldi(trifluoropropyl)disilazane, hydroxyldimethyl-terminated polydimethylmethylvinylsiloxane, octamethylcyclotetrasiloxane, and methyltrimethoxysilane, dimethoxydimethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, chlorotrimethylsilane, dichlorodimethylsilane, and trichloromethylsilane. Small amounts of water can be added together with the silica treatment agent as a processing aid.

[0055] Surface treatment can be performed before introduction into the composition or in situ (i.e., by mixing these components together at room temperature until the filler is completely treated in the presence of at least some of the other raw materials of the composition herein). Typically, an untreated reinforcing filler (C) is treated in situ with a treatment agent in the presence of a polydiorganosiloxane polymer (A) to prepare a base material for a silicone elastomer that can later be mixed with the other raw materials.

[0056] The reinforcing filler (C) is present in an amount of 5.0 to 40% by weight of the solid content of the composition, or 7.5 to 35% by weight of the solid content of the composition, or 10.0 to 35% by weight based on the weight percentage of the solid content of the composition. Thus, the amount of the reinforcing filler (C), such as pulverized silica and / or silicone resin, may be, for example, 2.0 to 20% by weight or 2.5 to 15% by weight of the total composition. In some cases, the amount of the reinforcing filler may be 5.0 to 15% by weight based on the weight of the total composition.

[0057] Non-reinforcement fillers may optionally be included in component (C) of this specification. These may include, by example, crushed quartz, calcium carbonate, diatomaceous earth, barium sulfate, iron oxide, titanium dioxide and carbon black, talc, wollastonite, bandstone, calcium sulfate (anhydrous gypsum), gypsum, calcium sulfate, magnesium carbonate, clay such as kaolin, aluminum trihydroxylate, magnesium hydroxide, i.e., talc, graphite, copper carbonate, i.e., malachite, nickel carbonate, i.e., zarachite, barium carbonate, i.e., withalite and / or strontium carbonate, i.e., strontianite.

[0058] Other non-reinforced fillers may include silicates from the group consisting of aluminum oxide, olivine group; garnet group; aluminosilicate; cyclic silicate; chain silicate; and layered silicate. The olivine group includes, but is not limited to, silicate minerals such as forsterite and Mg2SiO4. The garnet group includes red garnet; Mg3Al2Si3O 12 ;Edmond garnet; and Ca2Al2Si3O 12 This includes, but is not limited to, pulverized silicate minerals such as sillimanite; Al2SiO5; mullite; 3Al2O3.2SiO2; kyanite; and pulverized silicate minerals such as Al2SiO5. Cyclic silicates may also be used as unreinforced fillers, such as cordierite and Al3(Mg,Fe)2[Si4AlO 18The silicate group includes, but is not limited to, silicate minerals such as ]. The chain silicate group includes, but is not limited to, crushed silicate minerals such as wollastonite and Ca[SiO3]. Layered silicates may be used as alternative or additional non-reinforcing fillers, and suitable groups include silicate minerals such as mica and K2AI. 14 [Si6Al2O 20 ](OH)4;phyllite;Al4[Si8O 20 ](OH)4; Talc, Mg6[Si8O 20 ](OH)4; serpentine, e.g., asbestos; kaolinite; Al4[Si4O 10 Examples include, but are not limited to, silicate minerals such as ](OH)8 and vermiculite. In one alternative example, the filler is selected from one or more of fumed silica, precipitated silica, calcium carbonate, talc, mica, quartz, and aluminum oxide.

[0059] As previously shown, each of the above components (D) contains at least one or at least two Si-H groups per molecule, and at least one or at least two functional groups per molecule, selected from anhydride groups and epoxy groups.

[0060] For example, the organopolysiloxane additive may be a phenylmethylpolysiloxane additive containing at least one or at least two Si-H groups per molecule, and at least one or at least two functional groups selected from anhydride groups and epoxy groups, or it may be a polydimethylsiloxane additive containing at least one or at least two Si-H groups per molecule, and at least one or at least two functional groups selected from anhydride groups and epoxy groups.

[0061] In one embodiment, the organopolysiloxane additive (D) or each of the organopolysiloxane additives (D) may be of the following formula: D(Z) d -(O)e -[Y]-(SiR 3 2- Z) d D In the formula, each D group is a cyclic siloxane with the following structure: [(O-Si(-)R 3 )(OSiR 3 H) m (OSiR 3 X) a ] In the formula, each R 3 The group is an alkyl group containing 1 to 6 carbon atoms, where each X is a group containing an anhydride or epoxide functional value, where m is at least 1, or 1 to 20, or 1 to 10, or 1 to 6, and a is at least 1, or 1 to 20, or 1 to 10, or 1 to 6, preferably m+a is 2 to 20, or 2 to 10, or 2 to 6. [Y] is structure [SiPhR] 3 O] n , (SiR 3 20) n , or [SiPh2O] n It is a linear siloxane group, or structure [SiPhR 3 O] n or (SiR 3 20) n It is a linear siloxane group, In the formula, Ph is a phenyl group, Z is an alkylene group having 2 to 10 or 2 to 6 carbon atoms, n is an integer from 2 to 20, and d=e=0 or 1. d+e=1, and when d=1, [Y] is (SiR 3 20) n That is the case.

[0062] In the latter case, [(O-Si(-)R in cyclic siloxane D] 3 The Si in the ) group is bonded to the linear siloxane group via oxygen. Each R 3 The groups may be the same or different, and may be alkyl groups or substituted alkyl groups containing 1 to 6 carbon atoms, or each R 3The groups may be the same or different, and may be methyl, ethyl, propyl, trifluoropropyl, or nonafluorohexyl, or alkyl or substituted alkyl groups selected from methyl or ethyl groups. Each X group is added to the ring of cyclic siloxane D by replacing the Si-H group in the ring with a Si-X group. Each cyclic siloxane D may have the same or different number of members in the ring, for example, 6 to 20 members, or 6 to 16 members, or 6 to 14 members, or 8 to 12 members, for example,

[0063] [ka] In the formulas, each p in either formula [2] or [3] above may independently be 1, 2, or 3 or more, and in fact, component (D) may contain one and / or other mixtures of the above, where each p per molecule is 1, 2, or 3 or more. If a mixture is present, the most abundant molecules are preferably p = 1. If component / additive (D) is a mixture, the mixture may further contain structures similar to those above, for example, but cyclic siloxane D is, for example, a 10-membered ring with p = 2, or a 12-membered ring with p = 3. In one embodiment, the mixture may contain about 50-80% molecules with p = 1, 20-49% molecules with p = 2, and the remainder (if present) are molecules with p = 3 or more, or molecules with p = 3.

[0064] For example, [Y] is a phenylmethylpolysiloxane, and X is a cyclic siloxane via an ether group (OSiR 3If the X) group is an epoxide functional group bonded to a silicon unit, this can be achieved by reacting an alkenyl glycidyl ether, such as allyl glycidyl ether, with the Si-H group, which is an intermediate of the cyclic siloxane described above. Therefore, for example, when m=2 and a=1, additive (D) may have the following structure, where the cyclic siloxane D is, for example, an 8-membered ring with p=1, but the X group may replace any of the Si-H groups on the ring of each cyclic siloxane D, and therefore is not necessarily in the position shown in the figure:

[0065] [ka] If component / additive (D) is a mixture containing the above, the mixture may further contain structures similar to those described above, for example, cyclic siloxane D having a 10-membered ring with p = 2 (in formula [2]) and / or a 12-membered ring with p = 3 (in formula [2]).

[0066] Similarly, when m=1 and a=2, additive (D) may have the following structure, but please understand that the X group may replace any of the Si-H groups on the ring of each cyclic siloxane D, and therefore is not necessarily in the position shown.

[0067] [ka] Similarly, if the component / additive (D) in this form is a mixture containing the above, the mixture may further contain structures similar to those described above, for example, the cyclic siloxane D being a 10-membered ring with p = 2 (in formula [3]) and / or a 12-membered ring with p = 3 (in formula [3]).

[0068] For example, [Y] is a phenylmethylpolysiloxane, and X is a cyclic siloxane via an ether group (OSiR 3If the X) group is an anhydride functional group bonded to a silicon unit, this can be achieved by reacting an alkenyl succinic anhydride, such as allyl succinic anhydride, with the Si-H group which is an intermediate of the cyclic siloxane described above. Therefore, for example, when m=2 and a=1, additive (D) may have the following structure, where the cyclic siloxane D is, for example, an 8-membered ring with p=1, but the X group may replace any of the Si-H groups on the ring of each cyclic siloxane, and therefore is not necessarily in the position shown in the figure:

[0069] [ka] Similarly, if component / additive (D) in this form is a mixture containing the above, the mixture may further contain structures similar to those described above, for example, cyclic siloxane D being a 10-membered ring and / or a 12-membered ring with p = 3.

[0070] The above-mentioned phenylmethylpolysiloxane-based additive (D), in which each X is a group containing an anhydride or an epoxide functional group, may be prepared according to the process described in International Application US19 / 064350 in the name of the present applicant.

[0071] Alternatively, if the organopolysiloxane additive (D) has a polydimethylsiloxane group [Y], then X is (OSiR in the cyclic siloxane) 3 X) is an epoxide functional group bonded to a silicon unit. Therefore, for example, when m=2 and a=1, additive (D) may have the following structure, where the cyclic siloxane D is, for example, an 8-membered ring with p=1, but the X group may replace any of the Si-H groups on the ring of each cyclic siloxane, and therefore should not necessarily be in the position shown in the figure. It may have the following structure

[0072] [ka] However, if the component / additive (D) in this form is a mixture containing the above, the mixture may further contain structures similar to those described above, for example, such that the cyclic siloxane D is a 10-membered ring with p = 2 and / or a 12-membered ring with p = 3.

[0073] The amount of component (D) present in the compositions herein is typically 0.01 to 25 weight percent, or 0.05 to 5 weight percent, most typically 0.25 to 4 weight percent, based on the total weight of the composition. If component (D) supports more than two Si-H groups per molecule, component (D) may also help to play a partial role in the Si-H component of component (B). In such cases, those skilled in the art will understand that a larger percentage of component (D) may be available.

[0074] Depending on the intended use of the curable silicone elastomer composition, optional additives may be present in the composition. Examples include one or more curing inhibitors, vinylized silicone gum, dimethyl vinyl polydiorganosiloxane having a viscosity of 10 to 750 mPa·s at 25°C, release agents, adhesion catalysts, and / or pigments. Other possible additives include conductive fillers, thermally conductive fillers, pot life extenders, flame retardants, lubricants, adhesion promoters, release agents, diluents, solvents, UV light stabilizers, bactericides, wetting agents, heat stabilizers, chain extenders, compression set additives, and plasticizers.

[0075] Curing inhibitors are used, if necessary, to prevent or delay the addition reaction curing process, particularly during storage. Optional addition 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 en-yines, hydroperoxides, nitriles, and diaziridines. Alkenyl-substituted siloxanes, such as those described in U.S. Patent No. 3,989,667, may also be used, with cyclic methylvinylsiloxanes being preferred.

[0076] One known class of hydrosilylation reaction inhibitors is the acetylene compounds disclosed in US3445420. Acetylene alcohols such as 2-methyl-3-butyne-2-ol are a preferred class of inhibitors that suppress the activity of platinum-containing catalysts at 25°C. Typically, compositions containing these inhibitors need to be heated to a temperature of 70°C or higher to cure at a practical rate.

[0077] Examples of acetylene alcohols and their derivatives include 1-ethynyl-1-cyclohexanol (ETCH), 2-methyl-3-butyne-2-ol, 3-butyne-1-ol, 3-butyne-2-ol, propargyl alcohol, 1-phenyl-2-propyne-1-ol, 3,5-dimethyl-1-hexyne-3-ol, 1-ethynylcyclopentanol, 3-methyl-1-penten-4-in-3-ol, and mixtures thereof. Derivatives of acetylene alcohols may include these compounds having at least one silicon atom.

[0078] In some cases, when present, a low inhibitor concentration of about 1 mole per mole of catalyst metal will provide satisfactory storage stability and curing rate. In other cases, an inhibitor concentration of up to 500 moles per mole of catalyst metal is required. The optimal concentration of a given inhibitor in a given composition can be easily determined by normal experiments. Depending on the concentration and form in which the selected inhibitor is commercially available, if present in the composition, the inhibitor is generally present in an amount of 0.0125 to 10% by weight of the composition.

[0079] If deemed necessary, the composition may further contain vinylized silicone gum. Such gums typically have a structure similar to component (A), with dimethylvinyl-terminated groups being polydimethylsiloxane polymer chains, although there may be some combination of vinylmethyl groups along the length of the polymer chain. In the case of these polymers, the main difference, in contrast to component (A), is the chain length and the resulting viscosity. Typically, this type of gum has a viscosity of at least 1,000,000 mPa·s at 25°C, and is often significantly higher. However, since it is difficult to measure viscosities above these values, gums tend to be described not by viscosity, but by Williams plasticity values ​​according to ASTM D-926-08. The types of gums described herein typically have Williams plasticity values ​​of 30 mm / 100, or at least 50 mm / 100, or at least 100 mm / 100, or in the range of 100 mm / 100 to 350 mm / 100, according to ASTM D-926-08.

[0080] Dimethylvinyl polydiorganosiloxanes have a viscosity of 10–750 mPa·s at 25°C. Such dimethylvinyl polydiorganosiloxanes typically have a structure similar to component (A), where the dimethylvinyl end groups are polydimethylsiloxane polymer chains, but there may be some combination of vinylmethyl groups along the length of the polymer chain. In the case of these polymers, the main difference is the chain length and the resulting viscosity, in contrast to component (A) polymers of this type, which have a zero shear viscosity of 10–750 mPa·s at 25°C. The zero shear viscosity is obtained by extrapolating to zero the value obtained at low shear rates where the viscosity-shear rate curve is rate-independent, and this is an independent value of the test method. The zero shear viscosity of a substance at 25°C is typically obtained using a viscometer such as a Brookfield® rotational viscometer, which uses a rheometer or spindle (LV-4) and adapts the rate according to the polymer viscosity.

[0081] Examples of conductive fillers include metal particles, metal oxide particles, metal-coated metal particles (such as silver-plated nickel), metal-coated non-metallic core particles (such as silver-plated talc, mica, or quartz), and combinations thereof. The metal particles may be in the form of powder, flakes, or filaments, or mixtures or derivatives thereof.

[0082] Examples of thermally conductive fillers include boron nitride, alumina, metal oxides (such as zinc oxide, magnesium oxide, and aluminum oxide), graphite, diamond, and mixtures or derivatives thereof.

[0083] Examples of chain extenders include linear organopolysiloxanes containing two silicon-bonded hydrogen groups at their terminal positions. Such chain extenders differ from component (B)(ii)(a) crosslinkers, which are in the form of organopolysiloxanes containing at least two or three silicon-bonded hydrogen atoms per molecule. Examples of chain extenders include, but are not limited to, disiloxanes or low molecular weight polyorganosiloxanes containing two silicon-bonded hydrogen atoms at their terminal positions. Chain extenders typically react with alkenyl radicals of polymer (A), thereby linking two or more molecules of polymer (A) together, increasing their effective molecular weight and the distance between potential crosslinking sites.

[0084] Disiloxanes typically have the general formula (HR a It is represented as 2Si)2O. If the chain extender is a polyorganosiloxane, it is represented by the general formula HR a 2SiO 1 / 2 Terminal units and formula R b It has 2SiO non-terminal units. In these formulas, R a and R b The term independently represents an unsubstituted or substituted monovalent hydrocarbon group that is ethylenically unsaturated and does not contain fluorine, and is not limited to, alkyl groups containing 1 to 10 carbon atoms, substituted alkyl groups containing 1 to 10 carbon atoms such as chloromethyl, cycloalkyl groups containing 3 to 10 carbon atoms, aryl groups containing 6 to 10 carbon atoms, alkaryl groups containing 7 to 10 carbon atoms such as tolyl and xylyl, and aralkyl groups containing 7 to 10 carbon atoms such as benzyl groups.

[0085] Further examples of chain extenders include tetramethyldihydrogendisiloxane or dimethylhydrogen-terminated polydimethylsiloxane.

[0086] The chain extender may be added in an amount of 1 to 10 parts by weight based on the weight of polymer (A), typically 1 to 10 parts per 100 parts of the polymer (A) combination.

[0087] Optionally, adhesion promoters may be present in the composition. Any suitable adhesion promoter may be used. These may include, or consist of, one or more alkoxysilanes containing a methacrylic group or an acrylic group, and / or one or more alkoxysilanes containing an epoxy group, and optionally, one or more condensation catalysts, if present, used to activate and / or accelerate the reaction of the adhesion promoter.

[0088] Examples of alkoxysilanes containing a methacrylic group or an acrylic group include methacryloxymethyl-trimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-methacryloxypropyl-methyldimethoxysilane, 3-methacryloxypropyl-dimethylmethoxysilane, 3-methacryloxypropyl-triethoxysilane, 3-methacryloxypropyl-methyldiethoxysilane, 3-methacryloxyisobutyl-trimethoxysilane, or similar methacryloxy-substituted alkoxysilanes; and alkoxysilanes containing a methacrylic group or an acrylic group, such as 3-acryloxypropyl-trimethoxysilane, 3-acryloxypropyl-methyldimethoxysilane, 3-acryloxypropyl-dimethyl-methoxysilane, 3-acryloxypropyl-triethoxysilane, or similar acryloxy-substituted alkyl-containing alkoxysilanes.

[0089] Examples of epoxy-containing alkoxysilanes that can be used as adhesion promoters include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 4-glycidoxybutyltrimethoxysilane, 5,6-epoxyhexyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

[0090] Adhesion catalysts, i.e., condensation catalysts used to activate and / or accelerate the reaction of the adhesion promoters described above, may also be utilized. Such condensation catalysts may be selected from organometallic catalysts, including titanates, e.g., tetrapropoxytitanate; zirconates, organoaluminum chelates, titanium chelates, and / or zirconium chelates.

[0091] For example, titanate-based catalysts and / or zirconate-based catalysts have the general formula Ti[OR 5 ]4 or Zr[OR 5 ]4(In the formula, each R 5 The compounds may include a monovalent primary, secondary, or tertiary aliphatic hydrocarbon group (which may be the same or different, and may be linear or branched, containing 1 to 20 carbon atoms, or 1 to 10 carbon atoms). Optionally, the titanate or zirconate may contain a partially unsaturated group. 5 Preferred examples include, but are not limited to, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, tertiary butyl groups, and branched secondary alkyl groups, such as 2,4-dimethyl-3-pentyl groups. 5 If the same, preferably R 5This is an isopropyl group, a branched secondary alkyl group or a tertiary alkyl group, and especially a tertiary butyl group. Specific examples include, but are not limited to, zirconium tetrapropylate and zirconium tetrabutyrate, tetra-isopropyl zirconate, zirconium(IV) tetraacetylacetonate (sometimes called zirconium AcAc), zirconium(IV) hexafluoroacetylacetonate, zirconium(IV) trifluoroacetylacetonate, tetrakis(ethyltrifluoroacetylacetonate)zirconium, tetrakis(2,2,6,6-tetramethyl-heptanethionate)zirconium, zirconium(IV) dibutoxybis(ethylacetonate), zirconium tributoxyacetylacetate, zirconium butoxyacetylacetonate bisethylacetoacetate, diisopropoxybis(2,2,6,6-tetramethyl-heptanethionate)zirconium, or similar zirconium complexes having β-diketones (including their alkyl-substituted and fluorine-substituted forms) used as ligands. The titanate equivalent of the above-mentioned zirconate is also included.

[0092] Suitable aluminum-based condensation catalysts include Al(OC3H7)3 and Al(OC3H7)2(CH3COCH2COC 12 H 25 ), Al(OC3H7)2(OCOCH3), and Al(OC3H7)2(OCOC 12 H 25 One or more of the following may be cited.

[0093] Where necessary and / or deemed beneficial, the adhesion promoter may also contain other raw materials, such as other silane coupling agents, and organic compounds containing two or more acrylate groups and / or reactive siloxanes.

[0094] Examples of adhesion promoters include silane coupling agents, such as methyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, and 1,6-bis(trimethylsilyl)hexane, 3-methacryloxypropyltrimethoxysilane, and / or glycidoxypropyltrimethoxysilane.

[0095] Examples of organic compounds containing two or more acrylate groups include, for example, hexanediol diacrylate, heptanediol diacrylate, octanediol diacrylate, nonanediol diacrylate, and / or undecanediol. 4-20 Examples include diacrylates such as alkanediol diacrylate, and / or pentaerythritol tetraacrylate.

[0096] Examples of reactive siloxanes include siloxanes such as hydroxy-terminated dimethyl-methylvinylsiloxane and trimethylsiloxy-terminated methyldimethylsiloxane, all of which optionally contain one or more perfluoroalkyl chains, such as trifluoropropyl or perfluorobutylethyl side chains. Typically, such siloxanes have a viscosity of 0.001 to 0.1 Pa·s at 25°C, or 0.001 to 0.05 Pa·s at 25°C.

[0097] If present, the adhesion promoter is typically present in the composition in an amount of about 0.1–6% by weight, or 0.1–4% by weight.

[0098] Examples of flame retardants include aluminum trihydrate, magnesium hydroxide, magnesium silicate, chlorinated paraffin, hexabromocyclododecane, triphenyl phosphate, dimethylmethylphosphonate, tris(2,3-dibromopropyl) phosphate (brominated tris), and mixtures or derivatives thereof.

[0099] Examples of pigments include iron oxide, carbon black, and mixtures or derivatives thereof.

[0100] Examples of lubricants include tetrafluoroethylene, resin powder, graphite, fluorinated graphite, talc, boron nitride, fluorinated oil, silicone oil, molybdenum disulfide, and mixtures or derivatives thereof.

[0101] Further additives include silicone fluids such as trimethylsilyl or OH-terminated siloxanes. Such trimethylsiloxy or OH-terminated polydimethylsiloxanes typically have a viscosity of less than 150 mPa·s (<) at 25°C. If present, such silicone fluids may be present in the curable silicone elastomer composition in an amount ranging from 0.1 to 5% by weight based on the total weight of the composition.

[0102] Curable silicone elastomer composition, This may include a curable silicone elastomer composition capable of achieving significant adhesion on a thermoplastic substrate, an organic resin substrate, or the surface of a thermoplastic resin and an organic resin substrate, and this includes:

[0103] Ingredient A 10-85% by weight based on the total weight of the composition, or 20-80% by weight based on the total weight of the composition, or 20-75% by weight based on the total weight of the composition, or 30-65% by weight based on the total weight of the composition.

[0104] When component (B) is (B)(i), the organic peroxide may be present in either case in an amount of 0.2–3% by weight or 0.2–2% by weight based on the weight of the composition.

[0105] Alternatively, if component (B) is (B)(ii), component (B)(ii)(a) contains at least two or three silicon-bonded hydrogen atoms per molecule and is present in an amount of 0.1 to 40% by weight of the total composition, or 0.5 to 20% by weight of the total composition, or 0.5 to 10% by weight of the total composition, or further 1% to 5% by weight of the total composition, Component (B)(ii)(b), at least one hydrosilylation catalyst in an amount of 0.01 to 10% by weight of the total composition, or 0.01% to 5% by weight of the total composition, or further 0.05% to 2% by weight of the total composition, Component (C), at least one reinforcing filler and one or more optional non-reinforcing fillers in an amount of 1 to 80% by weight based on the total weight of the composition, or 1 to 50% by weight based on the total weight of the composition, or 5 to 50% by weight based on the total weight of the composition, or further 8 to 30% by weight based on the total weight of the composition. This disclosure is intended to include any of the above combinations that provide a total composition percentage of components (A) to (C), and any optional additive constitutes 100% by weight of the composition. The above compositions, excluding component (D), are 100% by weight. Component (D) is added in an amount calculated with the remainder of the composition being 100%.

[0106] When curing is performed by hydrosilylation, it is important that the catalyst (B)(ii)(b) is stored separately from the crosslinking agent (B)(ii)(a) to prevent premature curing during storage. Typically, the catalyst (B)(ii)(b) is included in the Part A composition and the crosslinking agent (B)(ii)(a), and an optional inhibitor is stored in the Part B composition. Similarly, a given component (D) contains multiple Si-H groups if the hydrosilylated curable component D should be stored separately from the catalyst (B)(ii)(b). Therefore, in the case of a hydrosilylated curable composition, typically, the crosslinking agent (B)(ii)(a), component D, and any inhibitor used are all included in the Part B composition.

[0107] Optional additives (excluding inhibitors) may be in part (A), part (B), or both. They may also be added to the final mixture after part (A) or part (B) has been combined.

[0108] Homogeneous mixing of the components of this curable silicone elastomer composition can be performed using suitable mixing means such as a kneader mixer, Z-blade mixer, two-roll mill (open mill), three-roll mill, Haake® Rheomix OS Lab mixer, screw extruder, or twin-screw extruder. For example, speed mixers such as those sold by Hauschild, and DC150.1FV, DAC400FVZ, or DAC600FVZ can be used as alternatives.

[0109] During use, the composition can be cured at any suitable temperature, for example, 80°C to 250°C or 120°C to 200°C. It was also determined that, in order to obtain a peak load / width of at least 3.5 kN / m, the sealant formulation must typically be applied to a thickness of at least 0.9 mm. The curing time of the compositions herein was found to be preferably at least 3 minutes or at least 4 minutes to ensure good adhesion.

[0110] As described above, in one embodiment, (i) Applying the first beads of the curable silicone elastomer composition described herein to the periphery of the first cloth sheet, (ii) Bringing the first beads of the curable silicone elastomer composition into contact with the surface of the second cloth sheet, (iii) A process is also provided for producing an inflatable article, comprising forming a non-suture seam containing a curable silicone elastomer product of a curable silicone elastomer composition, thereby bonding a first fabric sheet to the fabric sheet through the non-suture seam, wherein the resulting non-suture seam bond has a peak load / width of at least 3.5 kN / m.

[0111] As described above, in one embodiment, (i) Applying the first beads of the curable silicone elastomer composition described herein to the periphery of the first cloth sheet, (ii) Applying the second beads of the curable silicone elastomer composition around the periphery of the second cloth sheet, as described above, (iii) To bring the first exposed surface of the first bead and the second exposed surface of the second bead into contact to form a single bead, (iv) A process is also provided for producing an inflatable article, comprising forming a non-suture seam containing a curable silicone elastomer product of a curable silicone elastomer composition, thereby bonding a first fabric sheet to a second fabric sheet through the non-suture seam, wherein the resulting non-suture seam bond has a peak load / width of at least 3.5 kN / m.

[0112] The peak load / width values ​​described herein are determined by using the methods described in the examples herein.

[0113] The beads of the above silicone composition may be applied to the airbag surface by a pneumatic gun, and the two-layer airbag is then heated using a suitable means, such as under a platen press, to perform a rapid curing process that intertwines the silicone coating and silicone adhesive placed on the two fabric layers of the airbag.

[0114] In either process, the surface of either or both of the fabric sheets may be pre-treated, for example, by plasma, corona, and / or UV-C, before applying the composition as described above.

[0115] The term "plasma" encompasses many systems whose density and temperature vary by orders of magnitude. Some plasmas are hot, and all their microscopic species (ions, electrons, etc.) are in near thermal equilibrium, with the energy input to the system being widely distributed by atomic / electron-level collisions. However, other plasmas, particularly those at low pressures (e.g., around 100 Pa) where collisions are relatively frequent, have their constituent species at a wide range of temperatures and are called "non-thermal equilibrium" plasmas. In these non-thermal equilibrium plasmas, free electrons have temperatures of several thousand Kelvins, while neutral and ionic species remain at low temperatures. Because the mass of free electrons is negligible, the total thermal content of the system is low, and the plasma operates at nearly room temperature, making it possible to process temperature-sensitive materials, such as plastics or polymers, without imposing a damaging thermal load on the substrate. However, hot electrons, through high-energy collisions, create a rich source of radicals and excited species with high chemical potential energy, which can result in very high chemical and physical reactivity. It is this combination of low-temperature operation and high reactivity that makes non-thermal plasmas a useful tool for surface treatment.

[0116] In this case, the substrate may be "plasma-treated" by exposing its surface to a gaseous state activated by the form of energy applied from the outside, including, but not limited to, plasma jets, dielectric barrier discharges, low-pressure glow discharges, atmospheric glow discharge treatments, and liquid precursor plasmas.

[0117] "Corona treatment" refers to the exposure of a surface to a locally strong electric field, i.e., a non-uniform electric field generated using a point, edge, and / or wire source, which is conventionally described as a corona discharge system. Corona discharge systems typically operate in ambient air, resulting in an oxidative deposition environment. The design of a corona discharge system is such that it generates locally strong discharges, which result in variations in the energy density throughout the process chamber.

[0118] The inflatable articles herein are primarily designed not to require pretreatment of the fabric sheets before bonding them together using the compositions herein. However, since the fabric sheets can be made impermeable to gas leakage by applying an elastomer coating, the combination of coating two sheets using the aforementioned compositions and the adhesive between them can make the fabric sheets impermeable to gas leakage so that they can function together as a seal to prevent gas from the inflator from leaking through the interlayer. The sheets may be coated with various elastomer coatings, such as silicone compositions, acrylics, polyurethanes, or other suitable materials. The coating can fill openings (or voids) formed between the threads (or fibers) of the fabric sheet, preventing or substantially reducing the escape of high-pressure inflation gas through holes in the woven fabric panel during airbag deployment. Where applicable, the coating may be applied to both sides of the airbag panel or selectively to only one side. Preferably, if present, the coating is in the form of a suitable liquid silicone rubber due to its high heat resistance, low gas permeability, and high non-flammability. Coated airbags generally have improved airtightness.

[0119] Where applicable, the coating can be applied by any desired process, such as spraying, gravure coating, bar coating, knife-over-roller coating, knife-over-air coating, padding, dipping, and screen printing. Such coatings generally have a density of at least 10 g / m². 2 Preferably at least 15 g / m² 2 Applicable to coat weights of up to 100 or 150 g / m². 2 It can be applied to this.

[0120] The fabric is preferably a woven fabric, especially a plain weave, but may also be, for example, knitted or nonwoven. The fabric may be made from synthetic fibers or blends of natural and synthetic fibers, such as polyamide fibers like nylon-6,6, polyester, polyimide, polyethylene, polypropylene, polyester cotton, or glass fibers. For use as airbag fabric, the fabric can be folded into a relatively small volume, but is also strong enough to withstand high-speed deployment, for example, under the influence of explosive loading. [Examples]

[0121] In the following examples, all viscosities were measured using a Brookfield® rotational viscometer with a spindle (LV-4) and a speed adjusted according to the polymer viscosity. Unless otherwise specified, all viscosity measurements were taken at 25°C.

[0122] [Table 1]

[0123] Masterbatch 1 contains 68.7% polymer 1 and 31.3% treated silica.

[0124] [Table 2]

[0125] Additive 1 shown in Table 1b above is a mixture of component (D) structures prepared according to the process described in U.S. Patent No. 7,429,636, and contains the majority (e.g., about 57.5-62%) of molecules having a structure in which [Y] is a polydimethylsiloxane chain, where d is 1, e is 0, m is 2, a is 1, the number of silicon atoms in the linear chain (n+2 in the following structures) is about 7 on average, each cyclic siloxane is an 8-membered ring, and the X group can replace any of the Si-H groups originally located on the ring of each cyclic siloxane, so the main component of the mixture may, but is not necessarily, have the following structure:-.

[0126] [ka] The remainder is a mixture of similar molecules in which the cyclic siloxane D in the structure is a 10-membered ring (approximately 35-40%) and the remaining portion (approximately >0-5%) is a 12-membered ring. The total amount to be added is a maximum of 100%.

[0127] Physical properties of hardened slabs Slabs for measuring physical properties were prepared using the formulations specified in the adhesive composition section. Parts A and B of each composition shown in Table 1 above were mixed in a 1:1 weight ratio using a speed mixer to prepare slabs for each sample, which were then cured at 150°C for 5 minutes. The physical properties were then determined as shown in Table 2 below. Elongation and modulus results were obtained by curing test specimens (ASTM D412-98A) using a DIN S2 die, and Shore A hardness was determined according to (ASTM D2240-97). Tear strength was measured according to ASTM D264.

[0128] [Table 3]

[0129] Laminates of cloth sheets were prepared using the compositions described herein, including the additives described above, for the purpose of evaluating the peak adhesive strength accompanied by tearing by delamination at 180 degrees. Similar to the peak adhesive strength, the estimated cohesive failure percentage is reported, which was determined by inspecting the newly exposed surface at the completion of the test and estimating the cohesive failure percentage. The methodology used was based on ASTM D 413-98, with the following differences in machine speed, sample width, and sample thickness.

[0130] The fabric was cut along the weft direction (approximately 12 inches) and then along the warp direction (approximately 16 inches) to obtain a base sheet (dimensions 12 inches (30.48 cm) x 16 inches (40.64 cm)). All base materials used were pre-dried in an oven at 150°C for 1 minute. The fabric was then removed and placed on a workbench. The chase mold was aligned so that it was positioned straight across the fabric in the weft direction (the chase used in this study had depths of 1.16 mm [leading to an adhesive line approximately 1 mm thick], and further depths of 0.65 mm [leading to an adhesive line approximately 0.5 mm thick], and 1.68 mm [leading to an adhesive line approximately 1.5 mm thick], with all internal dimensions being 10 mm x 10 inches). The Part A and Part B compositions were mixed in a speed mixer in a 1:1 weight ratio.

[0131] Using a plastic spatula, the chase was filled with adhesive. The chase was removed, and the second piece of each substrate was placed on top of the sample beads. The beads were then gently moistened using a styrofoam roller. The sample was then cured in a 150°C oven for 5 minutes.

[0132] As can be seen below, several substrate samples were plasma-treated before use. Plasma treatment was performed after the substrate sheets were oven-treated. For the plasma-treated samples, marks were made on the fabric at the center of the plasma treatment line, but not where adhesive would be applied. The bottom piece of the fabric was plasma-treated using a Plasmatreat FG3001 plasma generator set to a speed of 125 mm / sec. The robot coordinates were set to x=82.24 mm, y=13.76 mm, z=117 mm (these coordinates result in a 7 mm gap from the plasma treatment head to the fabric). After treatment, the samples were applied according to the process described above. A second substrate sheet was plasma-treated, and the plasma-treated surface was applied to the sealant beads. The samples were then cured as described above.

[0133] The samples were left to stand at room temperature for approximately 20 hours before the analysis was performed. Four samples were cut from each specimen, which consisted of a 10-inch seam. The outer 1 inch (2.54 cm) of the specimen was discarded, and four 2-inch (5.08 cm) samples were cut. The length of the cloth was then cut to approximately 6 inches (15.24 cm) in each sample. The thickness of each sample was measured. This was done by subtracting the width of two cloth pieces from the width of the entire sample structure.

[0134] Similar to the peak adhesive strength, we report the peak adhesive strength accompanied by tearing by delaminating the laminate at 180 degrees, and the estimated cohesive failure percentage, which was determined by inspecting the newly exposed surface at the completion of the test and estimating the cohesive failure percentage. These tests were initiated immediately after curing, as described above.

[0135] For peak load / width specimens, testing was performed using an MTS Alliance RF / 100 tensile testing machine. The bonded specimen was placed in the specimen holder, the crosshead speed was set to 8 inches / min (200 mm / min), and the peak load / width was determined. The results provided in the table below were the average of four data points.

[0136] For cohesive failure measurement, this was achieved by analyzing the peak load / width under which the sample was pulled for cohesive failure percentage. A template containing a 2×10 grid (4mm×4mm squares) was placed in the center of the pulled seam, ignoring approximately 5mm on each side of the seam and 2mm on the top and bottom. Each square represented 5% of the area. The cohesive failure percentage was determined for each sample, and then the average was taken for each of the four replicas. The seam thickness was determined using a digital caliper. First, the total seam thickness was measured. The thickness of the fabric substrate was subtracted from the total seam thickness to obtain the thickness of the adhesive layer, the value of which is shown in the table below.

[0137] Results for polyester. The 470 DTEX substrate is shown in Table 3a.

[0138] [Table 4]

[0139] While control tests without additives or zirconate did not achieve adhesion, other examples in Table 3 did, and it will be understood that the peak load / width values ​​disclosed herein were obtained for compositions with a seam thickness of at least 0.9 mm. It should also be noted that the results for cohesive failure % were improved with seam thicknesses of at least 0.9 mm.

[0140] [Table 5]

[0141] It was found that adhesion was not achieved when curing at room temperature. A seam thickness of 0.5 mm led to an acceptable peak load / width, but adhesive failure was more frequent than cohesive failure. The latter was improved by having a seam thickness of 1 mm when cured at a temperature of 150°C. It was also found that curing for at least 3 minutes typically yielded good results at 5 minutes. Adhesion was obtained with plasma-treated cloth when the sample was cured at 150°C or 180°C for 5 minutes.

[0142] Similar results were achieved on a nylon 66 substrate, as shown in Table 4a below, as obtained on a polyester substrate in Table 3a.

[0143] [Table 6] TFCF = Thin Film Aggregative Fracture

[0144] As previously shown, the control sample containing no additive (D) did not adhere. For example, it is preferable to activate the substrate before use by plasma activation. It was found that much better cohesive failure occurred in seam seals of at least 0.9 mm, especially when cured at temperatures above 120°C, and especially when cured for at least 3 minutes, preferably 5 minutes or more, with the additive at about 150°C. As in the above case, the tests shown in Table 3b were repeated on nylon substrates using the formulation shown as Example 5 in Table 1b. The results are shown in Table 4b below.

[0145] [Table 7] TFCF = Thin Film Aggregative Fracture

[0146] When cured at room temperature, adhesion was not achieved. Sufficient results were rarely provided with a seam thickness of 0.5 mm, and at least with seals of 0.9 mm thickness, adhesive failure was generally more frequent than cohesive failure, resulting in better peak load / width outcomes. Similarly, short curing times of less than 3 minutes were generally found not to yield good, sufficient peak load / width results. For example, good results were achieved for adhesion on plasma-treated fabric when the sample was cured at a temperature of 150°C–190°C for 5 minutes.

[0147] The above tests for peak load / width (kN / m) and cohesive failure were repeated using the formulation of Example 5, but the main components of the mixture may, but may not necessarily, have the following structure, since the X group can replace any of the Si-H groups originally located on the ring of each cyclic siloxane.

[0148] [ka]

[0149] The remainder is a mixture of similar molecules in which the cyclic siloxane in the structure is a 10-membered ring (approximately 40-45%) and the remaining (approximately >0-5%) is a cyclic siloxane with a 12-membered ring. Total amount to be added up to 100% The composition was cured at 150°C for 5 minutes, and the seam thickness was 1 mm. The results are shown in Tables 5a (Polyester) and 5d (Nylon 66) below.

[0150] [Table 8]

[0151] It can be seen that adhesion was achieved with the anhydrous version of X without plasma treatment.

[0152] The same test was also performed using additives 2 and 3 and 4, which were two further compounds containing epoxy groups. Additive 3, which was a mixture of component (D) structures prepared according to the process described in International Application US19 / 064350, contains most molecules (e.g., about 51-55%) having a structure in which [Y] is a polymethylphenylsiloxane chain, e is 1, d is zero, m is 2, a is 1, n is 6-7, each cyclic siloxane D is an 8-membered ring, and each X is an epoxy-containing group, and the X group can replace any of the Si-H groups originally located on the ring of each cyclic siloxane, so the main component of the mixture may, but is not necessarily, have the following structure:

[0153] [ka]

[0154] The remainder is a mixture of similar molecules in which the cyclic siloxane in the structure is a 10-membered ring (approximately 40-45%) and the rest (approximately >0-5%) is a 12-membered ring. The total amount to be added is a maximum of 100%.

[0155] Additive 4 is also a mixture of component (D) structures prepared according to the process described in international application US19 / 064350, and contains the majority (about 51-55%) of molecules with a structure equivalent to that of Additive 3, with one difference being that it contains four epoxy groups, with m being 1 and a being 2, in contrast to the 2 in Additive 3. Therefore, the main component of the mixture may, but is not necessarily, have the following structure.

[0156] [ka]

[0157] The remainder of additive 4 is a mixture of similar molecules in which the cyclic siloxane D in the structure is a 10-membered ring (approximately 40-45%) and the remainder (approximately >0-5%). Total amount added up to a maximum of 100%.

[0158] The results obtained using additives 2-4 in the Part B composition of Example 5 were as follows.

[0159] [Table 9]

[0160] Adhesion was achieved with anhydrous materials, regardless of whether or not the substrate was plasma-treated. Similar results were obtained with nylon using both epoxides.

Claims

1. (A) One or more organopolysiloxanes containing at least two alkenyl groups per molecule and having a viscosity in the range of 1,000 mPa·s to 500,000 mPa·s at 25°C, (B) A hardening agent, (B) (ii) Hydrosilylation curing catalyst package, a. Organosilicon compounds having at least two or at least three Si-H groups per molecule, and b. A curing agent comprising a hydrosilylation catalyst package containing a hydrosilylation catalyst, (C) at least one reinforcing filler and optionally one or more non-reinforcing fillers, (D) A curable silicone elastomer composition for curing into a cured silicone adhesive in an expandable article, comprising one or more organopolysiloxane additives, each containing at least one or at least two Si-H groups per molecule, and at least one or at least two functional groups selected from anhydride groups and epoxy groups per molecule, The component (D) of the curable silicone elastomer composition comprises one or more organopolysiloxanes of the following formulas: D(Z) ｄ -(O) ｅ -[Y]-(SiR ３ ２－ Z) ｄ D In the formula, each D group is a cyclic siloxane with the following structure: [(O-Si(-)R ３ )(OSiR ３ H) ｍ (OSiR ３ X) ａ ] In the formula, each R ３ The group is an alkyl group containing 1 to 6 carbon atoms, where each X is a group containing anhydride or epoxide functionality, where m is at least an integer of 1, and a is at least an integer of 1. [Y] is structure [SiPhR ３ O] ｎ (SiR ３ ２ O) ｎ , or [SiPh ２ O] ｎ It is a linear siloxane group, In the formula, Ph is a phenyl group, Z is an alkylene group having 2 to 10 or 2 to 6 carbon atoms, n is an integer from 2 to 20, d = 0 or 1, and e = 0 or 1. d + e = 1, and when d = 1, [Y] is (SiR ３ ２ O) ｎ And, Component D is as follows: A compound in which [Y] is a polydimethylsiloxane chain, d is 1, e is zero, m is 2, a is 1, the average value of n is 4 to 10, and X contains an epoxy functional group. [Y] is a polymethylphenylsiloxane chain, e is 1, d is zero, m is 2, a is 1, the average value of n is 4 to 10, and X contains anhydride functionality, A compound in which [Y] is a polymethylphenylsiloxane chain, e is 1, d is zero, m is 2, a is 1, the average value of n is 4 to 10, and X contains epoxy functionality. [Y] is a polymethylphenylsiloxane chain, e is 1, d is zero, m is 1, a is 2, the average value of n is 4 to 10, and X is a compound containing epoxy functionality. A compound selected from one or more of the following, or containing the same Component (B) is different from component (D), Curing is performed after activating the fabric sheet contained in the expandable article with plasma, and then applying the curable silicone elastomer composition to the peripheral edge of the activated fabric sheet to a thickness of 0.9 mm or more. A curable silicone elastomer composition further comprising zirconate and / or titanate.

2. The curable silicone elastomer composition according to claim 1, wherein the article is an airbag.

3. The curable silicone elastomer composition according to claim 2, wherein the airbag is an uncoated airbag.

4. The use of a curable silicone elastomer composition as a seam sealant for an expandable article, wherein the curable silicone elastomer composition is (A) One or more organopolysiloxanes containing at least two alkenyl groups per molecule and having a viscosity in the range of 1,000 mPa·s to 500,000 mPa·s at 25°C, (B) A hardening agent, (B) (ii) Hydrosilylation curing catalyst package, a. Organosilicon compounds having at least two or at least three Si-H groups per molecule, and b. A curing agent comprising a hydrosilylation catalyst package containing a hydrosilylation catalyst, (C) at least one reinforcing filler and optionally one or more non-reinforcing fillers, (D) comprising one or more organopolysiloxane additives, each molecule containing at least one or at least two Si-H groups and at least one or at least two functional groups selected from anhydride groups and epoxy groups, The curable silicone elastomer composition further comprises zirconate and / or titanate, The component (D) of the curable silicone elastomer composition comprises one or more organopolysiloxanes of the following formulas: D(Z) ｄ -(O) ｅ -[Y]-(SiR ３ ２－ Z) ｄ D In the formula, each D group is a cyclic siloxane with the following structure: [(O-Si(-)R ３ )(OSiR ３ H) ｍ (OSiR ３ X) ａ ] In the formula, each R ３ The group is an alkyl group containing 1 to 6 carbon atoms, where each X is a group containing anhydride or epoxide functionality, where m is at least an integer of 1, and a is at least an integer of 1. [Y] is structure [SiPhR ３ O] ｎ (SiR ３ ２ O) ｎ , or [SiPh ２ O] ｎ It is a linear siloxane group, In the formula, Ph is a phenyl group, Z is an alkylene group having 2 to 10 or 2 to 6 carbon atoms, n is an integer from 2 to 20, d = 0 or 1, and e = 0 or 1. d + e = 1, and when d = 1, [Y] is (SiR ３ ２ O) ｎ And, Component D is as follows: A compound in which [Y] is a polydimethylsiloxane chain, d is 1, e is zero, m is 2, a is 1, the average value of n is 4 to 10, and X contains an epoxy functional group. [Y] is a polymethylphenylsiloxane chain, e is 1, d is zero, m is 2, a is 1, the average value of n is 4 to 10, and X contains anhydride functionality, A compound in which [Y] is a polymethylphenylsiloxane chain, e is 1, d is zero, m is 2, a is 1, the average value of n is 4 to 10, and X contains epoxy functionality. [Y] is a polymethylphenylsiloxane chain, e is 1, d is zero, m is 1, a is 2, the average value of n is 4 to 10, and X is a compound containing epoxy functionality. A compound selected from one or more of the following, or containing the same Component (B) is different from component (D), The application involves applying the curable silicone elastomer composition in a bead-like manner to the periphery of a fabric sheet with a thickness of 0.9 mm or more. The use of a curable silicone elastomer composition, wherein the cloth sheet is activated by plasma before the curable silicone elastomer composition is applied.

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