coated fabric items

Abstract

The present disclosure relates to an airbag and an airbag fabric article coated with a cured product of a hydrosilylated curable silicone rubber coating composition containing pre-formed silicone elastomer microparticles, and a method of coating said article, such as an airbag or an airbag fabric article, with said hydrosilylated curable silicone rubber coating composition containing pre-formed silicone elastomer microparticles.

Description

Technology Field

[0001] The present disclosure relates to an airbag and an airbag fabric article coated with a cured product of a hydrosilylated curable silicone rubber coating composition containing pre-formed silicone elastomer microparticles, and a method of coating said article, such as an airbag or an airbag fabric article, with said hydrosilylated curable silicone rubber coating composition containing pre-formed silicone elastomer microparticles.

[0002] Textiles and fabrics are often treated with one or more coatings to provide them with various properties. Silicone coating compositions are used to provide textiles and / or fabrics with a wide variety of different properties. One of the main applications of treated textiles and fabrics is their use in or as in inflatable safety restraints, particularly in airbags.

[0003] Airbags are widely used to cushion vehicle occupants in the event of a collision or accident. They are designed to protect drivers and passengers from injury between the initial impact and subsequent impacts by inflating within 0.02 to 0.12 seconds of the initial impact during a traffic accident. Inflatable safety restraint devices, such as airbags, generally consist of a fabric bag (sometimes referred to as a cushion), sensors, and an inflation mechanism. In the event of an accident, sensors within the vehicle detect abnormal deceleration and activate the inflator, thereby effectively and immediately inflating the airbag. Inflating gas travels through ducts to inflate the airbag(s), cushioning the vehicle occupants (driver or passenger) and protecting them from any additional harmful impacts inside the vehicle, such as in a passenger car.

[0004] Airbag and / or airbag fabric articles may be manufactured from woven or knitted fabrics made of synthetic fibers, for example, thermoplastic resins, such as polyamides, such as nylon-6,6, or polyesters, such as polyethylene terephthalate (PET), and benefit from the application of a silicone coating composition that, upon curing, typically provides a silicone elastomer coating having a low modulus, high elongation, low coefficient of friction, and / or high flame retardancy of the silicone elastomer. These characteristics can improve the airbag in a number of ways, including the following:

[0005] 1) Improved thermal protection from high-temperature gases and particulates (600°C to 1,000°C) generated during airbag inflation using a chemical generator;

[0006] 2) Improved flame retardancy of the fabric;

[0007] 3) Improved resistance to bag shrinkage;

[0008] 4) Improved resistance to stress when the airbag cushion deploys; and

[0009] 5) Due to the flexibility and lightness of the silicone coating, it provides very good flexibility to the airbags, allowing them to be folded into more compact modules.

[0010] The airbag can be manufactured by coating flat fabric pieces and then sewing them together to provide sufficient mechanical strength, or it can be woven as a single piece with an integrally woven seam (commonly referred to as "integral weave" or OPW).

[0011] Sewn flat fabric airbags are typically assembled with a coated fabric surface inside the airbag, but the coating may be applied to the inside and / or outside. Monolithic woven airbags are coated on the exterior of the airbag. Some airbags are designed to retain gas pressure after deployment, allowing them to remain inflated for a longer period after an impact, such as with side cushion airbags. These tend to be monolithic woven airbags, but are not necessarily so.

[0012] Today, it is generally mandatory to equip vehicles with multiple airbags as a means of providing safety to occupants in the event of a collision. These include front airbags, front center airbags, side airbags, side curtain airbags, chest airbags, and / or knee airbags. Typically, airbags are concealed within the vehicle trim and are not visible during normal vehicle operation.

[0013] For example, front airbags can be installed on the steering wheel on the driver's side and the dashboard on the passenger's side. They are provided to act as cushions at the point of impact, particularly in the event of a collision with the front or rear of the vehicle. They exhibit relatively high air permeability so that the inflated airbag can deflate rapidly after the initial impact. Typically, these airbags are flat pieces of cloth sewn together.

[0014] Side curtain airbags are becoming increasingly common; they are most frequently mounted within the headliner above the doors and windows and positioned along the side windows near the ceiling to protect vehicle occupants from side collisions and subsequent rollovers (when the vehicle tips over sideways, inverts, or flips over two or more times). For this reason, side curtain airbags are designed to maintain their inflated state for extended periods (e.g., shown to retain at least 50% of the initial pressure after 5 seconds of high-pressure inflation); that is, they must maintain high gas pressure as well as a large volume of gas throughout the entire potential rollover over a longer duration. They are typically released from packing containers stored within the roofline along the vehicle's side windows (thus, they exist only at the rear and front). Therefore, side curtain airbags provide not only cushioning but also protection from broken glass and other debris.

[0015] One-piece woven airbags are commonly used in side curtain airbags in combination with a silicone sealant coating to provide the low permeability (and thus longer gas evacuation time) required for side curtain airbags.

[0016] The silicone coating used on airbags is designed not only to prevent air leakage but also to keep the airbag flexible and resist temperature changes, aging, and wear. Airbags require these properties because they may remain unused for extended periods, for example, before a collision triggers deployment. To achieve this, the silicone coating must remain highly stable over long periods to prevent the airbag from seizing up and to ensure smooth deployment even after many years.

[0017] Accordingly, coated fabric articles, such as airbags and airbag fabric articles coated with a cured product of a hydrosilylated curable silicone rubber coating composition, provide the user with a number of advantages due to their physical properties.

[0018] However, vehicle manufacturers and source equipment manufacturers (OEMs) supplying the automotive industry are continuously striving to meet targets for lowering the "carbon footprint" in vehicle manufacturing. Therefore, there is a need to reduce the carbon footprint associated with manufacturing new silicone compositions used to produce silicone elastomers, such as those used in airbag coatings.

[0019] Given that these are thermosetting materials, silicone elastomers cannot be melted and reprocessed into polymers suitable for their intended applications; therefore, it is difficult to provide effective recycling and / or regeneration methods for incineration or landfill at the end of their lifecycle to meet the desired "carbon footprint" reduction targets for the manufacture of products such as vehicle airbags.

[0020] There are two main types of methods for recycling / regenerating elastomer materials, which tend to be carried out through "chemical processes," such as pyrolysis, chemical decomposition, and chemical reversal, and "physical processes," namely mechanical processes, such as mechanical regeneration, thermomechanical regeneration, and cryogenic mechanical regeneration and wet / solution grinding methods. Given that silicon elastomers are thermosetting materials, chemical recycling of silicon elastomers is not ideal because regeneration / recycling requires significant separation and typically generates low-value solid residues.

[0021] However, it is known that microparticles manufactured from elastomeric silicone materials can be produced, and that one means of achieving this is through recycling and / or regeneration. Nevertheless, these recycled and / or regenerated silicone elastomer microparticles are typically incorporated as fillers along with a binder material that serves as a matrix. The binder may be a new silicone composition or an organic polymer material, which may also be combined with inorganic mixtures, such as asphalt or cement mixtures, and performs the function of capturing and / or encapsulating distinct materials. However, due to inconsistencies and variability in performance, they have not been considered useful in higher-value applications; consequently, the value proposition for these recycled and / or regenerated silicone elastomer microparticles is low, the microparticles are deployed only in lower-value applications, and as a result, the economic and technical incentives for reuse are low:

[0022] (i) Poor incorporation of silicone elastomer microparticles within the binder matrix;

[0023] (ii) Interfacial adhesion and bonding between the silicone elastomer microparticles and the matrix are typically poor, so the pre-formed silicone elastomer microparticles act as defects in the matrix, degrading the properties of the new silicone elastomer by creating voids, surface protrusions, or other heterogeneities in the matrix.

[0024] A more sustainable liquid silicone rubber (LSR) coating composition is provided for use in the manufacture of the silicone rubber-coated airbags described herein, which provides a lower carbon footprint by allowing a significant amount of the new liquid silicone composition (greater than 10 weight percent) to be replaced with pre-formed silicone elastomer microparticles that can be recycled and / or regenerated. It was surprisingly discovered that pre-formed silicone elastomer microparticles from various sources that are recycled, regenerated, or otherwise obtained are compatible with the hydrosilylated curable airbag coating compositions used to manufacture the coated airbags and coated airbag materials.

[0025] Coated fabric articles are provided herein, and the articles are

[0026] i) a substrate having a surface - where the substrate comprises a fabric suitable for manufacturing an airbag -;

[0027] ii) comprises a cured product of a hydrosilylation reaction-curable silicone rubber coating composition attached to the surface of a substrate, and the hydrosilylation reaction-curable silicone rubber composition

[0028] a) one or more organopolysiloxane polymers having a viscosity of 100 to 200,000 mPa·s at 25°C and at least two unsaturated groups per molecule—wherein the unsaturated groups are selected from alkenyl groups and / or alkynyl groups—;

[0029] b) Optionally one or more reinforcing fillers comprising fumed silica, precipitated silica, and / or calcium carbonate;

[0030] c) an organosilicon compound having an average of at least 2 or alternatively at least 3 Si-H groups per molecule;

[0031] d) Hydrosilylated hardening catalyst;

[0032] e) Pre-formed silicone elastomer microparticles (e)(i) having an average non-swelling particle size of 1 mm or less - where the pre-formed silicone elastomer microparticles (e)(i) are swollen by being infiltrated with an organopolysiloxane polymer swelling agent (e)(ii) having a zero shear viscosity of 15,000 mPa·s or less (≤) at 25°C -;

[0033] f) adhesion promoter; and optionally

[0034] g) Includes one or more silicone resins selected from T silicone resin (silsesquioxane), DT silicone resin, MQ silicone resin, MDT silicone resin, MTQ silicone resin, QDT silicone resin, or mixtures thereof.

[0035] In one embodiment, the fabric article is an airbag or an airbag fabric article.

[0036] A method for coating fabric articles is also provided, and the method includes the following steps:

[0037] (1) A step of forming component (e) by mixing pre-formed silicone elastomer microparticles (e)(i) having an average non-swelling particle size of 1 mm or less with an organopolysiloxane polymer swelling agent (e)(ii) having a zero shear viscosity of 15,000 mPa·s or less (≤) at 25°C, so that the organopolysiloxane polymer swelling agent (e)(ii) can penetrate into and swell the pre-formed silicone elastomer microparticles (e)(i);

[0038] (2) Step (2) forming a mixture comprising at least a portion of component (e) and component (a) and optionally one or more of components (c), (d), (f) and when (b), (g), or (b) and (g) are present - where,

[0039] a) is one or more organopolysiloxane polymers having a viscosity of 100 to 200,000 mPa·s at 25°C and at least two unsaturated groups per molecule, wherein the unsaturated groups are selected from alkenyl groups and / or alkynyl groups;

[0040] b) is optionally one or more reinforcing fillers comprising fumed silica, precipitated silica, and / or calcium carbonate;

[0041] c) is an organosilicon compound having an average of at least 2 or alternatively at least 3 Si-H groups per molecule;

[0042] d) is a hydrosilylated hardening catalyst;

[0043] f) is an adhesion promoter; optionally

[0044] g) is T silicone resin (silsesquioxane), DT silicone resin, MQ silicone resin, MDT silicone resin, MTQ silicone resin, QDT silicone resin, or a mixture thereof -;

[0045] (3) Step (2) mixing the mixture with the remainder of components (a), (c), (d), (f) and, when present, (b), (g), or (b) and (g) to produce a hydrosilylated curable silicone rubber coating composition;

[0046] (4) A step of applying a hydrosilylated curable silicone rubber coating composition onto a substrate having a surface—wherein the substrate comprises a fabric suitable for manufacturing an airbag—;

[0047] (5) A step of curing the coating on the substrate having a surface—wherein the substrate comprises a fabric suitable for manufacturing an airbag at a temperature of 100°C to 200°C for a set time.

[0048] In one embodiment, steps (1) and (2) and optionally step (3) may be undertaken together as a single step. A fabric article coated with a cured product of a hydrosilylated curable silicone rubber coating composition prepared according to the method is also provided herein.

[0049] In one embodiment, the fabric article is an airbag or an airbag fabric article.

[0050] The use of pre-formed silicone elastomer microparticles (e)(i) having an average non-swelling particle size of 1 mm or less in a hydrosilylated curable silicone rubber coating composition for coating a fabric article comprising a substrate having a surface is also provided herein, wherein the pre-formed silicone elastomer microparticles (e)(i) are swollen by being infiltrated with an organopolysiloxane polymer swelling agent (e)(ii) having a zero shear viscosity of 15,000 mPa·s or less (≤) at 25°C;

[0051] In addition to, the hydrosilylated curable silicone rubber coating composition,

[0052] a) one or more organopolysiloxane polymers having a viscosity of 100 to 200,000 mPa·s at 25°C and at least two unsaturated groups per molecule—wherein the unsaturated groups are selected from alkenyl groups and / or alkynyl groups—;

[0053] b) Optionally one or more reinforcing fillers comprising fumed silica, precipitated silica, and / or calcium carbonate;

[0054] c) an organosilicon compound having an average of at least 2 or alternatively at least 3 Si-H groups per molecule;

[0055] d) Hydrosilylated hardening catalyst;

[0056] f) adhesion promoter; and optionally

[0057] g) comprising T silicone resin (silsesquioxane), DT silicone resin, MQ silicone resin, MDT silicone resin, MTQ silicone resin, QDT silicone resin, or a mixture thereof;

[0058] The material includes a fabric suitable for manufacturing airbags.

[0059] In one embodiment, the fabric article is an airbag or an airbag fabric article.

[0060] To avoid any doubt, the term average non-swelling particle size is intended to mean the average particle size after manufacturing before mixing with the “swelling agent” otherwise identified as component (e)(ii) and / or the organopolysiloxane polymer (e)(ii).

[0061] The pre-formed silicone elastomer microparticles (e)(i) can be manufactured from a new composition or are physically recycled and / or regenerated silicone elastomer microparticles (e)(i). In one embodiment, the pre-formed silicone elastomer microparticles (e)(i) are physically recycled and / or regenerated silicone elastomer microparticles (e)(i).

[0062] As used herein, the terms recycling and / or regeneration are intended to define the function of recovering and converting waste into new materials and usable products.

[0063] The term “average non-swelling particle size” is intended to mean the average particle size of the fine particles before mixing with the “swelling agent” otherwise identified as component (e)(ii) and / or the organopolysiloxane polymer (e)(ii), regardless of their manufacturing method.

[0064] For example, in the case of physically recycled and / or regenerated silicone elastomer microparticles (e)(i), this is the average particle size of the microparticles after the physical recycling and / or regeneration of the source of the silicone elastomer microparticles (e)(i) and before mixing with the “swelling agent” otherwise identified as component (e)(ii) and / or the organopolysiloxane polymer (e)(ii).

[0065] The use of recycled / regenerated silicone elastomer microparticles (e)(i) provides a more sustainable hydrosilylated cured silicone rubber coating for fabric articles, particularly airbags and airbag fabric articles, and provides a lower carbon footprint to the user by allowing a significant amount of new liquid silicone composition, e.g., at least 10 weight percent of the composition, to be replaced with mechanically recycled cured silicone elastomer microparticles from various sources that are sufficiently compatible with a hydrosilylated curable silicone rubber coating composition that provides elastomer properties useful for coating. Thus, this solution offers the benefits of both reducing the carbon footprint associated with creating a new hydrosilylated cured silicone rubber coating on coated fabric articles, such as airbags and airbag fabric pieces, and providing a high-value alternative to incineration or landfill at the end-of-life stage for the silicone elastomer used in the manufacture of pre-formed silicone elastomer microparticles.

[0066] The ability to infiltrate and swell pre-formed silicone elastomer microparticles (e)(i) into the organopolysiloxane polymer swelling agent (e)(ii) described above forms an interpenetrating network between the new silicone composition and the pre-formed silicone elastomer microparticles, thereby allowing pre-formed silicone elastomer microparticles of various origin to be present without significantly degrading (and potentially even "upcycling" through improved characteristics) the mechanical properties of the elastomer coating formed on the coated airbag and / or airbag fabric of the present invention. This has a direct advantage in the life cycle assessment (LCA) of the coating composition by replacing the carbon dioxide equivalent required for the manufacture of components used in the hydrosilylated curable silicone rubber coating composition with mechanically recycled materials that do not require capital and energy-intensive molecular-level purification steps such as distillation.

[0067] Pre-formed silicone elastomer microparticles (e)(i)

[0068] The pre-formed silicone elastomer microparticles (e)(i) may be produced as new microparticles or may be derived from a recycling / regeneration process derived primarily from post-industrial or post-consumer waste, derived from any suitable source, such as condensation-cured (RTV) silicone elastomers previously used as adhesives, refrigerant spacers, potting agents, coatings, and sealants, such as weather-resistant sealants and coatings and / or tire sealants, or from silicone rubber elastomers produced from hydrosilylated curable compositions, peroxide free radical curable compositions, or UV curable compositions using a photoinitiator or photocatalyst, and the elastomers may have been used in applications such as airbag coatings, gasket and seal adhesives, coatings, foams, molded rubber articles, piping such as hoses and medical tubing, encapsulating agents, and potting agents. The original elastomers and the physically recycled and / or regenerated silicone rubber microparticles produced may have high density or contain inclusions or voids as in foams.

[0069] However, a silicone elastomer produced from any suitable curing system can be utilized as a source of pre-formed silicone elastomer microparticles.

[0070] The newly manufactured microparticles used as the pre-manufactured silicone elastomer microparticles of the present invention may be manufactured from a condensation-cured (RTV) silicone elastomer composition, or may be manufactured from a hydrosilylated curable composition, a peroxide free radical curable composition, or a UV curable composition using a photoinitiator or photocatalyst, which are obtained as slabs / lumps, etc., through their general curing processes and then physically (e.g., mechanically) crushed, ground, or otherwise reduced in size into distinct microparticles using a grinding device described elsewhere in the present invention, or the curable silicone composition may be cured into microparticles by spraying using a spraying device, e.g., a spray dryer; or by dispersing and curing the composition in an aqueous surfactant solution. The latter is generally preferred due to their ability to form spherical cured silicone microparticles.

[0071] When pre-formed silicone elastomer microparticles are the result of physical recycling or regeneration. A physical recycling method is utilized to transform the silicone elastomer into powder, granules, crumbs, or pellets (collectively referred to herein as “microparticles”). The source of the silicone elastomer may be, for example, from post-industrial scrap or waste rubber, pre-consumer scrap or waste rubber, or post-consumer scrap or waste rubber. To avoid any doubt and for the sake of this disclosure, physically (mechanically) recycled / regenerated microparticles retain their original cross-linked structure, whereas chemically recycled materials do not.

[0072] When the origin of cured silicone rubber elastomer microparticles is not known a priori, the cured rubber or physically recycled or regenerated microparticles from which they originate can be characterized by various known methods, including Fourier transform infrared (FTIR) spectroscopy, attenuated total reflection infrared spectroscopy (ATR-IR), infrared microscopy, Raman spectroscopy, Raman microscopy, solid-state nuclear magnetic resonance (NMR) spectroscopy; chemical derivatization and titration techniques; chromatography such as gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS), and liquid chromatography (LC) after chemical decomposition, or spectroscopic techniques including various known elemental or ion analysis techniques such as inductively coupled plasma-optical emission spectroscopy (ICP-OES), X-ray fluorescence analysis (XRF), and neutron activation analysis (NAA), to identify the composition.

[0073] When pre-formed silicone elastomer microparticles are physically recycled or regenerated silicone elastomer microparticles, any suitable physical recycling method including mechanical regeneration, thermomechanical regeneration, cryogenic mechanical regeneration, and wet / solution milling can be utilized to obtain microparticles. Examples of methods that may be utilized to produce microparticles include cryogenic milling (at liquid nitrogen temperatures) using milling equipment known in the art, such as ball milling, pin milling, tornado milling (which may be performed in a solid state at ambient or cryogenic temperatures), and wet jet milling (e.g., wet milling) in which rubber is pulverized by a powerful stream of water.

[0074] The pre-formed silicon elastomer microparticles have an average particle size of 1 mm or less. Although a smaller particle size is desirable to minimize stress concentration defects in the new article, satisfactory performance was achieved even with pre-formed silicon elastomer microparticles milled to a relatively large size of 1 mm. In one embodiment, the average particle size of the pre-formed silicon elastomer microparticles was 600 μm or less, alternatively, the average particle size of the pre-formed silicon elastomer microparticles was 500 μm or less, alternatively, the average particle size of the pre-formed silicon elastomer microparticles was 400 μm or less, alternatively, the average particle size of the pre-formed silicon elastomer microparticles was 300 μm or less, and alternatively, the average particle size of the pre-formed silicon elastomer microparticles was 200 μm or less. Microparticles of an acceptable size can be obtained by mechanical screening through a sized mesh. Smaller particles are obtained by filtration through progressively smaller meshes.

[0075] In one embodiment, the aforementioned silicone elastomer microparticles are physically recycled and / or regenerated silicone elastomer microparticles (e)(i).

[0076] When silicone elastomers produced from physically recycled or regenerated microparticles are attached to another material before use, they are preferably separated or peeled off. For example, if an airbag article is to be recycled, the first step is to recover the silicone elastomer by peeling it off from the fabric / fabric support. Subsequently, the resulting coating may be broken down into microparticles using one of the physical (mechanical) processes listed above. However, it should be understood that the peeling or separation of the silicone material from a specific substrate or article may not be perfect and may result in a small residual fraction of accidental non-silicone contaminants, such as small fragments of the fabric or plastic substrate, which may be present in an amount of less than 10 weight percent, preferably 5 weight percent or less, of the microparticle mixture in the physically recycled and / or regenerated silicone elastomer microparticles (e)(i) produced, and that the smaller this amount, the more desirable it is.

[0077] Physical recycling and / or regeneration using one or more of the different methods described above provides the following:

[0078] 1) Advantage of being reusable as a weapon filler,

[0079] 2) The ability to incorporate contaminated feedstock from developed silicon elastomers and the ability to allow residual Si-H from hydrosilylated cured silicon elastomers without the need to undergo depolymerization, neutralization, filtration, and stripping steps associated with chemical recycling processes.

[0080] In one example, a cured silicone rubber sample is a commercially available Mikro from Hosokawa Micron Corporation. TMBefore being fed into a mill such as the UMP-B mill, the rubber sample was shredded with a paper shredder or cut with scissors until it reached a predetermined size, e.g., less than 2 cm. The shredded / cut rubber sample may be mixed with dry ice (which can be ground into powder using a mortar and pestle) in an approximate 1:1 weight ratio to help lower the temperature of the rubber and prepare it for milling. Subsequently, the rubber / dry ice mixture may be fed into a suitable mill using a knife-blade rotor rotating at > 10,000 rpm. The rubber may then exit the milling chamber through a stainless steel screen when cut finer than the hole size of the screen, for example, round holes with a diameter of 2 to 3 mm may be used for the first pass. Subsequently, the rubber milled during the first pass may undergo a second pass using dry ice as before, and Mikro during the second pass time using a 1 mm slot screen TM It can be supplied through the UMP-B mill.

[0081] If more accurate particle size is desired, the size measurement sample can be a Beckman Coulter with a tornado (dry) commercially available, for example, from Beckman Coulter Inc. TM It can be measured using laser diffraction with an LS 13 320 particle size analyzer, which is Beckman Coulter TM The diffraction signal is deconvoluted using software into a particle size distribution determined using the Fraunhofer diffraction model.

[0082] Penetration and swelling of pre-formed silicone elastomer microparticles (e)(i) by an organopolysiloxane polymer swelling agent (e)(ii) having a zero shear viscosity of 15,000 mPa·s or less (≤) at 25℃

[0083] As discussed above, the pre-formed silicone elastomer microparticles (e)(i) in the hydrosilylated curable silicone rubber coating composition cured herein have an average non-swelling particle size of 1 mm or less. However, recycled and / or regenerated pre-formed silicone elastomer microparticles (e)(i) are not merely directly mixed into the standard hydrosilylated curable silicone rubber coating composition, but are encapsulated therein as the composition cures. These are initially immersed in and / or contained in a low-viscosity organopolysiloxane polymer having a zero shear viscosity (e)(ii) of 15,000 mPa·s or less (≤) at 25°C, alternatively a zero shear viscosity (e)(ii) of 100 to 13,000 mPa·s at 25°C, alternatively a zero shear viscosity (e)(ii) of 100 to 10,000 mPa·s at 25°C, alternatively a zero shear viscosity (e)(ii) of 100 to 7,500 mPa·s at 25°C, alternatively a zero shear viscosity (e)(ii) of 100 to 5,000 mPa·s at 25°C, or alternatively a zero shear viscosity (e)(ii) of 100 to 2,000 mPa·s at 25°C. Examples of (e)(ii) include vinyl dimethyl-terminated divinyl functional polydimethylsiloxane, hydroxyl-terminated polydiorganosiloxane, alkoxy-terminated polydiorganosiloxane, or siloxane crosslinking agents defined herein as component (c), such as polymethylhydrogen dimethylsiloxane copolymer. These may also be unreacted silicone crosslinking agents, such as trimethyl-terminated polydimethylsiloxane. Organopolysiloxane polymer swelling agent (e)(ii) is present in the hydrosilylated curable silicone rubber coating composition in an amount of about 1.0 to 5.0 weight percent of the composition.

[0084] The pre-formed silicone elastomer microparticles (e)(i) may or may not be reactive with the organopolysiloxane polymer (e)(ii) having a zero shear viscosity of ≤ 15,000 mPa·s at 25°C, and likewise may or may not be reactive with the components of the coating composition on which it is to be located.

[0085] It has been discovered that the inclusion of a pre-cured phase of pre-formed silicone elastomer microparticles (e)(i) within a second curable network with an organopolysiloxane polymer (e)(ii) having a zero shear viscosity of ≤ 15,000 mPa·s at 25°C, capable of penetrating and swelling the pre-formed silicone elastomer microparticles (e)(i), provides a means of forming a dual network or an interpenetrating network (IPN). Without relying on currently accepted theory, it is believed that the pre-formed silicone elastomer microparticle component (e)(i) consists of a pre-cured cross-linked "mesh" component, and the composition in which component (e)(ii) forms part also forms a cross-linked network, and due to the ability of component (e)(ii) to penetrate and swell component (e)(i), the two networks are physically intertwined and physically bonded rather than merely encapsulated. It was found that the lower the viscosity value of component (e)(ii), the greater the penetration and swelling of component (e)(i).

[0086] Additionally, penetration and swelling did not occur or occurred minimally when component (e)(ii) had a zero shear viscosity greater than 15,000 mPa·s at 25°C. Components (e)(i) and (e)(ii) were compatible, so there were no problems with component (e)(ii) penetrating and swelling into component (e)(i) when the zero shear viscosity of component (e)(ii) was within the specified range. However, considering that the pre-formed silicone elastomer microparticles (e)(i) are thermosetting materials, due to their cross-linked nature, they cannot be dissolved in component (e)(ii). Therefore, the silicone elastomer microparticles (e)(i) instead swell to accommodate the organopolysiloxane polymer of component (e)(ii). Therefore, the pre-formed silicone elastomer microparticles (e)(i) are physically bonded to the matrix and may not act as defects in the matrix, which can cause voids, surface protrusions, and / or other heterogeneity that are usually problematic when encapsulated and used as fillers.

[0087] In the first embodiment, the pre-formed silicone elastomer microparticles (e)(i) may be infiltrated and immersed in an organopolysiloxane polymer swelling agent (e)(ii) having a zero shear viscosity of 15,000 mPa·s or less (≤) at 25°C for a suitable period. In this embodiment, the organopolysiloxane polymer swelling agent (e)(ii) is preferably nit or pure. The suitable period may be at least 1 hour, alternatively at least 12 hours, alternatively at least 24 hours, or alternatively at least 48 hours. This allows the organopolysiloxane polymer swelling agent (e)(ii) to infiltrate and swell the pre-formed silicone elastomer microparticles (e)(i) to form component (e). This corresponds to step (2) of the method. Subsequently, the resulting mixture of the swollen (e)(i) and the residual (e)(ii) is added to a hydrosilylated curable silicone rubber coating composition or a part thereof, typically to a part B composition comprising step (3) in the method.

[0088] As previously specified, steps (1), (2), and optionally (3) may alternatively be performed simultaneously. In this embodiment, component (e) may be produced by swelling pre-formed silicone elastomer microparticles (e)(i) in a hydroxylated curable silicone rubber coating composition containing component (e)(ii) or, when stored in a number of parts before use, more typically in a part composition of a hydroxylated curable silicone rubber coating composition.

[0089] In this embodiment, swelling may occur over a period of time in which pre-formed silicone elastomer microparticles (e)(i) are stored in the presence of component (e)(ii) in the part of a hydroxylated curable silicone rubber coating composition containing component (e)(ii).

[0090] When the organopolysiloxane polymer swelling agent (e)(ii) is initially stored in one part of the two-part composition, e.g., in the part B composition, it may be present in an amount of 2% to 10% by weight of the part B composition before being mixed with part A in a 1:1 weight ratio. Typically, the part B composition is used when it does not contain any catalyst, and the pre-formed silicone elastomer microparticles may contain Si-H groups that can initiate some curing during storage when mixed with a catalyst.

[0091] In this embodiment, the organopolysiloxane polymer swelling agent (e)(ii) may comprise or be composed of component (c) crosslinking agent or at least 1.0 weight% of component (a) or a mixture of component (c) and at least 1.0 weight% of component (a), or may be an organopolysiloxane polymer plasticizer. The pre-formed silicone elastomer microparticles (e)(i) are swollen after being added to the relevant part of the composition containing component (e)(ii).

[0092] For example, a swelling agent may be introduced into the Part B composition (described in more detail below), and pre-formed silicone elastomer microparticles (e)(i) are swollen in the Part B composition for a set period, then the Part A composition and the Part B composition are mixed together, and the hydrosilylated curable silicone rubber coating composition is cured.

[0093] Typically, pre-formed silicone elastomer microparticles (e)(i) will remain in a swollen state in the presence of an organopolysiloxane polymer swelling agent (e)(ii) throughout their service life, even after curing.

[0094] In one embodiment of the present invention, when component (e)(i) is known to be derived from hydrosilylated cured silicone rubber, the resulting pre-formed silicone elastomer microparticles will contain residual Si-H, which react with the matrix during curing and may cause weak parts in the final article, leading to cracking at lower elongation. In such cases, simultaneously with or prior to the penetration and swelling steps, the component (e)(i) microparticles may be treated with a monofunctional capping agent (e)(iii), which may be, for example, a polydiorganosiloxane having one unsaturated group per molecule, i.e., one alkenyl group per molecule. In practice, the monofunctional capping agent (e)(iii) may also function as a swelling agent by interacting with the residual Si-H groups while swelling the pre-formed silicone elastomer microparticles. Conversely, if residual vinyl is present in the pre-formed silicone elastomer microparticles, it may be beneficial to treat the microparticles, and the swelling agent may also include a mono-Si-H functional capping agent (e)(iii). When capping, the non-reactive component (e)(ii) is mainly added to expose the Si-H trapped inside the microparticles to improve the efficiency of the capping reaction, and the monofunctional capping agent is typically a monoalkenyl functional monomer or oligomer or a monoalkyne functional monomer or oligomer, for example, a linear or branched alkene or alkyne having 2 to 20 carbons, or alternatively 6 to 15 carbons, having one reactive alkene or alkyne group per molecule, such as 1-dodecane.

[0095] If an alkene or alkyne group is available for interaction with Si-H of pre-formed silicone elastomer microparticles that have been hydrosily cured, other compounds having a single alkene or alkyne group may alternatively be utilized as capping agents (e)(iii). Examples include alkyl vinyl ethers, e.g., ethyl vinyl ether and dodecyl vinyl ether; monovinyl polydimethylsiloxane; acrylates and methacrylates, e.g., methyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, iso-octyl acrylate, stearyl methacrylate, trimethoxysilylpropyl methacrylate, isobornyl methacrylate, and hexafluoroisopropyl methacrylate; polyalkylene glycols comprising one alkenyl and / or alkyneyl group, e.g., monovinyl polyethylene glycol, monovinyl polypropylene glycol, and monovinyl polyethylene polypropylene glycol copolymer; Monoallyloxy polyalkylene glycol, e.g., monoallyloxy polyethylene glycol and monoallyloxy polypropylene glycol and monoallyloxy polyethylene polypropylene glycol copolymer; styrene, α-methyl styrene, acrylic acid, and hexafluoroisopropyl methacrylate.

[0096] When the pre-formed silicone elastomer microparticles (e)(i) are condensed and cured, the microparticles can be capped with a compound having a single reactive group, which will react, for example, with the reactive group of the pre-formed silicone elastomer microparticles.

[0097] Alkoxysilanes, e.g., n-octyltrimethoxysilane, n-undecyltrimethoxysilane, methyltrimethoxysilane, isobutyltrimethoxysilane, n-propyldimethylmethoxysilane, n-butyltrimethoxysilane, ethyltrimethoxysilane, n-octylmethyldimethoxysilane, and n-propylmethyldimethoxysilane; alkenyl trialkoxysilanes, e.g., vinyltrimethoxysilane, allyltrimethoxysilane, hexenyltrimethoxysilane, and undecylenyltrimethoxysilane; alkenyldialkoxyalkylsilanes, e.g., vinyldimethoxymethylsilane, allyldimethoxymethylsilane, hexenyldimethoxymethylsilane, and undecylenyldimethoxymethylsilane; Alkenyl alkoxydialkyl silanes, e.g., vinyl methoxydimethylsilane, allyl methoxydimethylsilane, hexenyl methoxydimethylsilane, and undecylenyl methoxydimethylsilane; glycidoxyalkyltrialkoxysilanes, e.g., glycidoxypropyltrimethoxysilane and glycidoxymethyltrimethoxysilane; glycidoxyalkyldialkoxyalkyl silanes, e.g., glycidoxypropyldimethoxymethylsilane, glycidoxymethyldimethoxymethylsilane; and glycidoxyalkyl alkoxydialkyl silanes, e.g., glycidoxypropylmethoxydimethylsilane, glycidoxymethylmethoxydimethylsilane and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

[0098] These monofunctional capping agents (e)(iii) are intended to function as network modification additives to "adjust" tensile properties by promoting the interface between the hydrosilylated curable silicone rubber coating composition and the pre-formed silicone elastomer particulate phase, and thus the physical entanglement between the hydrosilylated curable silicone rubber coating composition and the particulate phase. The capping step may also be performed simultaneously with steps (1), (2), and optionally step (3).

[0099] When pre-formed silicone elastomer microparticles are capped, they can be mixed into a hydrosilylated curable silicone rubber coating composition. Generally, it is easier to first mix the capped pre-formed silicone elastomer microparticles into the hydrosilylated curable silicone rubber coating composition, e.g., Part B mentioned above. In this situation, the swelling step may occur during capping and / or after adding the capped pre-formed silicone elastomer microparticles to the hydrosilylated curable silicone rubber coating composition.

[0100] Swollen component (e)

[0101] Typically, after component (e)(i) is swollen by component (e)(ii) and optionally passivated for a set time by capping agent (e)(iii), said component (e) is present in an amount of 5% to 80% by weight of the hydrosilylated reaction-curable silicone rubber coating composition, alternatively in an amount of 5% to 50% by weight of the composition, alternatively in an amount of 7.5% to 35% by weight of the composition, alternatively in an amount of 7.5% to 30% by weight of the composition, and alternatively in an amount of 9.0% to 25% by weight of the composition.

[0102] In addition to components (e)(i) and (e)(ii), a hydrosilylated curable silicone rubber coating composition used to manufacture coated fabric articles, such as airbags or airbag fabric articles, comprises the following components:

[0103] Component (a)

[0104] A component (a) of a hydrosilylated curable silicone rubber coating composition used to manufacture coated fabric articles, such as airbags or airbag fabric articles coated with a cured product, is one or more organopolysiloxane polymers having a viscosity of 100 to 200,000 mPa·s at 25°C and at least two unsaturated groups per molecule, wherein the unsaturated groups are selected from alkenyl groups and / or alkynyl groups. Each organopolysiloxane polymer of component (a) comprises a plurality of siloxy units of the following chemical formula (I):

[0105] R' a SiO (4-a) / 2 (I)

[0106] The subscript "a" is 0, 1, 2, or 3.

[0107] When R' is as described above, or alternatively an alkyl group, typically a methyl group, the siloxy unit may be denoted by abbreviated nomenclature, namely "M", "D", "T", and "Q". The M unit is a siloxy unit where a = 3, i.e., R'3SiO 1 / 2 It corresponds to; the unit of D is the siloxy unit where a = 2, i.e., R'2SiO 2 / 2 It corresponds to; the unit of T is the siloxy unit where a = 1, i.e., R'1SiO 3 / 2 It corresponds to; the Q unit is the siloxy unit where a = 0, i.e., SiO 4 / 2 It corresponds to. The organopolysiloxane polymer of component (a) is substantially linear, but may contain some branches due to the presence of T units (as previously described) within the molecule, so the average value of a in structure (I) is about 2.

[0108] The unsaturated group of component (a) may be located at a terminal or suspended position on the organopolysiloxane polymer, or at both positions. The unsaturated group of component (a) may be an alkenyl group or an alkenyl group as described above. Each alkenyl group may comprise, when present, 2 to 30, alternatively 2 to 24, alternatively 2 to 20, alternatively 2 to 12, alternatively 2 to 10, and alternatively 2 to 6 carbon atoms. When present, the alkenyl group may be exemplified by, but is not limited to, vinyl, allyl, metallyl, propenyl, and hexenyl and cyclohexenyl groups. Each alkynyl group, when present, may also have 2 to 30, alternatively 2 to 24, alternatively 2 to 20, alternatively 2 to 12, alternatively 2 to 10, and alternatively 2 to 6 carbon atoms. Examples of alkynyl groups may be exemplified by, but are not limited to, ethynyl, propynyl, and butynyl groups. Preferred examples of unsaturated groups of component (a) include vinyl, propphenyl, isopropphenyl, butenyl, allyl, and 5-hexenyl.

[0109] In formula (I), each R' other than the unsaturated group described above is independently selected from an aliphatic hydrocarbyl group, a substituted aliphatic hydrocarbyl group, an aromatic group, or a substituted aromatic group. Each aliphatic hydrocarbyl group may be exemplified as an alkyl group having 1 to 20 carbons per group, alternatively 1 to 15 carbons per group, alternatively 1 to 12 carbons per group, alternatively 1 to 10 carbons per group, alternatively 1 to 6 carbons per group, or a cycloalkyl group such as cyclohexyl, but is not limited thereto. Specific examples of alkyl groups may include methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl groups, alternatively methyl and ethyl groups. The substituted aliphatic hydrocarbyl group is preferably a non-halogenated substituted alkyl group.

[0110] Aliphatic non-halogenated organyl groups are exemplified by, but are not limited to, suitable nitrogen-containing groups, e.g., amido groups, imido groups; oxygen-containing groups, e.g., polyoxyalkylene groups, carbonyl groups, alkoxy groups, and alkyl groups having substituents such as hydroxyl groups as described above. Additional organyl groups may include sulfur-containing groups, phosphorus-containing groups, and boron-containing groups. Examples of aromatic groups or substituted aromatic groups are phenyl groups and substituted phenyl groups having substituents as described above.

[0111] Component (a) may be selected from, for example, polydimethylsiloxane, alkylmethylpolysiloxane, alkylarylpolysiloxane or copolymers thereof (wherein the reference to alkyl means any suitable alkyl group, alternatively an alkyl group having two or more carbons), provided that the viscosity of the organopolysiloxane polymer (a) of each polymer must be 100 to 200,000 mPa·s at 25°C.

[0112] Therefore, component (a) can be the following as an example:

[0113] Dialkylalkenyl-terminated polydimethylsiloxane, e.g., dimethylvinyl-terminated polydimethylsiloxane; dialkylalkenyl-terminated dimethylmethylphenylsiloxane, e.g., dimethylvinyl-terminated dimethylmethylphenylsiloxane; trialkyl-terminated dimethylmethylvinyl polysiloxane; dialkylvinyl-terminated dimethylmethylvinyl polysiloxane copolymer; dialkylvinyl-terminated methylphenylpolysiloxane, dialkylalkenyl-terminated methylvinylmethylphenylsiloxane; dialkylalkenyl-terminated methylvinyldiphenylsiloxane; dialkylalkenyl-terminated methylvinylmethylphenyldimethylsiloxane; trimethyl-terminated methylvinylmethylphenylsiloxane; trimethyl-terminated methylvinyldiphenylsiloxane; or trimethyl-terminated methylvinylmethylphenyldimethylsiloxane.

[0114] In each case, the viscosity of component (a) organopolysiloxane polymer (a) must be 100 to 200,000 mPa.s at 25°C, alternatively 1000 to 150,000 mPa.s at 25°C, alternatively 1000 mPa.s to 125,000 mPa.s at 25°C, or alternatively 1000 mPa.s to 100,000 mPa.s at 25°C.

[0115] Unless otherwise specified, all given viscosity measurements are the zero shear viscosity (η) obtained by extrapolating the values ​​obtained at low shear rates to zero (or simply taking the average of the values) from the viscosity-shear rate curve at the rate-independent limit. o It is a value that is independent of the test method if a suitable and properly functioning rheometer is used. For example, at 25°C, the zero-shear viscosity of a material is 0.01 s without exceeding the transducer's torque limit. -1 , 0.1 s -1 , and 1.0 s -1This can be obtained using a commercial rheometer, such as the Anton-Parr MCR-301 rheometer or the TA Instruments AR-2000 rheometer, equipped with cone and plate fixtures of suitable diameter that generate an appropriate torque signal at a series of low shear rates. Alternatively, 0.1 to 10 s at a 25 mm cone and plate -1 Viscosity measurements can be obtained using the commercially available ARES-G2 rotational rheometer from TA Instruments with a constant speed sweep. If a zero-shear flat region cannot be observed at a shear rate accessible by the rheometer or viscometer, 0.1 s at 25°C -1 Report the viscosity measured at the standard shear rate.

[0116] Typically, the alkenyl and / or alkynyl content of the polymer, e.g., vinyl content, is 0.01 to 3 wt% for each organopolysiloxane polymer containing at least two silicon-bonded alkenyl groups per molecule of component (a), alternatively 0.01 to 2.5 wt% of component (a), alternatively 0.001 to 2.0 wt%, alternatively 0.01 to 1.5 wt% of component (a) of an organopolysiloxane polymer containing at least two unsaturated groups per molecule or each organopolysiloxane polymer, and the unsaturated groups are selected from alkenyl groups or alkynyl groups per molecule of component (a). The alkenyl / alkynyl content of component (a) is determined using quantitative infrared analysis according to ASTM E168.

[0117] Component (a) may be present in the hydrosilylated curable silicone rubber coating composition in an amount of 40% to about 80% by weight of the hydrosilylated curable silicone rubber coating composition, alternatively 45% to 80% by weight of the composition, or alternatively 50% to 80% by weight of the hydrosilylated curable silicone rubber coating composition. Typically, component (a) is present in an amount that is the difference between 100% by weight and the cumulative weight percentage of other components / components of the composition.

[0118] Component (b)

[0119] Component (b) of the hydrosilylated curable silicone rubber coating composition used to manufacture coated fabric articles, such as airbags or airbag fabric articles coated with a cured product, is a reinforcing filler comprising fumed silica, precipitated silica, or a mixture thereof, but may also include calcium carbonate, typically precipitated calcium carbonate. The reinforcing filler is provided to enhance the physical properties of the elastomer provided when the composition is cured. Silica in a finely divided form is preferred. The reinforcing filler (b), for example, a silica filler having a relatively high surface area, typically at least 50 m² / g (BET method according to ISO 9277:2010), is utilized. For example, 50 to 450 m² 2 / g, alternatively 50 to 400 m 2 / g, alternatively 50 to 300 m 2 / g, alternatively 100 to 300 m 2 A filler having a surface area of ​​ / g (BET method according to ISO 9277: 2010) (e.g., fumed silica) is typically used.

[0120] Typically, reinforcing filler(s)(b) are naturally hydrophilic (e.g., untreated) silica fillers and are therefore treated with a treatment agent to make them hydrophobic. These surface-modified reinforcing fillers (b) can be homogeneously incorporated into the organopolysiloxane polymer (a) without clumping, as described below, because the surface treatment makes the filler easily wetted by the organopolysiloxane polymer (a).

[0121] Typically, reinforcing filler (b) is surface-treated with any low molecular weight organosilicon compound disclosed in the art applicable to prevent creeping of the organosiloxane composition during processing. For example, the filler(s) can be made hydrophobic using an organosilane, polydiorganosiloxane, or organosilazane, such as a hexaalkyl disilazane, a short-chain siloxane diol, or a fatty acid or fatty acid ester, such as a stearate, thereby making handling easier and making it easier to obtain a homogeneous mixture with other components. Specific examples include, but are not limited to, silanol-terminated trifluoropropylmethylsiloxane, silanol-terminated vinylmethylsiloxane, tetramethyldi(trifluoropropyl)disilazane, tetramethyldivinyldisilazane, hexamethyldisilazane (HMDZ), silanol-terminated MePh siloxane, liquid hydroxyl-terminated polydiorganosiloxane, hexaorganodisiloxane, and hexaorganodisilazane containing an average of 2 to 20 repeating units of diorganosiloxane within each molecule. A small amount of water may be added along with the silica treatment agent(s) as a processing aid.

[0122] The reinforcing silica filler (b) may be pretreated or treated in situ (i.e., in the presence of at least some of the other components of the hydrosilylated curable silicone rubber coating composition of the present invention by blending these components together at room temperature or above until the filler is completely treated) before being introduced into the hydrosilylated curable silicone rubber coating composition. Typically, when present, the untreated reinforcing filler (b) is treated in situ with a treatment agent in the presence of the organopolysiloxane polymer (a), which produces a silicone rubber base material that can subsequently be mixed with other components.

[0123] When present, reinforcing filler (b) is present in an amount of 1.0 to 40 weight% of the composition, alternatively 1 to 30 weight% of the composition, or alternatively 5.0 to 25 weight% of the composition, in a hydrosilylated curable silicone rubber coating composition used to manufacture an airbag or airbag fabric article coated with a cured product.

[0124] Ingredients (c)

[0125] Component (c) of the hydrosilylated curable silicone rubber coating composition used to manufacture coated fabric articles, such as airbags or airbag fabric articles coated with a cured product, functions as a crosslinking agent and is provided in the form of an organosilicon compound having an average of at least two or alternatively at least three Si-H groups per molecule. Component (c) is typically a linear, branched, or silicone resin. Component (c) usually contains three or more silicon-bonded hydrogen atoms so that the hydrogen atoms react with the unsaturated groups (alkenyl and / or alkynyl groups) of component (a) and / or the rest of the composition to form a network structure together, thereby causing the composition to cure. Part or all of component (c) may alternatively have two silicon-bonded hydrogen atoms per molecule. However, such molecules are used as the sole crosslinking agent only when, for example, the polymer (a) has more than two unsaturated groups per molecule, in which case a network may be formed during the curing process. Otherwise, when component (c) partially contains a molecule having an average of 2 silicon-bonded hydrogen atoms per molecule, said molecule can function as a chain extender.

[0126] The molecular composition of the organosilicon compound having at least two, or alternatively at least three, Si-H groups per molecule (c) is not particularly limited and may be a silane or a straight-chain, branched (straight-chain with some branching through the presence of T units), or a cyclic polymer or a silicone resin system.

[0127] All viscosities are measured at 25°C and are zero-shear measurements using the previously described method. The silicon-bonded organic group used in component (c) may be exemplified by an alkyl group, e.g., methyl, ethyl, propyl, n-butyl, t-butyl, pentyl, hexyl; an aryl group, e.g., phenyl, tolyl, xylyl, or similar aryl groups; 3-chloropropyl, 3,3,3-trifluoropropyl, or similar halogenated alkyl groups, preferably alkyl groups having 1 to 6 carbons, in particular methyl, ethyl, or propyl groups, or phenyl groups. Alternatively, the silicon-bonded organic group used in component (c) is an alkyl group, alternatively a methyl group, ethyl group, or propyl group.

[0128] An example of an organosilicon compound (c) having at least two or alternatively at least three Si-H groups per molecule is

[0129] (a') Trimethylsiloxy-terminated methylhydrogenpolysiloxane,

[0130] (b') Trimethylsiloxy-terminated polydimethylsiloxane-methylhydrogensiloxane,

[0131] (c') Dimethylhydrogensiloxy-terminated dimethylsiloxane-methylhydrogensiloxane copolymer,

[0132] (d') Dimethylsiloxane-methylhydrogensiloxane cyclic copolymer,

[0133] (e') (CH3)2HSiO 1 / 2 Unit, (CH3)3SiO 1 / 2 Units, and SiO 4 / 2 Copolymer and / or silicone resin composed of units,

[0134] (f') (CH3)2HSiO 1 / 2 Units and SiO 4 / 2 Copolymer and / or silicone resin composed of units,

[0135] (g') It comprises, but is not limited to, a methylhydrogensiloxane cyclic homopolymer having 3 to 10 silicon atoms per molecule;

[0136] Alternatively, component (c), the crosslinking agent may be a filler, such as silica treated with one of the above and a mixture thereof.

[0137] In one embodiment, component (c) is selected from methylhydrogenpolysiloxane capped with trimethylsiloxy groups at both ends of the molecule; a copolymer of methylhydrogensiloxane and dimethylsiloxane capped with trimethylsiloxy groups at both ends of the molecule; dimethylsiloxane capped with dimethylhydrogensiloxy groups at both ends of the molecule; and a copolymer of methylhydrogensiloxane and dimethylsiloxane capped with dimethylhydrogensiloxy groups at both ends of the molecule.

[0138] The crosslinking agent (c) is generally present in the hydrosilylated reaction-curable silicone rubber coating composition such that the molar ratio of silicon-bonded hydrogen atoms of component (c) to total unsaturated groups selected from alkenyl groups and / or alkynyl groups of the composition is 0.5:1 to 20:1. When this ratio is less than 0.5:1, a well-cured composition will not be obtained. When the ratio exceeds 20:1, the hardness of the cured hydrosilylated reaction-curable silicone rubber coating composition tends to increase when heated.

[0139] The molar ratio of silicon-bonded hydrogen atoms of component (c) to total unsaturated groups selected from alkenyl groups and / or alkynyl groups of organopolysiloxane (a) is preferably at least 0.8:1 and may be up to 8:1 or 10:1. Most preferably, the molar ratio of Si-H groups to aliphatic unsaturated groups is in the range of 1.1:1 to 5:1.

[0140] The silicon-bonded hydrogen (Si-H) content of component (c) is determined using quantitative infrared analysis according to ASTM E168. In this case, the ratio of silicon-bonded hydrogen to alkenyl (vinyl) and / or alkynyl is important when relying on the hydrosilylation curing process. Generally, this is determined by calculating the total weight% of alkenyl groups, e.g., vinyl [V], in the hydrosilylation-curable silicone rubber coating composition and the total weight% of silicon-bonded hydrogen [H] in the composition, and considering that the molecular weight of hydrogen is 1 and the molecular weight of vinyl is 27, the molar ratio of silicon-bonded hydrogen to vinyl is 27[H] / [V].

[0141] Typically, depending on the number of unsaturated groups in component (a) and the remainder of the hydrosilylated curable silicone rubber coating composition as well as the number of Si-H groups in component (c), component (c) will be present in an amount of 0.1 to 10 weight% of the hydrosilylated curable silicone rubber coating composition, alternatively 0.1 to 7.5 weight% of the hydrosilylated curable silicone rubber coating composition, alternatively 0.25 to 7.5 weight%, and further alternatively 0.25 to 5 weight% of the hydrosilylated curable silicone rubber coating composition.

[0142] (d) Hydrosilylation catalyst

[0143] Component (d) of the hydrosilylated curable silicone rubber coating composition used to manufacture coated fabric articles, such as airbags or airbag fabric articles coated with a cured product, is a hydrosilylation catalyst comprising or composed of platinum group metals or compounds thereof. These are generally selected from catalysts of platinum group metals (platinum, ruthenium, osmium, rhodium, iridium, and palladium) or compounds of one or more of these metals. Alternatively, platinum and rhodium compounds are preferred due to the high activity levels of these catalysts in the hydrosilylation reaction, and platinum compounds are most preferred. In the hydrosilylation (or addition) reaction, a hydrosilylation catalyst such as component (d) of the present invention catalyzes the reaction between an unsaturated group, generally an alkenyl group, such as vinyl, and a Si-H group.

[0144] The hydrosilylation catalyst of component (d) may be a platinum group metal, a platinum group metal deposited on a carrier such as activated carbon, a metal oxide such as silicon dioxide, silica gel or powdered charcoal, or a compound or complex of a platinum group metal. Preferably, the platinum group metal is platinum.

[0145] Examples of preferred hydrosilylation catalysts of component (d) include platinum-based catalysts, e.g., platinum black, platinum oxide (Adams catalyst), platinum on various solid supports, chloroplatinic acid, e.g., hexachloroplatinic acid (Pt oxidation state IV) (Spire catalyst), chloroplatinic acid in solution of alcohol, e.g., isooctanol or amyl alcohol (Lamorrow catalyst), and complexes of chloroplatinic acid having an ethylene-based unsaturated compound such as an olefin and an organosiloxane containing an ethylene-based unsaturated silicon-bonded hydrocarbon group, e.g., tetra-vinyl-tetramethylcyclotetrasiloxane-platinum complex (Ashby catalyst). Soluble platinum compounds that may be used include, for example, platinum-olefin complexes of the formulas (PtCl2.(olefin)2 and H(PtCl3.olefin); in this context, it is preferable to use 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. Other soluble platinum catalysts are, for example, platinum-cyclopropane complexes of the formula (PtCl2C3H6)2, reaction products of hexachloroplatinic 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 ethanol solution. Platinum catalysts having phosphorus, sulfur, and amine ligands, for example, (Ph3P)2PtCl2; and a complex of vinylsiloxane and platinum, such as sym-divinyltetramethyldisiloxane (Carsted catalyst), may also be used.

[0146] Accordingly, specific examples of suitable platinum-based catalysts of component (d) include the following:

[0147] (i) a complex of an organosiloxane containing an ethylene-based unsaturated hydrocarbon group and a chloroplatinic acid as described in U.S. Patent No. 3,419,593;

[0148] (ii) chloroplatinic acid in the hexahydrate or anhydrous form;

[0149] (iii) a platinum-containing catalyst obtained by a method comprising the step of reacting a chloroplatinic acid with an aliphatic unsaturated organosilicon compound, e.g., divinyltetramethyldisiloxane;

[0150] (iv) an alkene-platinum-silyl complex as described in U.S. Patent No. 6,605,734, e.g., (COD)Pt(SiMeCl2)2, where “COD” is 1,5-cyclooctadiene; and / or

[0151] (v) Karstedt catalyst, typically a platinum divinyl tetramethyl disiloxane complex containing about 1 wt% platinum in a vinyl siloxane polymer. Historically, solvents such as toluene and similar organic solvents have been used as alternatives, but the use of vinyl siloxane polymers has been the preferred choice to date. These are described in U.S. Patent No. 3,715,334 and U.S. Patent No. 3,814,730. In a preferred embodiment, component (d) may be selected from platinum coordination compounds. In one embodiment, hexachloroplatinic acid having a vinyl-containing siloxane and its conversion product, Karstedt catalyst, and Spire catalyst are preferred. In one embodiment, the catalyst may be encapsulated during storage, particularly for one part composition, to prevent premature curing.

[0152] The amount of the hydrosilylation catalyst is generally 0.01 ppm to 10,000 parts by weight per million parts (ppm) of the weight of the hydrosilylation curable silicone rubber coating composition; alternatively, 0.1 to 7500 ppm; alternatively, 100 to 75000 ppm; and alternatively, 500 to 6,000 ppm of a platinum group metal. These ranges may relate solely to the metal content within the catalyst or to the specified catalyst as a whole (including its ligands), but typically, these ranges relate solely to the metal content within the catalyst. 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, for example in a polymer or solvent, the amount of component (d) present will be in the range of 0.001 to 3.0 wt% of the hydrosilylated curable silicone rubber coating composition, alternatively 0.001 to 1.5 wt% of the composition, alternatively 0.01 to 1.5 wt%, or alternatively 0.01 to 0.1 wt% of the hydrosilylated curable silicone coating composition.

[0153] (f) Adhesion promoter

[0154] Component (f) of the hydrosilylated curable silicone rubber coating composition used to manufacture coated fabric articles, such as airbags or airbag fabric articles coated with a cured product, is any suitable adhesion promoter. The adhesion promoter may be, for example, an alkoxysilane coupling agent. Examples of adhesion promoters that may be incorporated into the moisture-curable composition according to the present invention include alkoxysilanes, for example, aminoalkylalkoxysilanes, for example, 3-aminopropyltriethoxysilane, epoxyalkylalkoxysilanes, for example, 3-glycidoxypropyltrimethoxysilane, and mercapto-alkylalkoxysilanes, (trimethoxysilyl)ethane and (meth)acryloxy type adhesion promoters, for example, methacryloxypropyltrimethoxysilane and reaction products of ethylenediamine and silyl acrylate. An isocyanurate containing silicon groups, such as 1,3,5-tris(trialkoxysilylalkyl) isocyanurate, may be additionally used. The adhesion promoter may be present in an amount of 0.1 to 5.0 weight% of the hydrosilylation reaction-curable silicone rubber coating composition, alternatively 0.1 to 3.5 weight% of the composition, alternatively 0.1 to 2.5 weight% of the composition, alternatively 0.1 to 2.25 weight% of the composition, or alternatively 0.2 to 2.0 weight% of the composition.

[0155] Additionally, suitable adhesion promoters are reaction products of epoxyalkylalkoxysilane, such as 3-glycidoxypropyltrimethoxysilane, amino-substituted alkoxysilane, such as 3-aminopropyltrimethoxysilane, and optionally alkylalkoxysilane, such as methyltrimethoxysilane.

[0156] In one alternative, the contact promoter may be a combination of an alkoxysilane coupling agent and an organometallic bonding catalyst, such as zirconium (IV) tetraacetyl acetonate (sometimes referred to as zirconium AcAc4) or aluminum (III) triacetyl acetonate (sometimes referred to as aluminum AcAc3). Typically, such a catalyst is introduced in an amount of 0.05 to 0.3 weight percent of the composition.

[0157] Ingredients (g) (Optional)

[0158] One or more optional silicone resins of the component (g) of the hydrosilylated curable silicone rubber coating composition used to manufacture coated fabric articles, such as airbags or airbag fabric articles coated with a cured product, are silicone resins containing unsaturated groups selected from T silicone resin (silsesquioxane), DT silicone resin, MQ silicone resin, MDT silicone resin, MTQ silicone resin, QDT silicone resin, or mixtures thereof, alkenyl groups, alkynyl groups, or mixtures of alkenyl groups.

[0159] These resins of component (g) using the MDTQ nomenclature are of the Q type (SiO2) as specified. 4 / 2 ) Siloxane unit, T type(R 2 1SiO 3 / 2 ) Siloxane unit; D type(R 2 1SiO 3 / 2 ) Siloxane unit, and R 2 3SiO 1 / 2 (M) Contains siloxane units. These resins can be classified into two broad categories: silsesquioxanes and silicates. Silsesquioxanes or T resins are composed mainly of T units and can be synthesized by the hydrolysis and condensation of alkoxysilanes, chlorosilanes, or mixtures thereof. Silicates or MQ resins are composed mainly of M units and Q units and can be synthesized by the hydrolysis and condensation of alkoxysilanes and chlorosilanes. Alternatively, MQ resins can be synthesized by polymerizing water-soluble alkali silicates in the presence of acid and then reacting them with triorganoalkoxysilanes, triorganochlorosilanes, hexaorganodisiloxanes, or mixtures thereof.

[0160] Preferably, component (g) is one or more MQ resins. Typically, the MQ resin of component (g) is SiO₂ when present. 4 / 2 (Q) Siloxane unit and R4 3SiO 1 / 2 (M) Contains a siloxane unit, wherein in the above formula, each R 2 may be the same or different and represents a monovalent group selected from hydrocarbon groups having 1 to 20 carbon atoms and alternatively 1 to 12 carbon atoms. Suitable R 2 Examples of groups include alkyl groups such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl; alicyclic groups such as cyclohexyl; alkenyl groups having 2 to 12 carbons such as vinyl, propenyl, butenyl, pentenyl, hexenyl, etc.; alkynyl groups selected from ethinyl, propynyl, butinyl, pentinyl, or hexinyl, etc.; aryl groups such as phenyl, tolyl, xylyl, benzyl, alpha-methyl styryl, and 2-phenylethyl; alternatively, R 2 The group is a vinyl, methyl, ethyl, or phenyl group, for example, a preferred R 2 3SiO 1 / 2 (M) An example of a siloxane unit is Me3SiO 1 / 2 , PhMe₂SiO 1 / 2 , ViMe2SiO 1 / 2 , and Ph2MeSiO 1 / 2 It includes, wherein Me represents methyl, Vi represents vinyl, and Ph represents phenyl. The T silicone resin may alternatively be referred to as silsesquioxane. The silicone resin may be a single silicone resin or a mixture comprising two or more different silicone resins, each as described above. Typically, these are ViMe2SiO 1 / 2 It is an MQ resin containing

[0161] Me3SiO 1 / 2 and / or PhMe2SiO 1 / 2 It is combined with roof tiles.

[0162] In addition, the silicone resin contains residual oz 5 It is an MQ resin that can contain Z 5 can represent hydrogen or an alkyl group. OZ5 The group remains in the Q component after the synthesis of silicon MQ resin, which indicates an incomplete condensation reaction during the reaction producing the MQ resin if the OZ content satisfies the aforementioned hydroxyl requirements among the molar Si requirements. Residual OZ 5 It is unique to the processes and reactions utilized to produce MQ resin. MQ resin also has residual OZ 5 To further minimize it, a subsequent silylation reaction may be performed.

[0163] When the silicone resin (g) is present, it is typically delivered in a hydrocarbon or silicone solvent, and the silicone resin without solvent is typically solid, but preferably in the present invention, the silicone resin (g) is delivered in a silicone solvent such as a non-functional polydimethylsiloxane or polydimethylsiloxane containing two or more alkenyl groups per molecule, for example, as component (a) in the present invention.

[0164] For example, any suitable MQ resin may be used as component (g) if required. The molar ratio of M siloxane units to Q siloxane units has a value of 0.5:1 to 1.2:1, alternatively 0.6:1 to 1.1:1, alternatively 0.8:1 to 1.1:1, or alternatively 0.9:1 to 1.1:1. In one embodiment, the MQ resin (e) has M units of SiO₂ 4 / 2 siloxane units (i.e., Q units) are bonded to each Q unit, and each Q unit is at least one other SiO 4 / 2It comprises a resin portion bonded to a siloxane unit. The molar ratio of M units to Q units is 0.3:1 to 1.2:1, alternatively 0.4:1 to 1.1:1, alternatively 0.5:1 to 1:1, and alternatively 0.6:1 to 0.9:1. Such MQ resins suitable as component (g) may have a number average molecular weight (Mn) of 2,000 to 50,000 g / mol, alternatively 3,000 to 30,000 g / mol. In one embodiment, the silicone resin may be described in terms of mole fraction as an MQ silicone resin having the following chemical formula:

[0165] (R 4 3SiO 1 / 2 ) u (SiO 4 / 2 ) v

[0166] In the above equation, R 4 is C1 to C without aliphatic unsaturation 10 It is a hydrocarbon group, u is 0.3 to 0.6, alternatively 0.37 to 0.52, v is 0.4 to 0.7, alternatively 0.48 to 0.63, and the value of u + v is 1.0.

[0167] Methods for manufacturing silicone resins are well known in the art. For example, they can be prepared by treating a resin copolymer produced by a silica hydrosol capping process with an alkyl and / or alkenyl-containing terminal blocker. This is preferably done by reacting the silica hydrosol under acidic conditions with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, and combinations thereof, and then M(R3SiO₂) containing 0.07 to 0.2 moles of hydroxyl per mole of silicon (Si). 1 / 2 ) units and Q(SiO 4 / 2It includes recovering a copolymer having ) units. The copolymer may further react with a terminal blocker containing saturated organic groups to achieve less than 0.06 moles of hydroxyl per mole Si. Suitable terminal blockers include silazanes, siloxanes, silanes, and combinations thereof.

[0168] When present, the component (g) may be present in an amount of 1 to 60 weight%, alternatively 1 to 40 weight%, in the hydrosilylated curable silicone rubber coating composition, preferably in the form of an MQ resin.

[0169] Methods for manufacturing silicone resins are well known in the art. For example, they can be prepared by treating a resin copolymer produced by a silica hydrosol capping process with an alkyl and / or alkenyl-containing terminal blocker. This is preferably done by reacting the silica hydrosol under acidic conditions with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, and combinations thereof, and then M(R3SiO₂) containing 0.07 to 0.2 moles of hydroxyl per mole of silicon (Si). 1 / 2 ) units and Q(SiO 4 / 2 It includes recovering a copolymer having ) units. The copolymer may further react with a terminal blocker containing saturated organic groups to achieve less than 0.06 moles of hydroxyl per mole Si. Suitable terminal blockers include silazanes, siloxanes, silanes, and combinations thereof.

[0170] Preferably, when component (b) is absent, component (g) is present to reinforce the coating. In this case, when (b) is absent and (g) is present, the silicone resin (g) comprises one or more unsaturated groups, such as vinyl groups, and alternatively, the silicone resin (g) is a vinylized MQ resin. Preferably, component (b) or component (g) is present, or a mixture of components (b) and (g) is present in the composition.

[0171] Components (a), (c), and (g) always consist of mixtures of macromolecular species with different degrees of polymerization and consequently different molecular weights. There are different types of average polymer molecular weights, which can be measured in different experiments. The two most important are the number average molecular weight (Mn) and the weight average molecular weight (Mw). The Mn and Mw of silicone polymers and / or resins can be determined via gel permeation chromatography (GPC) using a polystyrene calibration standard. This technique is the standard and yields Mw, Mn, and the polydispersity index (PI). Degree of polymerization (DP) = Mn / Mu, where Mn is derived from GPC measurements and Mu is the molecular weight of the monomer unit. PI = Mw / Mn. DP is linked to the viscosity of the polymer through Mw, and the higher the DP, the higher the viscosity. Silicone resins typically have a weight average molecular weight (M) of 2,000 to 50,000 daltons, alternatively 3,000 to 40,000, alternatively 3,000 to 30,000, alternatively 4,000 to 30,000, and alternatively 5,000 to 25,000. w It has ), and the molecular weight is determined by gel permeation chromatography using a triple detector system, such as a light scattering detector, a refractive index detector, and / or a viscosity detector and a polystyrene standard.

[0172] Additional optional components

[0173] Additional optional components may be present in the hydrosilylated curable silicone rubber coating composition used to manufacture the coated fabric articles described herein, such as airbags or airbag fabric articles coated with a cured product, depending on the intended end use thereof. Examples of such optional components include curing inhibitors, pot life extenders, flame retardants, lubricants, non-reinforcing fillers, pigments, dyes and / or colorants, fungicides, wetting agents, heat stabilizers, compression set additives, metal deactivators, plasticizers, and mixtures thereof.

[0174] As described herein, when a hydrosilylated curable silicone rubber coating composition is cured via an addition / hydrosilylation reaction, a curing inhibitor may be utilized to inhibit the curing of the composition. Such curing inhibitors are utilized to prevent premature curing during storage and / or to obtain a longer working time or pot life of the hydrosilylated cured composition by delaying or inhibiting the activity of the catalyst. Curing inhibitors for hydrosilylation catalysts (d), e.g., platinum metal-based catalysts, are well known in the art and include hydrazine, triazole, phosphine, mercaptan, organic nitrogen compounds, acetylene alcohols, silylated acetylene alcohols, maleates, e.g., dibutyl maleate; fumarates, ethylene-based or aromatic unsaturated amides, ethylene-based unsaturated isocyanates, olefinic siloxanes, e.g., tetramethyltetravinylcyclotetrasiloxane; It may include unsaturated hydrocarbon monoesters and diesters, conjugated n-phosphorus, hydroperoxides, nitriles, and diaziridines. Alkenyl-substituted siloxanes described in U.S. Patent No. 3,989,667 may be used, among which cyclic methylvinylsiloxane is preferred.

[0175] One type of known curing inhibitor for a hydrosilylation catalyst, e.g., a platinum catalyst (d), includes an acetylene-based compound disclosed in U.S. Patent No. 3,445,420. Acetylene-based alcohols, e.g., 2-methyl-3-butyn-2-ol, constitute a preferred class of curing inhibitors that inhibit the activity of a platinum-containing catalyst at 25°C. Compositions containing such curing inhibitors typically require heating at a temperature of 70°C or higher to cure at a substantial rate.

[0176] Examples of acetylene-based alcohols and derivatives thereof include 1-ethynyl-1-cyclohexanol (ETCH), 2-methyl-3-butyn-2-ol, 3-butyn-1-ol, 3-methylbutynol 3-butyn-2-ol, propargyl alcohol, 2-phenyl-2-propin-1-ol, 3,5-dimethyl-1-hexin-3-ol, 1-ethynylcyclopentanol, 1-phenyl-2-propinol, 3-methyl-1-penten-4-phosph-3-ol, and mixtures thereof. In one alternative, the curing inhibitor is selected from one or more of 1-ethynyl-1-cyclohexanol (ETCH), tetramethyltetravinylcyclotetrasiloxane, 3-methylbutynol and / or dibutyl maleate.

[0177] When present, a curing inhibitor concentration as low as 1 mole per mole of metal of catalyst (d) will impart satisfactory storage stability and curing rate in some cases. In other cases, a curing inhibitor concentration of up to 500 moles per mole of metal of catalyst (d) is required. The optimal concentration for a given curing inhibitor in a given hydrosilylated curable silicone rubber coating composition herein is easily determined through conventional experimentation. The above mixture may also be used. When present in the composition, depending on the concentration and form in which the selected inhibitor is provided / commercially available, the curing inhibitor is typically present in an amount of 0.0001 to 10 weight% of the composition, alternatively 0.001 to 5% curing inhibitor, or alternatively 0.0125 to 5 weight%.

[0178] Pot life extenders, such as triazoles, may be used, but are not considered essential within the scope of the present invention. Accordingly, hydrosilylated curable silicone rubber coating compositions used to manufacture airbags or airbag fabric articles coated with a cured product may not have pot life extenders.

[0179] flame retardant Examples include calcium carbonate, such as precipitated calcium carbonate, aluminum trihydrate (ATH), magnesium dihydroxide (MDH) and HMH (a mixture of hydromagnesite and huntite), chlorinated paraffin, hexabromocyclododecane, triphenyl phosphate, dimethyl methylphosphonate, tris(2,3-dibromopropyl) phosphate (tris bromide), and mixtures or derivatives thereof. When present in the composition, the flame retardant may be present in an amount of 5 to 50 weight percent of the composition, as needed.

[0180] slush Examples include tetrafluoroethylene, resin powder, graphite, fluorinated graphite, talc, boron nitride, fluorine oil, silicone oil, molybdenum disulfide, and mixtures or derivatives thereof. When present in a hydrosilylated curable silicone rubber coating composition, the flame retardant is typically present in an amount of 0.1 to 5 weight percent of the composition.

[0181] Non-reinforced filler It may include crushed quartz, diatomaceous earth, barium sulfate, iron oxide, titanium dioxide and carbon black, talc, crushed calcium carbonate, and wollastonite. Other fillers that may be used alone or in addition to the above include aluminite, calcium sulfate (anhydrous stone), gypsum, calcium sulfate, magnesium carbonate, clay, e.g. kaolin, magnesium hydroxide, e.g. hydrotalc, graphite, copper carbonate, e.g. malachite, nickel carbonate, e.g. jarachite, barium carbonate, e.g. witherite and / or strontium carbonate, e.g. strontianite.

[0182] Other fillers may include silicates selected from the group consisting of olivine; garnet; aluminosilicate; ring silicate; chain silicate; and sheet silicate. The olivine group includes silicate minerals, e.g., forsterite and Mg2SiO4, to a lesser extent. The garnet group includes crushed silicate minerals, e.g., pyrope and Mg3Al2Si3O4, to a lesser extent. 12 ; Grosula; and Ca2Al2Si3O 12 Includes. Aluminosilicates include pulverized silicate minerals, e.g., non-limitedly sillimanite; Al2SiO5; mullite; 3Al2O3.2SiO2; kyanite; and Al2SiO5. Ring silicates can be utilized as non-reinforcing fillers, and these include silicate minerals, e.g., non-limitedly cordierite and Al3(Mg,Fe)2[Si4AlO 18 Includes ]. The chain silicate group includes crushed silicate minerals, e.g., wollastonite and Ca[SiO3], to the non-limiting extent. Sheet silicates may alternatively or additionally be used as non-reinforcing fillers, and a suitable group includes silicate minerals, e.g., mica, to the non-limiting extent; K2AI 14 [Si6Al2O 20 ](OH)4; pyrophyllite; Al4[Si8O 20 ](OH)4; Talc; Mg6[Si8O 20 ](OH)4; serpentine, e.g., asbestos; kaolite; Al4[Si4O 10 Includes ](OH)8; and vermiculite.

[0183] Examples of pigments include titanium dioxide, chromium oxide, bismuth and vanadium oxide, iron oxide, and mixtures thereof.

[0184] Hydrosilylated curable silicone rubber coating compositions that can be utilized coloring agentExamples include pigments, dry dyes, reactive dyes, acid dyes, chrome dyes, disperse dyes, cationic dyes, and mixtures thereof. The hydrosilylated curable silicone rubber coating compositions described herein may further comprise one or more pigments and / or colorants that may be added if desired. The pigments and / or colorants may be colored, white, black, metallic, and luminescent, such as fluorescent and phosphorescent. Pigments are utilized to color the composition as needed. Any suitable pigment may be utilized provided it is compatible with the composition of the present invention.

[0185] Suitable white pigments and / or colorants include titanium dioxide, zinc oxide, lead oxide, zinc sulfide, lithophone, zirconium oxide, and antimony oxide.

[0186] Suitable non-white inorganic pigments and / or colorants include, but are not limited to, iron oxide pigments, such as goethite, lepidocrosite, hematite, maghemite, and magnetite, black iron oxide, yellow iron oxide, brown iron oxide, and red iron oxide; blue iron pigments; chrome oxide pigments; cadmium pigments, such as cadmium yellow, cadmium red, and cadmium cinnabar; bismuth pigments, such as bismuth vanadate and bismuth vanadate molybdate; mixed metal oxide pigments, such as cobalt titanate green; chromate and molybdate pigments, such as chrome yellow, molybdate red, and molybdate orange; ultramarine pigments; cobalt oxide pigments; nickel antimony titanate; lead chrome; carbon black; lamp black; and metallic effect pigments, such as aluminum, copper, copper oxide, bronze, stainless steel, nickel, zinc, and brass.

[0187] Suitable organic non-white pigments and / or colorants are phthalocyanine pigments, e.g., phthalocyanine blue and phthalocyanine green; monoarylide yellow, diarylide yellow, benzimidazolone yellow, heterocyclic yellow, DAN orange, quinacridone pigments, e.g., quinacridone magenta and quinacridone violet; Organic red and other azo pigments including metallized azo red and non-metallized azo red, monoazo pigments, diazo pigments, azo pigment lakes, β-naphthol pigments, naphthol AS pigments, benzimidazolone pigments, diazo condensation pigments, isoindolinone and isoindoline pigments, polycyclic pigments, perylene and perinone pigments, thioindigo pigments, anthrapyrimidone pigments, flavantron pigments, antantron pigments, dioxazine pigments, triarylcarbonium pigments, quinophthalone pigments, and diketopyrrolopyrrole pigments.

[0188] Typically, pigments and / or colorants have an average particle diameter in the range of 10 nm to 50 μm, preferably in the range of 40 nm to 2 μm. Pigments and dyes may be used in the form of a pigment masterbatch composed of these dispersed in component (a) in a ratio of 25:75 to 70:30.

[0189] Hydrosilylated curable silicone rubber coating compositions used to manufacture airbags or airbag fabric articles coated with a cured product can be heat-stabilized. heat stabilizerExamples of may include metal compounds such as red iron oxide, yellow iron oxide, ferrous hydroxide, cerium oxide, cerium hydroxide, lanthanum oxide, copper phthalocyanine, fumed titanium dioxide, iron naphthenate, cerium naphthenate, cerium dimethylpolysilanolate, and acetylacetone salts of metals selected from copper, zinc, aluminum, iron, cerium, zirconium, titanium, etc. Other examples of heat stabilizers may include suitable antioxidants or metal scavengers such as salicylaminotriazole, 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine, 2-hydroxy-N-1H-1,2,4-triazole-3-ylbenzamide, and N'1,N'12-bis(2-hydroxybenzoyl)dodecanedihydrazide. When present in a hydrosilylated curable silicone rubber coating composition, the amount of heat stabilizer may be in the range of 0.01 to 1.0 weight% of the hydrosilylated curable silicone rubber coating composition.

[0190] Accordingly, a hydrosilylated curable silicone rubber coating composition used to manufacture an airbag or airbag fabric article coated with a cured product comprises the following:

[0191] a) an organopolysiloxane polymer having a zero shear viscosity of 100 to 200,000 mPa·s at 25°C, alternatively 1,000 to 150,000 mPa·s at 25°C, alternatively 1,000 mPa·s to 125,000 mPa·s, alternatively 1,000 mPa·s to 70,000 mPa·s at 25°C, having at least two unsaturated groups per molecule selected from alkenyl groups and / or alkynyl groups, in an amount of 40% to about 80% by weight of the composition, alternatively 45% to 80% by weight of the composition, or alternatively 50% to 80% by weight of the composition; all predetermined viscosity measurements are zero shear viscosities (η) determined as described above and in the examples. o ) value, taken at 25℃.

[0192] b) preferably one or more reinforcing fillers comprising fumed silica, precipitated silica, or a mixture thereof; at least 50 m² / g (BET method according to ISO 9277: 2010), alternatively 50 to 450 m 2 / g, alternatively 50 to 400 m 2 / gm 2 / g, alternatively 50 to 300 m 2 / g, alternatively 100 to 300 m 2 Having a particle size of / g (BET method according to ISO 9277: 2010); the reinforcing filler (b) is typically treated to make them hydrophobic and is present in an amount of 1.0 to 50 weight% of the composition, alternatively 1 to 30 weight% of the composition, or alternatively 5.0 to 25 weight% based on the weight% of the composition;

[0193] c) an organosilicon compound having an average of at least 2, or alternatively, an average of at least 3, Si-H groups per molecule, preferably, the molar ratio of silicon-bonded hydrogen atoms of component (c) to total unsaturated groups selected from alkenyl groups and / or alkynyl groups of the composition is 0.5:1 to 20:1, alternatively, the molar ratio of silicon-bonded hydrogen atoms of component (c) to total unsaturated groups selected from alkenyl groups and / or alkynyl groups of organopolysiloxane (a) is preferably at least 0.8:1 and may be up to 8:1 or 10:1. Most preferably, the molar ratio of Si-H groups to aliphatic unsaturated groups is in the range of 1.1:1 to 5:1; The organosilicon compound having at least two, alternatively at least three, Si-H groups per molecule is present in an amount of 0.1% to 10% by weight of the hydrosilylated curable silicone rubber coating composition, alternatively 0.1% to 7.5% by weight of the hydrosilylated curable silicone coating composition, alternatively 0.5% to 7.5% by weight of the hydrosilylated curable silicone coating composition, and additionally alternatively 0.5% to 6% by weight of the hydrosilylated curable silicone coating composition. Component (c) functions as a crosslinking agent;

[0194] (d) a hydrosilylation curing catalyst, wherein the catalyst amount of the hydrosilylation catalyst is 0.01 ppm to 10,000 parts by weight of a platinum group metal per million parts (ppm) based on the weight of the hydrosilylation curable silicone rubber coating composition; alternatively, 0.1 to 7,500 ppm; Alternatively, the amount of component (d) present is a metal of 100 to 75,000 ppm and, alternatively, 500 to 6,000 ppm based on the weight of the composition, and, depending on the form / concentration in which the catalyst is provided in, for example, a polymer or solvent, the amount of which is present is within the range of 0.001 to 3.0 wt% of the composition, alternatively, 0.001 to 1.5 wt% of the composition, alternatively, 0.01 to 1.5 wt%, or alternatively, 0.01 to 0.1 wt% of the hydrosilylation reaction-curable silicone rubber coating composition;

[0195] (e) pre-formed silicone elastomer microparticles (e)(i) having an average non-swelling particle size of 1 mm or less, wherein the pre-formed silicone elastomer microparticles (e)(i) are swollen by being infiltrated with an organopolysiloxane polymer swelling agent (e)(ii) having a zero shear viscosity of 15,000 mPa·s or less (≤) at 25°C; after the component (e)(i) is swollen by the component (e)(ii) for a set time, the component (e) is present in the composition in an amount of 7.5 wt% to 30 wt% of the composition, alternatively in an amount of 7.5 wt% to 25 wt% of the composition, or alternatively in an amount of 9.0 wt% to 20 wt% of the composition.

[0196] (f) an adhesion promoter as described above; said adhesion promoter (f) is typically present in the composition in an amount of 0.1 to 5.0 weight% of the composition, alternatively 0.1 to 3.5 weight% of the composition, alternatively 0.1 to 2.5 weight% of the composition, alternatively 0.1 to 2.25 weight% of the composition, or alternatively 0.2 to 2.0 weight% of the composition. When the contact promoter is a combination of an alkoxysilane coupling agent and an organometallic adhesion catalyst, the catalyst is introduced in an amount of 0.05 to 0.3 weight% of the composition; and optionally

[0197] g) 1 to 60 weight% of the composition, alternatively 1 to 40 weight%, of one or more silicone resins selected from T silicone resin (silsesquioxane), DT silicone resin, MQ silicone resin, MDT silicone resin, MTQ silicone resin, QDT silicone resin, or mixtures thereof.

[0198] The hydrosilylated reaction-curable silicone rubber coating composition is any suitable combination of the above, and the total weight% (weight%) of the composition is 100 weight%.

[0199] When component (g) is present, it is preferably an MQ-type resin, alternatively a vinylized MQ resin. Additionally, as specified above, in one alternative, when component (b) is not present, component (g) is present to reinforce the coating. In this case, when (b) is absent and (g) is present, the silicone resin (g) contains one or more unsaturated groups, such as vinyl groups, and alternatively, the silicone resin (g) is a vinylized MQ resin. In one embodiment, component (b) or component (g) is present, or a mixture of component (b) and (g) is present in the composition.

[0200] Typically, a hydrosilylated curable silicone rubber coating composition used to manufacture coated fabric articles before use, such as airbags or airbag fabric articles coated with a cured product, is stored in two parts, Part A and Part B, along with components (c) a crosslinking agent and (d) a hydrosilylation catalyst to prevent premature curing. Typically, the Part A composition will comprise components (a) a polymer, (b) a reinforcing filler (when present), and (d) a hydrosilylation curing catalyst, and Part B will comprise components (a), (c) a crosslinking agent, when present, a reinforcing filler (b), and when present, a curing inhibitor. Components (f) an adhesion promoter are typically stored in the Part B composition, but may be stored in Part A or in both Parts A and B. Components (g) may be added to either of the two parts depending on their composition. Typically, components (g) are preferably added to at least Part A when containing unsaturated groups.

[0201] Additionally, component (e) is also introduced into the Part B composition. In one alternative, some of component (a) may have a viscosity low enough to function as component (e)(ii) when reactive, and in this case, component (e)(i) and component (e)(ii) may be mixed together as a premix, or component (e)(i) may be added directly to Part B and swollen for a period of time as previously discussed when some of component (a) has a viscosity low enough (i.e., less than 15,000 mPa·s). When component (e)(i) and component (e)(ii) are mixed together as a premix, the premix of component (e) may be added directly to Part B when the period allowed for swelling of component (e)(i) expires, or it may be kept separately in the Part C composition alone along with additional component (a), and Part C is then mixed into the final composition simultaneously when Part A and Part B are mixed together.

[0202] When present in a hydrosilylated curable silicone rubber coating composition used to manufacture coated fabric articles, such as airbags or airbag fabric articles coated with a cured product, the additive may be present in either Part A or Part B, provided that it does not have a negative effect on the properties of any other component present (e.g., catalyst inactivation).

[0203] Part A and Part B of the hydrosilylated curable silicone coating composition described herein are mixed together immediately before use to initiate curing of the entire composition into a silicone elastomer material. The composition of Part (A) and the composition of Part (B) (and an optional Part C containing component (e)) can be designed to be mixed in any suitable weight ratio, for example, Part A:Part B can be mixed together in a weight ratio of 10:1 to 1:10, alternatively 5:1 to 1:5, or alternatively 2:1 to 1:2, but most preferred is a weight ratio of 1:1.

[0204] Each component of Part A and / or Part B may be mixed individually, for example, and may be introduced into the composition as a pre-prepared combination to facilitate mixing of the final composition.

[0205] For example, components (a) and (b) are typically mixed together before adding other components to form an LSR polymer base or masterbatch. Similarly, component (e) may also be pre-mixed with component (a) if desired. These can then be mixed with other components of the directly manufactured part B or used to produce a pre-manufactured concentrate, which is commonly referred to in the industry as a masterbatch.

[0206] In this case, to facilitate mixing of the components, one or more masterbatches may be utilized to successfully mix the components and form the compositions of Part A and / or Part B. For example, a "fumed silica" masterbatch may be prepared. This is an LSR silicone rubber base having silica effectively processed in situ.

[0207] Parts A and B of the hydrosilylated curable silicone rubber coating composition can be prepared by combining all of their respective components at ambient temperature. Any mixing technique and apparatus described in the prior art may be used for this purpose. The specific apparatus to be used will be determined by the viscosity of the components and the final composition. Suitable mixers include, but are not limited to, paddle-type mixers, e.g., oil mixers and kneader-type mixers. It may be desirable to cool the components during mixing to avoid premature curing of the composition.

[0208] Before use, each composition of Part A and Part B is mixed together in the desired proportion.

[0209] As part of the method of the present invention, a coating composition as described herein may be applied onto a substrate, for example, an integral woven or flat fabric airbag substrate, by any suitable known technique. These include spraying, gravure coating, bar coating, knife coating, e.g., knife-over-roller coating, knife-over-air coating; padding, dipping, and screen printing.

[0210] The hydrosilylated curable silicone rubber coating composition can be applied to one or both sides of a fabric or fabric material substrate, such as airbag fabric, which is cut into pieces and sewn to assemble an airbag, or can be applied to an integral woven airbag.

[0211] Curing of the hydrosilylated curable silicone coating composition of the present invention applied on a woven fabric is typically carried out by heating the composition at a temperature of 150 to 200°C for 45 seconds to 2 minutes, which can be achieved by using a suitable oven or through the drying tunnel of a circulating hot air oven.

[0212] Although not desirable, it is possible to apply the composition in multiple layers having a predetermined average dry coat weight that can be measured according to ISO 3801. Additionally, if deemed necessary, it is also possible to apply an additional compatible coating, such as a material providing low friction, on the coating composition.

[0213] For example, 15 to 150 g / m² determined according to ISO 3801 2 , alternatively 15 to 100 g / m² 2 , alternatively 20 to 75 g / m² 2 Any suitable desired coating weight can be applied to a fabric or textile material such as an airbag. The thickness of the coating layer is in the range of 20 to 80 μm depending on the coating weight.

[0214] When a coated airbag article is formed by coating and curing on an uncoated airbag fabric with a typical coating weight, the composition of the present invention demonstrates essential performance characteristics of maintaining pressure upon deployment and / or protecting the bag, vehicle, or occupant against thermal, abrasion, or impact-induced damage upon deployment.

[0215] When using physically recycled and / or regenerated silicone elastomer microparticles as the pre-formed silicone elastomer microparticles of the present invention, in addition to providing a proportionally lower carbon footprint, coated fabric articles produced with a silicone airbag coating in which a portion of the hydrosilylated curable silicone rubber coating composition is directly replaced with physically recycled and / or regenerated silicone elastomer microparticles may have lower manufacturing costs because less new hydrosilylated curable silicone rubber coating is required per coated fabric article.

[0216] Fabric or textile material

[0217] The fabric or fabric substrate to which the hydrosilylated curable silicone rubber coating composition is applied may be made of any suitable woven fabric, particularly plain weave fabric, but may be, for example, knitted or non-woven fabric. The fabric or fabric material may be made of synthetic fibers or blends of natural fibers and synthetic fibers, such as polyamide fibers like nylon-6, nylon-6,6, and nylon-4,6; polyester fibers like polyethylene terephthalate and polybutylene terephthalate; polyimide, polyethylene, polypropylene, polyester-cotton, polyacrylonitrile fiber fabric, aramid fiber fabric, polyetherimide fiber fabric, polysulfone fiber fabric, carbon fiber fabric, rayon fiber fabric, and / or glass fiber.

[0218] Typically, one side of the fabric or fabric substrate is processed, but more than one side may be processed if desired depending on the intended end use.

[0219] When processing airbags, the airbag may be a monolithic woven airbag or a flat piece of fabric sewn to provide sufficient mechanical strength after coating. Such airbags are generally manufactured from polyamide fiber fabric or polyester fiber fabric for applications requiring high strength, particularly monolithic woven airbags for automobiles. Before coating with the hydrosilylated curable silicone rubber coating composition described herein, the woven fabric is preferably washed with water and dried.

[0220] To be used as an airbag fabric, the fabric must be flexible enough to be folded into a relatively small volume, but strong enough to withstand high-speed deployment under, for example, explosive charge effects. Polyamide and polyester fibers are particularly preferred for manufacturing airbag fabrics; however, since it can be difficult to attach coatings to polyamide and polyester airbags, the adhesion promoter described herein is required.

[0221] The hydrosilylated curable silicone rubber coating compositions used to manufacture the coated fabric articles of the present invention are designed to have particularly good adhesion and film-forming properties immediately upon contact with a substrate, thereby ensuring uniform film formation on the surface of the coated substrate. Preferably, they also have good penetration into the fabric used as the substrate and a high level of elongation.

[0222] An airbag obtained by coating a substrate, e.g., an uncoated airbag fabric, with the hydrosilylated curable silicone coating composition described herein has at least one coating layer formed from the cured product of the hydrosilylated curable silicone coating composition described herein. However, if necessary, one or more additional layers may be provided on the substrate. Such additional layers are typically applied to improve the tactile sensation of the surface of the treated article, e.g., the coated woven fabric, to improve the abrasion resistance of the surface, and / or to improve the strength of the treated article. The additional coating layer(s) may be exemplified by a coating layer formed of a plastic film, a woven fabric, a nonwoven fabric, or an elastic coating material other than the cured silicone rubber disclosed herein, but preferably, the additional layer is not required or desired. Additionally, sections of the fabric coated by the cured silicone surface may be further overcoated or treated with a continuous, semi-continuous, or dispersed topcoat, ink, sealant, or adhesive according to specific airbag design requirements.

[0223] This technology can be used for any suitable fabric and / or fabric applications, but is particularly suitable for airbag applications in the automotive market as well as, for example, escape suits from aircraft, sails, clothing, etc.

[0224] The substrate may be coated on any resulting side or multiple sides of the article assembled by the method of the present invention. For example, in an integral woven (OPW) airbag, the resulting airbag is typically coated on the surface(s) that eventually become the exposed upper and lower surfaces of the final article, and a continuous, semi-continuous, or discontinuous topcoat may optionally be additionally coated on both sides to minimize any tendency for contacting outer surfaces to stick together or “clog.” In a flat fabric airbag design, the coated fabric is typically assembled so that the coated surface eventually becomes the interior of the bag, which is formed after cutting, sewing, and seaming the edges of two pieces of fabric forming the article. In such a design, an uncoated outer surface may also be additionally coated in one or more areas to provide additional protection to the fabric, the vehicle, or the occupant upon deployment.

[0225] The coating formed by curing the hydrosilylated curable silicone rubber coating composition described herein has excellent adhesion to the substrate used in airbag fabric. The excellent adhesive durability to various fabrics improves airbag reliability by providing long-term stability to the coated fabric under thermal and humidity aging conditions.

[0226] Accordingly, the coating applied to a substrate to manufacture the coated fabric article of the present invention provides good mechanical strength, adhesion to woven fabric, as well as high elongation.

[0227] To our advantage, the inventors provide a coated fabric article that is a piece of airbag fabric sewn together to manufacture an airbag incorporating pre-formed silicone elastomer microparticles obtained from post-industrial or post-consumer waste. As will be known from the examples, various pre-formed silicone elastomer microparticles may be incorporated into the composition used to produce the coated fabric article. In practice, the coating composition used to manufacture the coated fabric article, e.g., the coated airbag and airbag material, may contain physically recycled and / or regenerated silicone elastomer microparticles from any of the following: recycled airbags, condensation-cured elastomers including coatings, gaskets and seals, weather-resistant sealants, tire sealants, and refrigerant spacers, peroxide-cured elastomers, and hydrosilylated-cured elastomers. It was surprisingly discovered that physically recycled and / or regenerated silicone elastomer microparticles are suitable for incorporation into liquid silicone elastomer compositions, which typically also contain a mixture of suitable adhesion promoters or contact promoters, to provide curable elastomer compositions with a lower carbon footprint, which can unexpectedly be coated onto woven airbags to maintain pressure and provide suitable mechanical properties known to be useful for airbag coating applications.

[0228] Industry requirements and demands to reduce carbon usage necessitate a shift in sustainable materials from being merely "good" characteristics to becoming an increasingly important consideration in the mobility and transport market. Accordingly, the present invention provides the ability to manufacture airbag coatings that can be used to produce coated airbags and coated airbag materials containing an interpenetrating silicone-silicon network as a means of incorporating pre-formed silicone elastomer microparticles into the airbag coating, thereby avoiding the previous problem of microparticles "spilling out" when merely encapsulated. This provides a lower carbon footprint alternative to liquid silicone rubber (LSR) coated airbags and enables the appropriate use of silicone elastomers for intended purposes.

[0229] Examples

[0230] In the following embodiments, unless otherwise specified, the composition is defined in weight% (weight%), and unless otherwise specified, all specified viscosity measurements are the zero shear viscosity (η) obtained by extrapolating the value obtained at a low shear rate at the rate-independent limit of the viscosity-shear rate curve to zero (or simply taking the average of the values). o It is a value that is independent of the test method if a suitable and properly functioning rheometer is used. For example, at 25°C, the zero-shear viscosity of a material is 0.01 s without exceeding the transducer's torque limit. -1 , 0.1 s -1 , and 1.0 s -1 This can be obtained using a commercial rheometer, such as the Anton-Parr MCR-301 rheometer or the TA Instruments AR-2000 rheometer, equipped with cone and plate fixtures of suitable diameter that generate appropriate torque signals at a series of low shear rates. Alternatively, 0.1 to 10 s at a 25 mm cone and plate. -1Viscosity measurements can be obtained using the commercially available ARES-G2 rotational rheometer from TA Instruments with a constant speed sweep. If a zero-shear flat region cannot be observed at a shear rate accessible by the rheometer or viscometer, 0.1 s at 25°C -1 The viscosity measured at the standard shear rate is reported. All Shore hardness measurements were taken using the Shore A method or the Shore 00 method defined in ASTM D2240-15 according to apparent ductility, and the Shore 00 method is used for more ductile elastomers.

[0231] Swelling reference example

[0232] To demonstrate that a low-viscosity organopolysiloxane polymer will swell a hydrosilylated cured silicone elastomer when the elastomer is immersed in a low-viscosity silicone fluid, the following experiment was conducted.

[0233] A slab of cured liquid silicone rubber material was prepared according to the instructions supplied with the product to mix the provided two-part composition. Three rectangular samples of 1 inch x 1 inch x 0.08 inch (2.54 cm x 2.54 cm x 2 mm) were cut from the slab. Three rectangular samples were immersed in three dimethylvinyl-terminated polydimethylsiloxanes having different viscosities, the first fluid having an approximate viscosity of 30 mPa·s, the second fluid having an approximate viscosity of 430 mPa·s, and the third fluid having an approximate viscosity of 44,000 mPa·s, and in each case, the provided value was the zero shear value measured at 25°C as described above. Each sample was immersed in each fluid for 24 hours, and then analyzed for changes.

[0234] It was found that a sample immersed in a fluid with a viscosity of 44,000 mPa·s did not increase in mass and did not change in size. A sample immersed in a fluid of 430 mPa·s increased in mass and size by 8%. A sample immersed in a fluid of 30 mPa·s increased in mass and size by 30%.

[0235] Therefore, it can be seen that swelling occurred when the sample was immersed in a low-viscosity silicone fluid, but no noticeable swelling occurred when immersed in a fluid with a viscosity of 44,000 mPa·sg.

[0236] A similar experiment was conducted to demonstrate that when an elastomer is immersed in a low-viscosity silicone fluid, the low-viscosity silicone fluid swells the condensation-cured silicone elastomer.

[0237] Condensation-cured slabs of silicone elastomer prepared from a two-part sealant composition using a tin catalyst were prepared, and the test was repeated. For the condensation-cured samples, it was found that the sample immersed in 44,000 mPa·s did not increase in mass and did not change in size. The sample immersed in a fluid of 430 mPa·s increased in mass and size by 8%. The sample immersed in a fluid of 30 mPa·s increased in mass and size by 30%.

[0238] Therefore, it can be seen that when a sample is immersed in a low-viscosity silicone fluid, swelling occurs, and consequently, similar swelling occurs in pre-formed silicone elastomer microparticles.

[0239] Laboratory manufacturing of microparticles

[0240] In one example, cured silicone rubber block samples were shredded with a paper shredder and cut with scissors until they reached a planned particle size of less than 2 cm. Subsequently, these were cut into commercially available Mikro from Hosokawa Micron Corporation. TMIt was fed into a UMP-B mill. The crushed / cut rubber sample could be mixed with dry ice (previously crushed into powder using a mortar and pestle) in an approximate 1:1 weight ratio to help lower the temperature of the rubber and prepare it for milling. Then, the rubber / dry ice mixture was fed into a mill using a knife-blade rotor rotating at > 10,000 rpm. Subsequently, the rubber was allowed to leave the milling chamber through a stainless steel screen when it was cut finer than the hole size of the screen. The screen had round holes with a diameter of 2 to 3 mm during the first pass. Then, the rubber milled during the first pass was applied to the second pass again using dry ice as before, and Mikro was used during the second pass time using a 1 mm slot screen. TM It was supplied through the UMP-B mill.

[0241] Analytical evaluation of particle size.

[0242] The particle size distribution of milled pre-formed silicon elastomer microparticles was measured using laser diffraction. A Beckman Coulter with a tornado (drying) module TM An LS 13 320 particle size analyzer was used. Approximately 25 mL of milled bulk solid sample was added to a vial, placed in an LS 13320 tornado module, and activated. Upon activation, the tornado module automatically vacuumed the sample to allow it to pass through the laser, and the diffraction signal of the sample was measured. Subsequently, Beckman Coulter TM The diffraction signal was deconvolved using software into a particle size distribution determined by the Fraunhofer diffraction model, and the average value is recorded below.

[0243] A hydrosilylated curable silicone rubber coating composition was prepared using the composition shown in Table 1.

[0244] [Table 1]

[0245]

[0246] The reactive swelling agent used was a vinyldimethyl-terminated polydimethylsiloxane fluid having a viscosity of 450 mPa·s.

[0247] The crosslinking agent used in the above composition was a trimethyl-terminated methylhydrogen dimethylsiloxane polymer having a zero shear viscosity of about 5 mPa·s at 25°C.

[0248] Subsequently, the above-mentioned hydrosilylated curable silicone rubber coating composition (LSR 1) was used in a series of examples in combination with various pre-formed silicone elastomer materials having an average particle size of 1 mm or less, either alone or together, as shown in Tables 2a and 2b below. Except for Reference Example 1, which did not contain mechanically recycled microparticles, and Example 2, which had 67.5 parts by weight per 100 parts by weight of Part B (1) of LSR 1, mechanically recycled microparticles were loaded in an amount of 22.5 parts by weight per 100 parts by weight of Part B (1) of LSR 1. Thus, when initially mixed, the mixture contained approximately 80 wt% of the composition of Part B (1) of LSR 1 and about 20 wt% of microparticles in Examples 1 and 3 to 5, and about 60 wt% of microparticles and 40 wt% of Part B (1) of LSR 1 in Example 2.

[0249] [Table 2a]

[0250]

[0251] In the table above,

[0252] LSR recycled rubber microparticles 1It was prepared from a hydrosilylated cured liquid silicone rubber (LSR) coating composition containing HMDZ-treated fumed silica designed to be a high-elongation coating with a Shore A hardness of approximately 10. Since Shore A hardness measurements are less accurate for soft materials exhibiting values ​​of 10 or less on the Shore A scale, measurements were also taken using the Shore 00 hardness scale. In this case, the original airbag LSR coating has an equivalent Shore 00 hardness value of approximately 80.

[0253] LSR recycled rubber microparticles 2 It was prepared from a hydrosilylated cured liquid silicone rubber (LSR) coating composition containing HMDZ-treated fumed silica having a Shore A hardness of about 50.

[0254] HCR Recycled Rubber Microparticles 1 It was manufactured from peroxide-cured high-viscosity rubber (HCR) with a Shore A hardness of about 60, which is used in gasket applications.

[0255] RTV Sealant Recycled Microparticles 1 It was prepared from two parts of tin-cured room-temperature vulcanized sealant having a Shore A hardness of about 40, which was cured into a sheet under ambient laboratory conditions for a period of 30 days.

[0256] The provided examples (Examples 1 to 5) rely on a swelling agent in the Part B (1) composition of LSR 1 to swell mechanically recycled silicone rubber microparticles using the Part B (1) composition shown in Table 1. The relevant mechanically recycled microparticles shown in Table 2a were prepared as described above and introduced into the Part B (1) composition. The microparticles were allowed to swell by interacting with the reactive swelling agent provided in the Part B (1) composition. Swelling occurred for approximately 24 hours.

[0257] After the completion of the swelling step, a resulting mixture containing 100 parts by weight of the Part B (1) composition incorporating the swollen microparticles was mixed with 100 parts by weight of the Part A composition of LSR 1 (a 1:1 weight ratio of Part A to Part B (1) excluding microparticles) to obtain about 10% by weight (non-swelling weight) of microparticles in the total composition of Part A + Part B (1) in Examples 1 and 3 to 5, and about 30% by weight (non-swelling weight) of microparticles in the total composition of Part A + Part B (1) in Example 2. The different compositions were compression molded at 150°C for 10 minutes in a rectangular slab of dimensions 5 inches x 5 inches x 0.08 inches (12.7 cm x 12.7 cm x 0.2 cm) to cure the resulting hydrosilylated curable silicone rubber coating composition.

[0258] An additional set of four examples was prepared using the composition of Part B (2) or Part B (3) of LSR 1 as shown in Table 2b below.

[0259] [Table 2b]

[0260]

[0261] In Table 2b, the amounts of utilized microparticles, capsules, and swelling agents are expressed in parts by weight per 100 parts by weight of each part B (2) or part B (3) composition.

[0262] In the case of Example 6, the composition used in Example 1 was repeated, but in this case, the microparticles were pre-swelled in a reactive swelling agent for 24 hours, then the swollen microparticles and the remaining swelling agent were added to the composition of Part B (2), stirred, then the composition of Part B (2) was mixed with the composition of Part A, and the resulting combined composition was cured in the same manner as described above.

[0263] For Examples 7, 8, and 9, a Part B (3) composition containing 5 wt% of a reactive swelling agent was utilized. In Example 7, fine particles were added to the Part B (3) composition and swollen by the reactive swelling agent therein. Swelling occurred for approximately 24 hours, and then the Part B (3) composition containing the swollen fine particles was mixed with 100 parts by weight of the Part A composition of LSR 1 (a 1:1 ratio of Part A to Part B (3) by weight, excluding the fine particles),

[0264] Fine particles of about 10% by weight (non-swelling weight) were obtained from the total composition of Part A + Part B (3).

[0265] Examples 8 and 9 underwent a capping procedure. In the case of Example 8, the microparticles were immersed in combination with a non-reactive swelling agent (plasticizer) combined with 1-dodecene and provided to react with any residual Si-H groups available for reaction within or on the microparticles. The microparticles were allowed to interact with 1-dodecene for approximately 3 days (72 hours) before being introduced into the pre-prepared Part B (3) composition, and the method thereafter was as described above. In Example 8, if the Part A composition and the Part B composition were mixed together, the final mixed formulation contains approximately 9.88 wt% of microparticles (dry / non-swelling weight), 2.27 wt% of non-reactive swelling agent, and 0.09 wt% of capping agent.

[0266] In Example 9, the microparticles were immersed and pre-swollen for 24 hours in combination with a reactive swelling agent and 1-dodecene in the amounts shown in Table 2b. After a period of 24 hours, the resulting microparticle mixture was introduced into the composition of Part B (3), and the method thereafter was the same as above.

[0267] In both Examples 8 and 9, the loading of the capping agent was chosen to be approximately the same as the number of moles of residual Si-H expected to be present in the particulates, assuming total vinyl conversion during the original curing of the elastomer before physical recycling.

[0268] Hydrosilylated curable silicone rubber coating compositions of Examples 6, 7, 8, and 9 were cured by compression molding different compositions in a rectangular slab of dimensions 5 inch x 5 inch x 2 inch (12.7 cm x 12.7 cm x 5.08 cm) at 150°C for 10 minutes.

[0269] Subsequently, the cured samples were analyzed for their physical properties. For the tensile test, a tensile bar with a gauge length of 40 mm was cut from a rectangular slab using a metal die, and the tensile strength, elongation at break, and modulus results were determined according to ASTM D412. This was repeated five times for each composition. Shore 00 hardness was determined using ASTM D2240-15. The results of the physical properties are shown in Table 3. The reference samples represent the physical property results obtained for standard cured airbag coating materials.

[0270] [Table 3]

[0271]

[0272] It can be seen from the examples of Examples 1 to 9 that by using the various types of mechanically recycled fine particles described herein, a material with a sufficiently high elongation capable of adequately capturing the tensile properties of the reference material can be produced. It was found that the physical properties were sufficient to provide adequate pressure maintenance during airbag deployment at an optimized coating weight.

[0273] In fact, the coatings of Examples 1 to 9 were coated onto a mini airbag comprising an integral woven PET fabric using a lab-scale blade coater from Mathis AG, Switzerland. The coating yielded 65 to 70 g / m² 2 It had an approximate coating weight. After the coating process, the coated airbag was cured at 190°C for 90 seconds. Suitability for use as an airbag coating was achieved. The deployment test was performed by inflating the bag to 70 kPa and monitoring the pressure drop as a function of time after deployment.

[0274] For example, in the case of a mini airbag coated with a layer of the coating composition of Example 5, 65 g / m² 2 It was found that the coated airbag meets the 6-second pressure maintenance requirement at the coating weight.

[0275] Despite having slightly lower tensile properties, this coating weight was comparable to the coating weight required for typical commercial materials, such as those similar to the coating prepared from the reference composition (Ref). Despite having nearly the same coating weight, Example 5 is expected to provide desired performance characteristics and an improved LCA at a lower cost compared to Reference Example 1, as it contains a proportionally smaller amount of the new silicon composition, as shown below in Table 1.

[0276] Although Examples 1 to 9 provide lower elongation and tensile strength values ​​than the reference example, it can be seen from Table 4 below that, when comparing the same airbag coating with Examples 1 and 3 except for using fine particles (e)(i) of smaller particle size, improved physical property results were provided due to the fine particles being smaller than those used in Table 3.

[0277] In Table 4, the results of Examples 1 and 3 are repeated. These contained microparticles with an average particle size of 1000 μm, had exactly the same composition, and were prepared in exactly the same manner, with the only difference being that they were compared to Example 1*, where the microparticles had an average particle size of 400 μm, and Example 3*, which had a similarly identical composition and was prepared in the same manner, but had microparticles with an average particle size of 200 μm.

[0278] [Table 4]

[0279]

Claims

Claim 1 A coated fabric article comprising: i) a substrate having a surface—wherein the substrate comprises a fabric suitable for manufacturing an airbag—; ii) a cured product of a hydrosilylation-curable silicone rubber coating composition attached to the surface of the substrate, wherein the hydrosilylation-curable silicone rubber composition comprises: a) one or more organopolysiloxane polymers having a viscosity of 100 to 200,000 mPa·s at 25°C and at least two unsaturated groups per molecule—wherein the unsaturated groups are selected from alkenyl groups and / or alkynyl groups—; b) optionally one or more reinforcing fillers comprising fumed silica, precipitated silica, and / or calcium carbonate; c) an organosilicon compound having an average of at least two or alternatively at least three Si-H groups per molecule; d) a hydrosilylation curing catalyst; e) pre-formed silicone elastomer microparticles having an average non-swelling particle size of 1 mm or less (e)(i)—wherein, The above-mentioned pre-formed silicone elastomer microparticles (e)(i) are swollen by being infiltrated with an organopolysiloxane polymer swelling agent (e)(ii) having a zero shear viscosity of 15,000 mPa·s or less (≤) at 25°C; f) an adhesion promoter; and optionally g) one or more silicone resins selected from T silicone resin (silsesquioxane), DT silicone resin, MQ silicone resin, MDT silicone resin, MTQ silicone resin, QDT silicone resin, or mixtures thereof, a coated fabric article. Claim 2 In paragraph 1, a coated fabric article which is an airbag or airbag fabric article. Claim 3 A coated fabric article according to claim 1 or 2, wherein the pre-formed silicone elastomer microparticles (e)(i) are physically recycled and / or regenerated silicone elastomer microparticles (e)(i) obtained from a condensation-cured (RTV) silicone elastomer or a silicone rubber elastomer prepared from a hydrosilylated curable composition, a peroxide free radical curable composition, or a UV curable composition using a photoinitiator or photocatalyst. Claim 4 In paragraph 3, the physically recycled and / or regenerated silicone condensation-cured (RTV) silicone elastomer microparticles (e)(i) were obtained from adhesives, refrigerant spacers, potting agents, coatings, and sealants; and the physically recycled and / or regenerated silicone rubber elastomer microparticles (e)(i) were obtained from airbag coatings, gaskets and seal adhesives, coatings, molded rubber articles, hoses and piping and potting agents, coated fabric articles. Claim 5 A coated fabric article according to claim 1, 2, 3, or 4, wherein the pre-formed silicone elastomer microparticles (e)(i) had an average particle size of less than 600 μm. Claim 6 A method for coating a fabric article comprising the following steps: (1) A step of forming component (e) by mixing pre-formed silicone elastomer microparticles (e)(i) having an average non-swelling particle size of 1 mm or less with an organopolysiloxane polymer swelling agent (e)(ii) having a zero shear viscosity of 15,000 mPa·s or less at 25°C for a defined period, so that the organopolysiloxane polymer swelling agent (e)(ii) can penetrate into and swell the pre-formed silicone elastomer microparticles (e)(i); (2) Step (2) forming a mixture comprising at least a portion of component (e) and component (a) and optionally one or more of components (c), (d), (f) and when present, (b), (g), or (b) and (g) — wherein a) is one or more organopolysiloxane polymers having a viscosity of 100 to 200,000 mPa·s at 25°C and at least two unsaturated groups per molecule, said unsaturated groups are selected from alkenyl groups and / or alkynyl groups; b) is optionally one or more reinforcing fillers comprising fumed silica, precipitated silica, and / or calcium carbonate; c) is an organosilicon compound having an average of at least two or alternatively an average of at least three Si-H groups per molecule; d) is a hydrosilylation curing catalyst; and f) is an adhesion promoter; Optionally, g) is one or more silicone resins selected from T silicone resin (silsesquioxane), DT silicone resin, MQ silicone resin, MDT silicone resin, MTQ silicone resin, QDT silicone resin, or mixtures thereof -;(3) Step (2) mixing the mixture with the remainder of components (a), (c), (d), (f) and, when present, (b), (g), or (b) and (g) to produce a hydrosilylated curable silicone rubber coating composition; (4) A step of applying the above hydrosilylated curable silicone rubber coating composition onto a substrate having a surface - wherein the substrate comprises a fabric suitable for manufacturing an airbag -;(5) A step of curing the coating on the substrate having a surface—wherein the substrate comprises a fabric suitable for manufacturing an airbag at a temperature of 100°C to 200°C for a set time. Claim 7 A method for coating a fabric article, wherein steps (1) and (2) and optionally step (3) are carried out together as a single step in claim 6. Claim 8 A method for coating a fabric article, wherein, in claim 6 or 7, component (e)(i) is a pre-formed silicone elastomer microparticle (e)(i), which is a physically recycled and / or regenerated silicone elastomer microparticle obtained from a silicone rubber elastomer prepared from a condensation-cured (RTV) silicone elastomer or a hydrosilylated curable composition or a peroxide free radical curable composition. Claim 9 In claim 8, the pre-formed silicone elastomer microparticles (e)(i) are produced by grinding, milling, or finely grinding the silicone elastomer into microparticles, a method for coating a fabric article. Claim 10 A method for coating a fabric article, wherein, in claim 6, 7, 8, or 9, the pre-formed silicone elastomer microparticles (e)(i) are treated with a monofunctional capping agent. Claim 11 A method for coating a fabric article according to claim 6, 7, 8, 9, or 10, wherein component (e)(ii) has a zero shear viscosity of 100 to 5,000 mPa·s at 25°C. Claim 12 A method for coating a fabric article according to claim 6, 7, 8, 9, 10, or 11, wherein the pre-formed silicone elastomer microparticles (e)(i) had an average particle size of less than 600 μm. Claim 13 A coated fabric article comprising a cured product of a hydrosilylated curable silicone rubber coating composition applied according to the method of claim 6, 7, 8, 9, 10, 11, or 12. Claim 14 In paragraph 13, a coated fabric article which is an airbag or airbag fabric article. Claim 15 In a hydrosilylated curable silicone rubber coating composition for coating a fabric article comprising a substrate having a surface, for use of pre-formed silicone elastomer microparticles (e)(i) having an average non-swelling particle size of 1 mm or less, said pre-formed silicone elastomer microparticles (e)(i) are swollen by being infiltrated with an organopolysiloxane polymer swelling agent (e)(ii) having a zero shear viscosity of 15,000 mPa·s or less (≤) at 25°C; the hydrosilylated curable silicone rubber coating composition further comprises: a) one or more organopolysiloxane polymers having a viscosity of 100 to 200,000 mPa·s at 25°C and at least two unsaturated groups per molecule—wherein the unsaturated groups are selected from alkenyl groups and / or alkynyl groups—; b) optionally one or more reinforcing fillers comprising fumed silica, precipitated silica, and / or calcium carbonate; c) An organosilicon compound having an average of at least two or alternatively at least three Si-H groups per molecule; d) a hydrosilylated curing catalyst; f) an adhesion promoter; and optionally g) one or more silicone resins selected from T silicone resin (silsesquioxane), DT silicone resin, MQ silicone resin, MDT silicone resin, MTQ silicone resin, QDT silicone resin, or mixtures thereof; wherein the substrate comprises a fabric suitable for manufacturing an airbag. Claim 16 In paragraph 15, the above fabric article is an airbag or an airbag fabric article. Claim 17 A coated fabric article according to any one of claims 1 to 4, a method of coating a fabric article according to any one of claims 5 to 12, or a use according to claim 15 or 16, wherein component (b) is present, component (g) is present, or both components (b) and (g) are present.

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