Patent Application
20080085942
In the field of side curtain airbags, the preferred fabrics are polyamides and polyesters, nylon being the most conventional fabric material, and one piece woven (OPW) being the most conventional construction. The present invention is not limited to the particular fabric or construction, and does not require a special construction or fabric material to deliver the improved gas retention times we have discovered.
Using conventional fabric coating equipment, the primer can be applied only at the seam area of the airbag, followed by application of the coating composition over the entire surfaces of both sides of the fabric, with excellent results. It is often advantageous, however, to prime the entire surfaces of the fabric with the primer, followed immediately by application of the coating composition, since applying primer only to the seams requires changes to current equipment and techniques.
When the coating is applied immediately after curing the primer, as can be easily accomplished with in line dual coating processes, the adhesion between the primer and coating layers is extremely good.
Adhesion can also be enhanced by adding emulsified polyorganosiloxanes to the primer, for example reactive silicone oils and/or silicone resins, and/or adhesion promoters, to the primer emulsion. Adhesion promoters such as silanes can be added to the coating composition as well.
The primer is a water based emulsion, free of organic solvents, with low viscosity which provides mechanical adhesion to the fabric substrate. The primer has excellent strength and very good stability after heat and aging. Furthermore, when dried, the primer has a physical profile similar to a high strength liquid silicone rubber.
The primer comprises water-soluble or water-dispersible initiator, ethylenically unsaturated monomer, functionalized polyorganosiloxane mixture, water, and emulsifying agent.
Examples of categories of suitable ethylenically unsaturated monomers for the primer include (i) monoethylenically unsaturated esters of a saturated carboxylic acid; (ii) saturated esters or monoethylenically unsaturated carboxamides; (iii) monoethylenically unsaturated nitrites; (iv) monoethylenically unsaturated carboxylic acids; (v) hydroxyalkyl or aminoalkyl esters of monoethylenically unsaturated carboxylic acids; (vi) vinylaromatic monomers; and (vii) dicyclopentadienyl acrylate or methacrylate.
Examples of suitable functionalized polyorganosiloxanes for the primer include any having the formula
wherein R are the same or different and represent a linear or branched C1-C18 alkyl group, a linear or branched C2-C20 alkenyl group, or a C6-C12 aryl or aralkyl group, and is optionally substituted with halogen atoms; X are the same or different and represent a reactive function linked to a silicon atom by an Si—C or Si—O—C bond and is an epoxy functional hydrocarbon group containing from 2 to 20 carbon atoms; Y are the same or different and represent an ethylenically unsaturated hydrocarbon residue which optionally contains one or more hetero elements O or N, the residue being linked to a silicon atom of the moiety of formula (I) by an Si—C bond and being capable of reacting via a radical route with at least one ethylenically unsaturated monomer; Z1, Z2 and Z3 represent numbers of moieties; the number of moieties Z2 and Z3 of formula (I) being such that the polyorganosiloxanes contain from 1 to 100 milliequivalents of functions X per 100 grams of polyorganosiloxane of formula (I); and from 10 to 500 milliequivalents of residues Y per 100 grams of polyorganosiloxane of formula (I).
Suitable emulsifying agents in the primer include standard anionic agents such as fatty acid salts, alkyl sulphates, alkyl sulphonates, alkyl aryl sulphonates, sulphosuccinates, alkyl phosphates of alkali metals, hydrogenated or nonhydrogenated salts of abietic acid, nonionic agents such as polyethoxylated fatty alcohols, polyethoxylated and optionally sulphated alkylphenols, polyethoxylated fatty acids, alone or in combination, for example. These emulsifying agents may be used at a proportion of 0.1 to 3% by weight relative to the total weight of ethylenically unsaturated monomer and functionalized polyorganosiloxane.
The initiators which may be used in the primer are of the water-soluble or water-dispersible type, for instance hydroperoxides such as aqueous hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide and diisopropylbenzene hydroperoxide, persulphates such as sodium persulphate, potassium persulphate, ammonium persulphate, for example. These initiators may be used at a proportion of 0.01 to 4%, preferably of 0.05 to 2%, by weight relative to the total weight of ethylenically unsaturated monomer and functionalized polyorganosiloxane. These initiators are optionally combined with a reducing agent, such as bisulphites or sodium formaldehydesulphoxylate, polyethyleneamines, sugars such as dextrose and sucrose, and metal salts of ascorbic acid. The amounts of reducing agent used may range up to 3% by weight relative to the weight of the monomer(s)+functionalized polyorganosiloxane mixture.
Chain-limiting agents may optionally be present in proportions ranging from 0 to 3% by weight relative to the monomer(s) and functionalized polyorganosiloxane mixture. They are generally chosen from mercaptans such as N-dodecylmercaptan and tert-dodecylmercaptan; cyclohexene; halogenated hydrocarbons such as chloroform, bromoform, carbon tetrachloride and carbon tetrabromide; and α-methylstyrene dimers, for example.
The polyorganosiloxanes used are preferably in the form of a reactive, stable aqueous dispersion generally having a solids content of about 5 to 60%, more preferably of about 25 to 50%, by weight. The aqueous dispersions may be obtained by radical polymerization in aqueous emulsion or in microsuspension of at least one ethylenically unsaturated monomer in the presence of the said functionalized polyorganosiloxane containing similar or different moieties of formula (I).
The respective amounts of ethylenically unsaturated monomer and of functionalized polyorganosiloxane which may be used in the primer correspond to a monomer/polyorganosiloxane weight ratio of about 98-50/2-50, preferably of about 95-75/5-25.
The compositions and methods of application of the primers have been disclosed as useful for other purposes (anti-adhesive agents and/or water repellents for sheets of polymer material or of paper, cardboard or the like, from tapes which are adhesive on their non-adhesive side, from intercalating films of double-sided adhesive tapes or from woven or non-woven fibrous supports and/or composites or non-composites) in U.S. Pat. No. 5,767,206, to Ariagno, et al., which is hereby incorporated by reference for its teaching of suitable compositions useful in the present invention as the primer. One preferred primer material is currently commercially available from Rhodia, Inc., as PC-800.
The rate of application of the primer can be about 10-30 g/m2 and is preferably applied at 15-20 g/m2 on each side, simultaneously or sequentially.
The polymerization of the emulsion, sometimes referred to as curing of the primer, takes place at or above the decomposition temperature of the initiator, preferably in most cases at 180° C. for about 10 seconds which are typical conditions for the type of industrial ovens.
After the primer emulsion is cured, the elastomer coating is applied, at a rate of about 35-90 g/m2 per side, more preferably at about 70-90 g/m2 per side, and most preferably from about 70-80 g/m2 per side. The respective amounts of primer and coating are selected so that the gas retention of the coated air bag meets the desired specifications. In the case of side curtain airbags, at least 10 seconds of air retention is needed. Depending on the test methods, i.e., from 70-40 kPa static, 100-50 kPa static, or 100-50 kPa dynamic, coat weights of 70 g/m2 have been found to meet the 10 seconds retention requirement.
The coating is a reinforcing mineral filler-free composition comprising a mixture of (1) at least one polyorganosiloxane with alkenyl groups bound to the silicon; (2) at least one polyorganosiloxane with hydrogen atoms bound to the silicon; (3) a cross-linking catalyst; (4) an adhesion promoter comprising (4.1) at least one alkoxylated organosilane, (4.2) at least one epoxy-functional organosilicon compound, and (4.3) at least one metal chelate and/or metal alkoxide wherein the metal is selected from the group which consists of Ti, Zr, Ge, Li, Mn, Fe, Al and Mg; (5) at least one polyorganosiloxane resin; and (6) optionally at least one cross-linking inhibitor. A non-reinforcing filler, calcium carbonate, can be included in the coating composition.
Preferred coating compositions are described in detail in U.S. Pat. No. 6,586,551, to Bohin, et al, which is hereby incorporated in reference for its disclosure of examples of suitable coating compositions. One especially preferred coating composition is available commercially from Rhodia, Inc. as TCS 7534, formerly TCS 7159.
The following examples, in which all parts and percentages are by weight unless otherwise indicated, are presented to illustrate a few embodiments of the invention but are not to be construed as limiting in any way.
A water based emulsion was prepared at a solids content of 40% silicone-grafted latex (SGL) formed from the following ingredients:
Methyl methacrylate, 35 parts; Butyl acrylate, 45 parts; Acrylic acid, 5 parts; Acrylate-grafted polydimethylsiloxane (PDMS) oil, 15 parts. The unsaturated organopolysiloxane oil assaying at 31 meq/100 g of glycidyl ether functions, of the following average formula was prepared according to Example 1 of U.S. Pat. No. 5,767,206.
The acrylic monomers and diorganopolysiloxane mixture was introduced into a solution of 180 g of deionized water and 3.9 g of a 38.5% by weight aqueous solution of sodium dodecylbenzenesulphonate (Na-DBS) to form a preemulsion of the latex primer. The emulsion was polymerized according to the aforementioned example of U.S. Pat. No. 5,767,206.
A silicone coating composition was prepared according to Example 1 of U.S. Pat. No. 6,586,551 and then adding 16% by weight based on the resin of calcium carbonate as non-reinforcing filler.
1.1 Preparation of Starting Materials.
1.2—Preparation of Part B of the Two-Component System
The following are mixed in a reactor at room temperature: 45 parts by weight of resin (5); 51 parts by weight of high-viscosity oil (1); 0.0215 parts by weight of platinum metal, introduced in the form of an organometallic complex (Karstedt catalyst) containing 10% by weight of platinum metal [this constituent being called hereafter platinum of the catalyst (3)]; and 4 parts by weight of compound (4.3) of the promoter (4), consisting of butyl titanate Ti(OBu)4 [this constituent being called hereafter Ti(OBu)4 (4.3)].
1.3—Preparation of the Two-Component System
The two-component system is obtained by mixing, at room temperature, 100 parts by weight of part A and 10 parts by weight of part B. Composition C1 is thus obtained, the proportions of the constituents of which are as follows:
The primer of Example 1 was applied to each side of several sheets of Nylon fabric using a J or I knife over a roll at approximately 15-20 g/m2 per side followed by heating at 180° C. for 10 seconds.
The coating composition of Example 2 was applied to the sheets immediately after the heating step of Example 3 at three different rates as reported in Table II, and the air retention at three different testing methods was measured and the results are also reported in Table II.
OPW Nylon 6,6 fabric bags were coated directly with the coating composition of Example 2 either with primer, with the total coatweight (primer and elastomeric coating weights) reported as “Invention” in Table II, or without first applying any latex primer, reported as “Comparative” in Table II.. The results show that less total coating is needed to achieve improved air retention times by the invention versus conventional systems.
The comparative results reported in Table II demonstrate that it is necessary to increase the total elastomer coatweight to greater than 100 g/m2 to pass the 10 seconds minimum dynamic test without the primer (Comparative) but that only 70-80 g/m2 of combined primer and elastomer coating is needed to pass such test.
The OPW bags coated according to Example 4 were exposed to standard heat and humidity aging conditions and measured according to [What are the units for the 38.64, 74.75, etc.?] The results in Table III below show average results at 72 hours after coating (Before Aging) versus after 14 days at 80° C. and 95% relative humidity.
While the invention and its advantages have been described and exemplified in detail, other embodiments, substitutions, and alterations should become readily apparent to those skilled in this art without departing from the spirit and scope of the invention.
