MXPA96004725A - Difficultly flammable safety belts, containing modified confosphorus polyester fibers, and the use of these depoliester fibers for the manufacture of deseguri belts - Google Patents

Abstract

The present invention relates to a safety belt, characterized in that it comprises a fabric having a twill weave of high tenacity filament yarns manufactured from a phosphorus-modified copolyester having a linear yarn density of less than 2000 dtex, a density linear of individual filament less equal to 25 dtex, a tenacity of more than 60 cN / tex and a stretch of break less than 30%, the copolyester modified with phosphorus having a polymer chain and containing in the polymer chain a bifunctional phosphorus compound in an amount from 0.1 to 5% by weight, based on the amount of phosphorus

Description

DIFFICULTLY FLAMMABLE SAFETY BELTS CONTAINING POLYESTER FIBERS MODIFIED WITH PHOSPHORUS, AND THE USE OF THESE POLYESTER FIBERS FOR THE MANUFACTURE OF BELTS OF SECURITY The present invention relates to safety belts, which are hardly flammable thanks to the use of phosphorus-modified polyester fibers. In recent years, safety belts have become an essential component of modern motor vehicles, especially automobiles. As a result of the increase in safety requirements, the number of safety stubs used in a vehicle has also increased considerably. r., e e? by vehicle, in the sense of this description, -all types of land, sea and air vehicles., The safety belts are manufactured mainly with fabrics, consisting essentially of high-strength polyester fibers. In the works of development of textile components of great importance for the safety, destined to the automobiles, the resistance occupies the first place. However, if the safety belt is released in the event of an accident, the cmturon remains inside the vehicle in the form of relatively large textile surfaces. This poses a danger to the occupants of the vehicle in case of fire, similar to what is already known in the case of the curtains of the houses. The hard-flammable safety catches have been neglected for a long time. Document 39A-07-165,422 has proposed polyester threads containing phosphorus compounds and which are also suitable, inter alia, for the production of safety belts. These already known threads have coarse-grained particles from 1 to 100 urn, which should be considered as a very large value compared to the typical fiber diameters of approx. 30 μm. These particles can cause a saw effect, especially at concentrations of up to 5% by weight. In addition, these particles have very high draw values, greater than 30%, due to the high traction forces. From document 3P-A-91-167,312, hardly inflammable polyester fibers for the manufacture of fabrics are known, which are in turn suitable for the manufacture of airbags for the protection against shocks. The text of said document describes only tissue airbags with a coating. Said document does not indicate any suggestion about the use of such fabrics for the manufacture of security pins. In view of the increasing safety requirements in vehicles, there is a demand for hardly inflammable safety belts, especially to reduce to a minimum the risk of fire, which exists in the event of an accident, and the danger to the occupants of the vehicle. vehicle that this causes. Therefore, the object of the present invention is to propose yarns and fabrics for safety belts, which have the necessary properties of known yarns and fabrics in terms of security and also have also properties retarding the propagation of the yarns and fabrics. calls. However, it has surprisingly been found that flame-retardant safety belts can be manufactured by using phosphorus-modified, highly flammable polyether filaments. The invention relates to safety belts containing a fabric, which in turn contains highly resistant filament yarns of phosphorus-modified copolyester, with a yarn count of less than 2,000 dtex, with a title of the individual fibers equal to or less than 25 dtex, as well as with a stretch of less than 30% under the maximum tensile force, containing the phosphorus-modified copolyester, in the polymer chain, a phosphorus bifunctional compound in an amount between 0.1 and 5% by weight, but preferably 0.2 and 0.8% by weight, based on the amount of forum. The safety belts advocated in the invention may consist entirely or only in a small part of the filaments of highly resistant and phosphorus-modified filaments defined above. It is thus possible, for example, to configure totally or only partially on the basis of these threads only one of the thread systems forming the safety belts recommended in the invention. The skilled technician can calculate, by means of routine tests, the amount needed in each specific case of the filaments of high resistance filaments and modified with phosphorus, defined above, for example, by orienting itself by the desired resistance for the fabrics. By using * polyester fibers modified with phosphorus, the difficulty of inflammation of the fabrics made with them can be increased. Hardly inflammable fabric is understood, in the sense of this description, as a raw fabric, which has, in the combustibility test according to DIN 4102 / B2, a total combustion time that is shorter, at least in the factor 5, but preferably in the factor 10, than that of a comparable raw material in polyether not modified with phosphorus, and in which no subsequent residual combustion takes place, when the flame is applied for a time of between 3 and 5 seconds, according to DIN 54336 and for a time of 3 seconds according to the DTM 54333 standard. In addition to the filaments of high strength filaments and modified with phosphorus mentioned above, a part of the yarns used in the safety belts recommended in the invention consists of filament yarns not modified with phosphorus and of high strength. Preferably, at least one direction of the fabrics, for example the direction of the weft or the direction of the warp, is entirely formed by the filaments of high strength filaments and modified with phosphorus defined above; but in a particularly preferred manner, both directions are formed with filament yarns of this type. The safety belts advocated in the invention may consist of fabrics containing two or more thread systems; Preferably, two yarn systems (warp and weft yarn bundles) are provided. Very particularly preferably fabrics are used, which consist of at least two yarn systems, which consist respectively of at least the < 30% of its composition, of the filaments of high resistance filaments and modified with phosphorus defined above. Especially preferred are safety belts, as defined above, whose high strength filament yarns have a maximum tensile strength of more than 60 cN / tex, but preferably more than 65 cN / tex, as regards their fineness, and a stretch of between 10 and 25% with the maximum traction force. The measurement of the maximum tensile strength and stretching with the maximum tensile strength of the polyether wires used is carried out in accordance with DIN 53 830, part I. Especially preferred are safety belts, as defined above, whose high-strength filament yarns have a shrinkage of less than 20% when subjected to air at a temperature of 200 ° C. The measurement of thermal contraction (contraction with air) at high temperature) of the polyester yarns used is carried out in accordance with DIN 53 866, part 3, at a temperature of 200 ° C in samples of wire that are hanging freely, with a treatment time of 15 minutes. 10 meters of skein section with a tension of 0.5 cN / tex on the winder are used. Another particularly preferred embodiment of the invention relates to safety belts, such as those defined above, whose fabric contains, in addition to filament yarns of high strength of copolyester modified with phosphorus, rnonofilaments with a diameter equal to or less than 1 to 0.5 mrn, containing the monofilaments in the polymer chain, a phosphorus-modified copolyester, which in turn has a bi-functional phosphorus compound in an amount of between 0.1 and 5% by weight, but preferably between 0.2 and 0.8% by weight, referred to the amount of phosphorus. The monofilaments give the safety belt an improved, highly elastic transverse rigidity; in this way the safety cmturon is prevented from twisting. In a further preferred embodiment of the security cmturon recommended in the invention, monofilaments are used, which have a maximum tensile strength of more than 35 cN / tex referred to the fineness and? N stretched with the maximum tensile force of more than 15 cm. % and / or a shrinkage of less than 20% under the action of air at a high temperature of 180 ° C. Very particularly preferably, fabrics are used, containing high strength filament yarns without sizing, made of phosphorus-modified copolyester . The non-recycled fabrics, recommended in the invention, can have different ligaments, preferably a twill weave, in particular a twill K2 / 2 weave or a "reps" ribbed weave. Fabrics with these ligaments are already known per se. The safety patches recommended in the invention preferably contain fabrics with a weight per unit area of less than 100 gr. for each linear meter with a width of 50 nm and a fabric thickness less than 1.5 m. An especially preferred fabric has a maximum tensile strength of more than 1,470 daN with 50 mm with 1,000 N and with a width of 50 nm, in both cases measured according to DIN 53 857, the part. The high strength filament yarns that are used according to the present invention contain polyester filaments, which are formed from a phosphorus-modified copolyester. The copolyester can be a random copolymer, with groups of repetitive esters, provided that the copolymer contains in the polymer chain a bifunctional phosphorus compound in the above-mentioned amount. Highly resistant filaments of phosphorus-modified copolyesters are preferably used, which contain the repeating structure units of the formula I: -O-OC-Orl-CO-O-Rl- '(I) and which in the polymer chain have component groups of Formula II: 0 0 -0-P-R2-C- (II) R3 wherein: Ari represents a bivalent aromatic radical, Ri is a bivalent aliphatic or cycloaliphatic radical, R 2 represents a bivalent aliphatic, cycloaliphatic, aromatic or araliphatic radical, and R 3 represents a monovalent radical aliphatic, cycloaliphatic, aromatic or araliphatic . Particularly preferred are used modified polyesters of the type indicated above, in which Ar means phenylene or naphthylene, and in particular 1,4-phenlene or 2,6-naphthylene. Modified polyesters of the above-mentioned type are also particularly preferably used, in which Ri represents a radical of the formula -CnH2n- / wherein n is an integer between 2 and 6, in particular ethylene, or represents a radical derived of the cyclohexanedimethanol. Modified polyesters of the above-mentioned type, in which R2 is a radical of the formula -CmH2m-, in which it is an integer between 2 and 10 ob in a cyclic radical of an alkanol with between 4 and 8 carbon atoms, but preferably with 6 carbon atoms and in which R 3 is Ci-C-alkyl, cyclohexyl, phenyl or benzyl. If in the formulas of structure defined above some radical means a bivalent aliphatic radical, it should be understood here as branched and especially straight-chain alkylene, for example alkylene with 2 to 10 carbon atoms, but preferably with between 2 and 8 atoms. of carbon.

Examples of radicals of this type are: ethan-L, 2-dn-1, propan-1,3-dial, butan-1, 4-dial, pentan-1, 5-d? it, hexan-1, 6-dial or octan-l, 8-dial. If in the structure formulas defined above some radical means a bivalent cycloaliphatic radical, then it should be understood that these are groups containing carbocyclic radicals having between 5 and 8 carbon atoms, but preferably with 6 nuclear carbon atoms. Examples of these radicals are cyclohexan-1, 4-dial or the group -CH 2 -C 6 H 10 -CH 2 - Si in the structure formulas defined above some radicals mean aromatic bivalent radicalsThey are then heterocyclic aromatic radicals, which may be mononuclear or polynuclear or, in particular, aromatic radicals of rnonuclear or polynuclear hydrocarbons. In the case of heterocyclic aromatic radicals, they have in particular one or two oxygen, nitrogen or sulfur atoms in the aromatic nucleus. The polynuclear aromatic radicals can be fused together or they can be combined with each other by means of C-C compounds or by means of groups of bridges, such as -O-, -S-, -CO- or -C0-NH-. The valence bonds of the aromatic divalent radicals can be in the "para" position or in a comparable position coaxially or parallel to each other, or else in a "meta" position with each other or in a comparable angular position. The valence links, which are in a coaxial or parallel position, are oriented in opposite directions. An example of coaxial links in opposite directions are the b? Feno-4,4'-dulo links. An example of links oriented in opposite directions to each other are the naphthalene-n-1,5 or naphthalene-n-2,6 bonds, while the naphthalam-1,8 bonds are all oriented in parallel in the same direction. Examples of preferred aromatic bivalent radicals, whose valence bonds are in the "para" position or in a comparable coaxial or parallel position, are aromatic mononuclear radicals, with free valences para-constants, especially 1.4 -femlene, or else condensed binuclear aromatic radicals with parallel bonds oriented in opposite directions to each other, in particular 1,4-, 1,5- and 2,6-naphthalene, or aromatic bmuclear radicals, bound by a CC- link, with coaxial links oriented in opposite directions, especially 4,4 '~ b? fen? leno. Examples of preferred aromatic bivalent radicals, whose valence bonds are to each other in a "meta" position or in a comparable angular position, are aromatic mononuclear radicals with constant free valencies to each other, especially 1,3-phen or condensed aromatic bmuclear radicals, with links oriented at an angle to each other, in particular 1, 6-naphthalene and 2,7-naphthalene, or aromatic bmuclear radicals linked by means of a CC bond, with links oriented at an angle to one another, especially 3,4'-b? fen? leno. If any type of radical means bivalent araliphatic radicals, it should be understood that these are groups that contain one or more aromatic bivalent radicals, which are combined with an alkyl ene radical through a valence or of the two valences. A preferred example of a radical of this type is the group -C6H4-CH-2-. If any type of radical means aliphatic monovalent radicals, it should be understood that these are branched alkyl and especially straight chain, for example, alkyl with between one and six carbon atoms, especially methyl. If any type of radicals means monovalent cycloaliphatic radicals, it should be understood that these are groups containing carbocyclic radicals with between five and eight carbon atoms, but preferably with six carbon atoms, nuclear. An example of a radical of this type is cyclohexyl. If any radicals are monovalent aromatic radicals, then they are heterocyclic aromatic radicals, which may be polynuclear mononuclear or, in particular, aromatic or mononuclear hydrocarbon radicals. In the case of heterocyclic aromatic radicals, they have in particular one or two oxygen, nitrogen or sulfur atoms in the aromatic nucleus. An example of a radical of this type is phenyl or naphthyl. If any type of radicals means araliphatic monovalent radicals, it can be understood that these are groups containing one or more aromatic radicals, which are combined by means of a valence with an alkylene radical. A preferred example of a radical of this type is the benzyl group. All these aliphatic radicals, cycloaliphatics, aromatics or araliphatics can be substituted with inert groups. Inert groups are understood as the substituents, which do not negatively influence the intended application. Examples of such substituents are alkyl, alkoxy or halogen. If any type of radical means halogen, it is in this case, for example, fluorine, bromine or especially chlorine. Particularly preferably in the case of the filament and / or monofilament yarns used according to the invention, they are filament or inonophil filaments of phosphorus-modified polyethylene terephthalate. High strength filament yarns or rhono-filaments used can be formed from modified polyesters, which generally have an intrinsic viscosity of at least 0.5 dl / g, but preferably between 0.6 and 1.5 dl / g. The intrinsic viscosity measurement is carried out in a polyester solution in chloracetic acid at 25 ° C. The high strength filament yarns used have monkey thread titers of 2,000 dtex, preferably between 280 and 1,700 dtex. Filament yarns used as warp yarns generally have a higher yarn count, for example between 1,100 and 1,700 dtex, while filament yarns used as weft yarns have between 550 and 1,100 dtex. The title of the individual fibers of the filaments in the high strength filament yarns used ranges around a value equal to or less than 25 dtex, but preferably between 4 and 20 dtex. Sections of the filaments in the filaments of high resistance filaments or rnonofilaments used can be optional. For example they can be ellipse-shaped, they can be bilobal or multi-lobed, they can be in the form of narrow bands or they can preferably be round. The high-strength filament yarns used, manufactured from phosphorus-modified copolyesters, are already known per se, for example from EP-A-661 393, whose description also forms an integral part of the present description. The production of the phosphorus-modified copolyesters is carried out according to known methods by polycondensation of the respective bifunctional component components, for example as described in the aforementioned EP-A-661 393. The fabrication of the high-strength filaments can be carried out according to already known methods of melt-spinning, for example as described in the aforementioned EP-A-661 393. The fabrics forming the safety belts recommended in the invention can be manufactured by known weaving techniques. The yarn densities of at least one of the yarn systems of the fabrics used according to the invention are generally at least 30 yarns per centimeter, but at least 35 yarns per centimeter and, most preferably, at least 35 yarns per centimeter. 40 threads per centimeter. The safety belts advocated in the invention may contain polyester fibers dyed in the spinning dough and / or may be added to a dyeing process already known per se, after the manufacture of the fabric. Polyester fibers of different shapes can also be used. If polyester fibers dyed in the spinning dough or provided with matting means are used, for example with titanium dioxide, these fibers preferably contain particles with an average diameter of less than 1 μm, but more preferably with a smaller diameter of 0.5 μrn. Examples of polyester fibers dyed in the spinning dough are the types dyed with carbon black. The invention also relates to the use of the phosphorus-modified fibers, defined above, for the production of security pins. The safety belts constructed according to the invention are usedfor example, in automobiles, but also in airplanes or other air transport vehicles, as well as in fast boats, especially in motor boats used for leisure time entertainment. The invention also relates to the use of security bolts in these vehicles.

Claims (18)

NOVELTY OF THE INVENTION CLAIMS

1. - Safety belt, which contains a fabric that contains high-strength filament yarns manufactured from a phosphorus-modified copolyester, with a yarn count of less than 2,000 dtex, with an individual fiber title equal or less than 25 dtex, as well as with a stretch less than 30% under the maximum traction force, containing the copolyester modified with phosphorus, in the polymer chain, a bifunctional compound of phosphorus in an amount between 0.1 and 5 % by weight, based on the amount of phosphorus.

2. Safety belt according to claim 1, further characterized in that the copolyester phosphorus-free copolyester contains in the polymer chain a bi-functional phosphorus compound in an amount of between 0.2 and 0.8% by weight, based on the amount of phosphorus.

3. Security commutator according to claim 1, further characterized in that its fabric consists of at least two systems of yarns, which consist respectively of at least 90% by weight of filaments of high strength filaments, manufactured from copolyester modified with phosphorus.

4. Safety belt according to claim 1, further characterized in that the high strength filament yarn has a maximum tensile force, referred to the fineness, of more than 60 cN / tex, but preferably more than 65 cN / tex. cN / tex, and a stretching of between 10 and 25% under the maximum traction force.

5. Safety belt according to claim 1, further characterized in that the high strength filament yarn has a shrie of less than 20% under hot air at a temperature of 200 ° C. 6.- Conformity safety belt with the remvindication 1, further characterized in that the fabric contains, in addition to the high strength filament yarns manufactured from phosphorus-modified copolyester, monofilaments having a diameter of 0.5 nm or less, containing the monofilaments in the chain of the polymer a phosphorus-modified copolyester, having an optional phosphorus compound, in an amount of between 0.1 and 5% by weight, but preferably 0.2 and 0.8% by weight, based on the amount of phosphorus. 7. Safety comma according to claim 6, further characterized in that the reinforcements have a maximum tensile force, referred to the figure, of more than 35 cN / tex and a stretch of more than 15% ba or the maximum force of traction. 8. Seatbelt according to claim 6, further characterized in that the monoflament has a shrie of less than 20% under hot air at a temperature of 180 ° C. 9.- Safety belt according to claim 1, characterized also because the high strength filament yarn lacks sizing. 10. Safety belt in accordance with claim 1, further characterized in that its fabric has a twill weave, in particular a K2 / 2 weave of a bream or an inflamed ligament "feμ1;". 11.- Safety belt according to claim 1, further characterized in that its fabric has a weight per unit area of less than 100 g per linear meter for a width of 50 mm and a fabric thickness less than 1.5 mm. . 12. Safety belt according to claim 1, further characterized in that its fabric has a maximum tensile force of more than 1470 daN with a width of 50 mm, and a reference stretch of less than 20% with 50 nm of width and with 1,000 N. 13.- Security commutator according to claim 1, further characterized in that the phosphorus modified copolyester contains the repetitive structure units of the formula I: -0-0C-Ar-l-C0 -0-Rl (T) and in the polymer chain has component groups of formula II: O O R3 in which formulas: Ar-i represents a bivalent aromatic monon-clear or polynuclear radicalR1 is a aliphatic or cycloaliphatic, aromatic or araliphatic bivalent radical, and R3 is a monovalent aliphatic, cycloaliphatic, aromatic or araliphatic radical. 14. Safety comformum according to claim 13, further characterized in that Ar-i means phenylene or naphthylene, especially 1,4-phenlene or full 2,6-naph. 15.- Safety commutator according to claim 13, further characterized in that R1 is a radical of the formula ~ CnH2n-, wherein n is an integer between 2 and 6, especially etiien, or represents a radical derived of cyclohexandi ethanol. 16.- Security commutator according to claim 13, further characterized in that R2 is a radical of the formula -CmH2m ~, where n is an integer between 2 and 10, or represents a cyclic radical of an alkanol with between 4 and 8 carbon atoms, but preferably with carbon atoms, and because R3 means Ci-Cβ-alkyl, cyclohexyl, phenyl or benzyl. 17.- Use of high strength filament yarns manufactured from phosphorus-modified copolyester, with a titre of monkeys yarns of 2,000 dtex, with a titre of individual fibers equal to or less than 25 dtex, as well as a stretched less than 30% under the maximum tensile force, for the manufacture of safety belts, the phosphorus-modified copolyester in the polymer chain containing a bi-functional phosphorus compound in an amount of between 0.1 and 5% by weight , referred to the amount of phosphorus. 18. Use of safety belts, manufactured according to claim 1, in automobiles, airplanes or motorboats.