EP0768405A1 - Woven fabric with adjustable gas and/or liquid permeability containing hybrid yarns, process for its further processing, textile structure with predetermined gas and/or fluid permeability and its use - Google Patents

Abstract

In (non)woven fabric containing at least 2 systems of parallel filaments, at least one of these systems has more than 10 filaments/cm and at least 10% of the system consists of hybrid yarn containing reinforcing filaments and matrix filaments of thermoplastic polymer with a lower m.pt. Also claimed are a method of making textile webs with predetermined gas permeability from this fabric and the textile webs per se.

Description

The present invention relates to fabrics and scrims with adjustable gas and / or liquid permeability from which textile fabrics with predetermined gas and / or liquid permeability can be produced in a simple manner. These textile fabrics can be used in many areas of application, in particular for the production of airbags.

Fabrics and scrims of this type are used, among other things, to produce airbags which are inflated explosively in the event of an accident and are intended to protect the occupants, in particular the driver of the automobile, from impact injuries. Airbags are made in part from gas-impermeable, coated fabrics which contain a gas-permeable filter fabric or filter fabric segment or an opening on one side of the bag.

It has already been proposed to use uncoated fabrics for the production of airbags, for example in EP-A-453,678. According to the description in this document, the production of such fabrics requires at least twice calendering the raw fabric in order to set the desired gas tightness. With this solution, the omission of the coating is purchased through additional process steps.

It has also already been proposed to produce fabrics for use in airbags from yarns or membranes that contain meltable components.

For example, DE-A-4,009,611 describes a gas-permeable woven fabric made of synthetic yarn which is spun from a staple fiber mixture, in addition to aramid fibers, thermally deformable fibers, such as fibers made of polyamides, polyvinyl chloride, polypropylene or polyester, are used. According to the description, it is important that the yarns forming the fabric are not made from filaments but from staple fibers in order to have laterally protruding fiber ends available over the entire length of the yarn, which make the yarn particularly bulky and thereby the filtering effect of the resulting fabric increase.

From DE-A-4,411,159 an airbag made of a fabric is known, which comprises warp and weft threads, which are each made of polymer material with a high melting point, and which additionally contains polymer threads with a low melting point, such as woven from polyamide or polyester. The polymer threads with a low melting point are arranged at predetermined intervals and extend along at least one of the warp and weft threads. By heating these polymer threads, they are welded to the warp and weft threads. This is to prevent the fabric from fraying when cut by a press or punch. Hybrid yarns can also be used in the manufacture of this fabric. In addition to these yarns, there are always yarns made of polymer material with a high melting point in these fabrics, these latter yarns making up the majority of the fabric.

JP-A-03-266,745 describes a flexible band of hybrid yarns which, in addition to a first filament yarn component, contain a matrix-forming elastomeric second filament yarn component. Such tapes will be wound on a mandrel and by melting the second filament yarn component, a flexible molded body is produced which is suitable for use as an airbag. This manufacturing route bypasses the manufacture of a textile surface, such as a woven or knitted fabric.

GB-A-2,251,410 describes the production of airbags, a melt fiber being used in the formation of seams.

From JP-A-05-338,510 a fabric for the production of airbags is known, one side of the fabric having meltable short fibers.

Finally, DE-A-4,142,884 discloses an airbag made of fabrics which are made up of bicomponent fibers of the core-sheath type or of the side-by-side type. The first component used is polyamide, polyester, aramid or ultra-high molecular weight polyethylene and the second component is low-melting polymer such as polyethylene, modified polyester, polyurethane or ethylene-vinyl acetate copolymer. According to the description, the difference between the melting points of the materials forming the two components should be at least 100 ° C. In a further embodiment, an airbag made of an elastic membrane is described which has an elongation at break of at least 100%. In a third embodiment, an airbag consisting of an elastomeric body and a shaping part attached to parts of this body is described, this part containing elastic fibers or threads and high-modulus filaments. In addition to the actual airbag, this embodiment therefore also requires an additive which keeps the inflated airbag in an optimal shape.

Furthermore, textile fabrics containing carrier fibers have already become known, which are provided with a coating that allows the textile fabric to be folded for placement in a small volume and / or provides excellent kink resistance. These include, for example PVC-coated tarpaulins or PVC-coated weather clothing. However, these products are manufactured by subsequently coating a textile fabric; Here, coating agents are used, the components of which are to be assigned to other chemical substance classes than the components of the textile fabric.

From JP-A-04-146,235, fabrics and knitted fabrics are known which contain a hybrid yarn made of a multi-component fiber and a conventional polyester fiber. The multi-component fiber consists of a thermoplastic elastomer, such as an elastomeric polyurethane or an elastomeric polyester, and a polyester. The fabrics described are intended for textile applications and are characterized by good elastic recovery and freedom from creasing. The fabrics are stabilized by melting the elastomer component during dyeing, and the result is a good distribution of the melted component in the fabric. This publication does not refer to the production of gas-tight fabrics.

JP-A-04-353,525 discloses prepregs made of hybrid yarns which, in addition to reinforcing fibers, are made up of filaments made of thermoplastic and elastomeric materials. Polyester and polyurethane are mentioned as thermoplastic and elastomeric components. The prepregs are used to manufacture composite materials; For this purpose, hybrid yarns can be produced from the two filament types, which are processed into fabrics and then converted into shaped structures by heating, or direct molding processes such as pultrusion or filament winding processes are used. Shaped structures with complicated shapes can be produced from the prepregs. The shaped structures are characterized by good damping properties, high flexibility and impact resistance and can be used as conveyor belts, shoe soles or sporting goods.

This publication does not refer to the production of textile fabrics with predetermined gas permeability.

Furthermore, from our older German patent application 19531001.2, scrims made of hybrid yarns are known, which can be used as a backing for nonwoven reinforcement. The thread densities of the fabrics specifically described there are relatively high at up to 10 threads per centimeter.

There is still a need for textile fabrics containing reinforcing filaments and matrix material, the gas and / or liquid permeability of which can be specifically adjusted, and which have a high kink resistance (even at low temperatures down to about - 25 ° C), as well as a high adhesive strength between Reinforcing filaments and matrix material, in particular on preliminary products, which can be processed in a simple manner into such textile fabrics.

It has now surprisingly been found that fabrics or scrims derived from special hybrid yarns can be processed in a simple manner into textile fabrics with selectively adjustable gas and / or liquid permeability. In comparison to conventionally coated fabrics, these textile fabrics allow the production of small-volume folded products that can be inflated suddenly and are outstandingly suitable for the manufacture of airbags.

The invention relates to fabrics or scrims containing at least two thread systems of parallel threads, at least one of these thread systems having more than 10 threads per centimeter and consisting of at least 10%, based on the thread system, of hybrid yarns containing reinforcing filaments and deep-melting matrix filaments made of thermoplastic polymers.

Depending on the intended use, the fabrics or scrims according to the invention can consist to a small extent or entirely of the hybrid yarns defined above. For example, it is possible to build up only one of the thread systems constructing the fabrics or scrims according to the invention entirely or only partially from hybrid yarns. The proportion of the hybrid yarns to be selected in the individual case will be determined in addition to the desired application purpose by the respective proportion of the matrix filaments in the hybrid yarn. The proportion of hybrid yarns in the fabric or in the scrim or the proportion of matrix filaments in the hybrid yarn is selected according to the requirement profile of the processor.

In addition to the hybrid yarns defined above, some of the yarns that make up the fabrics or scrims can only consist of carrier filaments or only binder filaments. The proportion of the hybrid yarns must in any case be selected so that its proportion in at least one of the thread systems constructing the fabric or scrim is at least 10%, preferably at least 50%, very particularly preferably at least 95%.

At least one direction is preferred, e.g. the weft or warp direction, the woven or non-woven fabric according to the invention is built entirely from the hybrid yarns defined above.

Depending on the intended use, the fabrics or scrims according to the invention can consist of two or more thread systems; two thread systems are preferably provided (warp and weft threads).

The thread densities of at least one of the thread systems of the fabrics or scrims according to the invention are at least 10 threads per centimeter, preferably at least 15 threads per centimeter, and particularly preferably at least 20 threads per centimeter.

Woven or laid fabrics are preferred which have two thread systems with thread densities of at least 15 threads per centimeter and which thread systems consist of at least 10%, preferably at least 50%, of hybrid yarns containing reinforcing filaments and low-melting matrix filaments made of thermoplastic polymers.

Fabrics or scrims which consist of two thread systems, each consisting of at least 95% hybrid yarns containing reinforcing filaments and deep-melting matrix filaments made of thermoplastic polymers, are very particularly preferred.

Another very particularly preferred embodiment of the fabrics or scrims according to the invention contains, in at least one thread system, a combination of hybrid yarns containing reinforcing filaments and low-melting matrix filaments and yarns made from carrier filaments, or that at least one thread system contains a combination of different hybrid yarns containing reinforcing filaments and different proportions of low-melting ones Matrix filaments are present, wherein several of the hybrid yarns and the carrier filament yarns or several of the different hybrid yarns are each arranged in a predetermined pattern.

With this embodiment, the gas and / or liquid permeability of parts of the textile surface resulting from further processing can be adjusted in a controlled manner.

The hybrid yarns used to produce the fabrics or scrims according to the invention contain matrix filaments made of thermoplastic polymers which have a melting point which is usually at least 10 ° C., preferably at least 30 ° C. below the melting point or the decomposition point of the reinforcing filaments.

The fabrics or scrims according to the invention can be produced using techniques known per se. Examples of this can be found in EP-A-442,373, -509,399 and -665,313.

The reinforcing or carrier filaments used can be filaments made from a large number of materials. Reinforcing or carrier filaments in the sense of this description mean filaments which take on a reinforcing function in the textile fabric to be produced from the fabrics or scrims.

In a first preferred embodiment, the reinforcement or carrier filaments are made up of individual filaments which have an initial modulus of more than 50 GPa.

Preferred reinforcement or carrier filaments of this type consist of glass; Carbon; Metals or metal alloys, such as steel, aluminum or tungsten; Non-metals such as boron; Metal, semimetal or non-metal oxides, carbides or nitrides, such as aluminum oxide, zirconium oxide, boron nitride, boron carbide, silicon carbide, silicon dioxide (quartz); Ceramics, or high-performance polymers (i.e. fibers that provide a very high initial modulus and a very high tensile strength with little or no stretching), such as liquid-crystalline polyesters (LCP), poly (bis-benzimidazo-benzophenanthrolines (BBB), poly (amide -imides) (PAI), polybenzimidazoles (PBI), poly (p-phenylene benzobisoxazoles (PBO), poly (p-phenylene benzobisthiazoles) (PBT), polyether ketones (PEK, PEEK, PEEKK), polyetherimides (PEI) , Polyether sulfones (PESU), polyimides (PI), poly (p-phenylenes) (PPP), polyarylene sulfides (PPS), polysulfones (PSU), polyolefins such as polyethylene (PE) or polypropylene (PP), and aramids (HMA) , such as poly- (m-phenylene-isophthalamide), poly- (m-phenylene-terephthalamide), poly- (p-phenylene-isophthalamide), poly- (p-phenylene-terephthalamide), or from organic solvents such as N- Methyl pyrrolidone, spinnable aramids derived from terephthalic acid dichloride and a mixture of two or more aromatic diamines, for example the combination p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 3,3'-dimethylbenzidine, or p-phenylenediamine, 1,4-bis (4-aminophenoxy ) -benzene, 3,4'-diaminodiphenyl ether, or p-phenylenediamine, m-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene.

Reinforcement or carrier filaments made of glass, carbon or aromatic polyamide are particularly preferred.

In a second particularly preferred embodiment, reinforcement or carrier filaments and matrix or binder filaments are used which consist of polymeric materials from one polymer class, for example polyolefins, polyamides or preferably polyesters, in particular polyethylene terephthalate.

In this embodiment, the individual filaments of the reinforcement or carrier filaments have an initial modulus of more than 10 GPa. Reinforcement or carrier filaments for this embodiment are preferably high-strength and low-shrinkage polyester filament yarns, in particular with a yarn titer of less than or equal to 750 dtex, a tenacity of greater than or equal to 55 cN / tex, a maximum tensile strength elongation of greater than or equal to 15% and a hot air shrinkage (measured at 200 ° C) less than or equal to 9%.

The maximum tensile force and the maximum tensile force elongation of the polyester yarns used are measured in accordance with DIN 53 830, Part 1.

The thermal shrinkage (hot air shrinkage) of the polyester yarns used is measured in accordance with DIN 53 866, Part 3 at a temperature of 200 ° C on free-hanging yarn samples with a treatment time of 15 minutes. 10 m of string are used with a reel tension of 0.5 cN / tex.

Matrix or binder filaments in the hybrid yarns used according to the invention consist of or contain thermoplastic polymers. These can be any melt-spinnable thermoplastics, as long as the filaments produced therefrom melt at a lower temperature than the melting or decomposition temperature of the reinforcing filaments used in the respective case.

Matrix or binder filaments made of a thermoplastic modified polyester, in particular a modified polyethylene terephthalate, are preferably used; the modification lowers the melting point compared to the filament made of unmodified polyester.

Ar¹

einen zweiwertigen ein- oder mehrkernigen aromatischen Rest darstellt, dessen freie Valenzen sich in para-Stellung oder in einer zu dieser Stellung vergleichbaren parallelen oder koaxialen Stellung zueinander befinden, vorzugsweise 1,4-Phenylen und/oder 2,6-Naphthylen darstellt,

R¹ und R³

unabhängig voneinander zweiwertige aliphatische oder cycloaliphatischen Reste darstellen, insbesondere Reste der Formel -C_nH_2n-, worin n eine ganze Zahl zwischen 2 und 6 ist, insbesondere Ethylen, oder einen von Cyclohexandimethanol abgeleiteten Rest darstellen, und

R²

einen zweiwertigen aliphatischen, cycloaliphatischen oder ein- oder mehrkernigen aromatischen Rest darstellt, dessen freie Valenzen sich in meta-Stellung oder in einer zu dieser Stellung vergleichbaren gewinkelten Stellung zueinander befinden, vorzugsweise 1,3-Phenylen darstellt.

Modified polyesters of this type particularly preferably contain the recurring structural units of the formulas I and II

-O-OC-Ar ¹ -CO-OR ¹ - (I),

and

-O-OC-R ² -CO-OR ³ - (II),

wherein

Ar ¹

represents a divalent mono- or polynuclear aromatic radical, the free valences of which are in the para position or in a parallel or coaxial position with respect to one another, preferably 1,4-phenylene and / or 2,6-naphthylene,

R ¹ and R ³

independently represent divalent aliphatic or cycloaliphatic radicals, in particular radicals of the formula -C _n H _2n -, in which n is an integer between 2 and 6, in particular ethylene, or a radical derived from cyclohexanedimethanol, and

R ²

represents a divalent aliphatic, cycloaliphatic or mononuclear or polynuclear aromatic radical, the free valences of which are found in meta position or in an angled position comparable to this position to each other, preferably represents 1,3-phenylene.

Very particularly preferred modified polyesters of this type contain 40 to 95 mol% of the repeating structural units of the formula I and 60 to 5 mol% of the repeating structural units of the formula II; Ar ^{1 is} 1,4-phenylene and / or 2,6-naphthylene, R ¹ and R ^{3 are} ethylene and R ^{2 is} 1,3-phenylene.

In a further preferred embodiment, matrix or binder filaments are used which consist of or contain a thermoplastic and elastomeric polymer. These can also be any melt-spinnable and elastomeric thermoplastics, as long as the filaments produced therefrom melt at a lower temperature than the melting or decomposition temperature of the reinforcing filaments used in the respective case.

In the context of this description, “elastomeric polymer” is understood to mean a polymer whose glass transition temperature is less than 23 ° C., preferably less than 0 ° C.

Examples of thermoplastic and elastomeric polymers are elastomeric polyamides, polyolefins, polyesters and polyurethanes.

Ar² und Ar³

unabhängig voneinander zweiwertige aromatische Reste darstellen,

R⁴

einen zweiwertigen aliphatischen oder cycloaliphatischen Rest darstellt, und

R⁵

den zweiwertigen Rest eines Polyalkylenethers bedeutet.

Hybrid yarns are particularly preferably used which contain matrix fibers made of thermoplastic and elastomeric polyester which contains the recurring structural units of the formulas III and IV

-O-OC-Ar ² -CO-OR ⁴ - (III),

and

-O-OC-Ar ³ -CO-OR ⁵ - (IV),

wherein

Ar ² and Ar ³

independently represent divalent aromatic radicals,

R ⁴

represents a divalent aliphatic or cycloaliphatic radical, and

R ⁵

means the divalent radical of a polyalkylene ether.

Ar ² and Ar ^{3 are} preferably independently of one another a phenylene and / or a naphthylene radical.

Ar ² and Ar ³ each particularly preferably denote 1,4-phenylene.

R ⁴ as a divalent aliphatic radical means straight-chain or branched alkylene or alkylidene; these are usually residues with two to twenty carbon atoms, preferably two to eight carbon atoms and in particular two to four carbon atoms.

R ⁴ is particularly preferably straight-chain alkylene having two to six carbon atoms, in particular ethylene.

R ⁴ as a divalent cycloaliphatic radical usually means a radical containing five to eight, preferably six ring carbon atoms; this carbocycle is particularly preferably part of an aliphatic chain. An example of a particularly preferred representative of this type is the rest of the cyclohexanedimethanol.

R ⁴ is particularly preferably a radical of the formula -C _n H _2n -, in which n is an integer between 2 and 6 or a radical derived from cyclohexanedimethanol.

R ⁵ as a divalent radical of a polyoxyalkylene usually means a polyether radical which has recurring oxyethylene, oxypropylene or in particular oxybutylene units or mixtures of these units.

R ⁵ particularly preferably represents a radical of the formula V.

- [C _o H _2o -O] _z -C _o H _2o - (V), (V),

wherein o is an integer from two to four and z is an integer from 1 to 50.

Most preferably o is four and z is an integer from 10 to 18.

Hybrid yarns made of thermoplastic and elastomeric polyester containing the recurring structural units of the formulas III and IV defined above are particularly preferred, wherein Ar ² and Ar ^{3 are} 1,4-phenylene, R ^{4 is} ethylene, R ^{5 is} a group of the formula V defined above is o is four, and in which the proportion of the recurring structural units of the formula V, based on the proportion of the polyester molecule, is 5 to 60% by weight.

Fibers made of such polyesters have different melting points depending on the proportion of the repeating structural units of the formula V; the higher the proportion of these structural units, the lower the melting point can be set. For example, fibers made of an elastomeric polyester of this type with a content of 13% by weight of polyoxybutylene have a melting point of about 220 ° C., while fibers made of an elastomeric polyester of this type with a content of 53% by weight of polyoxybutylene have a melting point of about 160 ° C.

R⁶, R⁷ und R⁸

unabhängig voneinander einen zweiwertigen aliphatischen, cycloaliphatischen, aromatischen oder araliphatischen Rest bedeuten,

R⁶ und R⁸

vorzugsweise zweiwertige ein- oder zweikernige aromatische Reste sind, insbesondere Phenylen und/oder Naphthylen,

R⁷

vorzugsweise ein Rest der Formel -C_pH_2p- ist, worin p eine ganze Zahl zwischen 2 und 6 ist oder ein von Cyclohexandimethanol abgeleiteter Rest ist, insbesondere Butan-1,4-diyl,

R⁹

einen Rest der Formeln VIII und/oder IX bedeutet

        -[C_qH_2q-O]_x-C_qH_2q-     (VIII),



        -[R¹⁰-O-OC-R¹¹-CO-O]_y-R¹⁰-     (IX),

worin

q

eine ganze Zahl von zwei bis vier bedeutet und x eine ganze Zahl von 1 bis 50,

R¹⁰

einen zweiwertigen aliphatischen oder cycloaliphatischen Rest oder einen Rest der Formel VIII darstellt,

R¹¹

ein zweiwertiger aliphatischer, cycloaliphatischer, aromatischer oder araliphatischer Rest ist, und

y

eine ganze Zahl von 1 bis 50 bedeutet.

Hybrid yarns are particularly preferably used which contain matrix fibers made of thermoplastic and elastomeric polyurethane which contains the recurring structural units of the formulas VI and VII

- [O-OC-NH-R ⁶ -NH-CO-OR ⁷ ] - (VI),



- [O-OC-NH-R ⁸ -NH-CO-OR ⁹ ] - (VII),

wherein

R ⁶ , R ⁷ and R ⁸

independently of one another represent a divalent aliphatic, cycloaliphatic, aromatic or araliphatic radical,

R ⁶ and R ⁸

are preferably divalent mono- or dinuclear aromatic radicals, in particular phenylene and / or naphthylene,

R ⁷

is preferably a radical of the formula -C _p H _2p -, in which p is an integer between 2 and 6 or is a radical derived from cyclohexanedimethanol, in particular butane-1,4-diyl,

R ⁹

represents a radical of the formulas VIII and / or IX

- [C _q H _2q -O] _x -C _q H _2q - (VIII),



- [R ¹⁰ -O-OC-R ¹¹ -CO-O] _y -R ¹⁰ - (IX),

wherein

q

is an integer from two to four and x is an integer from 1 to 50,

R ¹⁰

represents a divalent aliphatic or cycloaliphatic radical or a radical of the formula VIII,

R ¹¹

is a divalent aliphatic, cycloaliphatic, aromatic or araliphatic radical, and

y

is an integer from 1 to 50.

Hybrid yarns made from thermoplastic and elastomeric polyurethane containing the recurring structural units of the formulas VI and VII defined above are particularly preferably used, wherein R ^{7 is} butane-1,4-diyl, R ^{9 is} a radical of the formula VIII defined above, wherein q is a whole Number from two to four, in particular four, and x is an integer from 1 to 50, preferably from 10 to 18 and in which R ⁶ and R ⁸ independently of one another are phenylene or naphthylene.

Preferred elastomeric polyamides are known per se and are described, for example, in Domininghaus: "The plastics and their properties", 3rd edition, VDI Verlag GmbH, Düsseldorf 1988, pp. 456-461.

If any radicals in the structural formulas defined above mean divalent aliphatic radicals, this means branched and in particular straight-chain alkylene, for example alkylene with two to twenty, preferably with two to eight, carbon atoms. Examples of such radicals are ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl or octane-1,8 -diyl.

If any radicals in the structural formulas defined above are divalent cycloaliphatic radicals, they are to be understood as meaning groups which contain carbocyclic radicals having five to eight, preferably six, ring carbon atoms. Examples of such radicals are cyclohexane-1,4-diyl or the group -CH ₂ -C ₆ H ₁₀ -CH ₂ -.

If any radicals in the structural formulas defined above mean divalent aromatic radicals, these are mono- or polynuclear aromatic hydrocarbon radicals or heterocyclic-aromatic radicals which can be mono- or polynuclear. In the case of heterocyclic-aromatic radicals, these have in particular one or two oxygen, nitrogen or sulfur atoms in the aromatic nucleus.

Polynuclear aromatic radicals can be condensed with one another or linked to one another via CC bonds or via bridging groups such as —O—, —S—, —CO— or —CO — NH groups.

The valence bonds of the divalent aromatic radicals can be in a para- or in a comparable coaxial or parallel position to one another, or also in a meta or in a comparable angled position to one another.

The valence bonds, which are in a coaxial or parallel position, are directed in opposite directions. An example of coaxial, oppositely directed bonds are the biphenyl-4,4'-diyl bonds. An example of parallel, opposite bonds are the naphthalene 1,5 or 2,6 bonds, while the naphthalene 1,8 bonds are parallel aligned.

Examples of preferred divalent aromatic radicals, the valence bonds of which are in para- or in a comparable coaxial or parallel position to one another, are mononuclear aromatic radicals with mutually para-free valences, in particular 1,4-phenylene or dinuclear fused aromatic radicals with parallel directed bonds, in particular 1,4-, 1,5- and 2,6-naphthylene, or dinuclear aromatic residues linked via a CC bond with coaxial, oppositely directed bonds, in particular 4,4'-biphenylene.

Examples of preferred divalent aromatic radicals whose valence bonds are in a meta or in a comparable angled position to one another are mononuclear aromatic radicals with free valences which are meta to one another, in particular 1,3-phenylene or dinuclear condensed aromatic radicals with bonds oriented at an angle to one another, in particular 1,6- and 2,7-naphthylene, or dinuclear aromatic residues linked via a CC bond with bonds oriented at an angle to one another, in particular 3,4'-biphenylene.

If any radicals mean divalent araliphatic radicals, this means groups which contain one or more divalent aromatic radicals contain which are combined with one or both valences with an alkylene radical. A preferred example of such a radical is the group -C ₆ H ₄ -CH ₂ -.

The recurring structural units of the formula III or VI or IV or VII are typical hard or soft segments. Thermoplastic polyesters or polyurethanes of this type are known and are described, for example, in Domininghaus: "The plastics and their properties", 3rd edition, VDI Verlag GmbH, Düsseldorf 1988, pp. 518-524.

R ⁶ and R ^{8 are} preferably divalent mono- or dinuclear aromatic radicals, in particular phenylene and / or naphthylene.

R ⁷ is preferably a radical of the formula -C _p H _2p -, in which p is an integer between 2 and 6 or a radical derived from cyclohexanedimethanol. R ⁷ butane-1,4-diyl is particularly preferred.

R ⁹ is preferably a radical of the formula VIII defined above.

R ⁹ particularly preferably represents a radical of the formula VIII, in which q is an integer from two to four, in particular four, and x is an integer from 1 to 50, preferably from 10 to 18.

R ⁹ likewise preferably represents a radical of the formula IX defined above, in which R ^{10 is} a radical of the formula VIII, and R ^{7 represents} a radical of the formula -C _p H _2p -, in which p is an integer between 2 and 6, in particular butane-1,4-diyl, or a radical derived from cyclohexanedimethanol or represents a phenylene and / or naphthylene radical.

Thermoplastic and elastomeric polyurethanes containing the recurring structural units of the formulas VI and VII defined above are very particularly preferably used, wherein R ^{7 is} butane-1,4-diyl, R ^{9 is} a radical of the formula VIII defined above, where q is an integer from two to four, in particular four, and x is an integer from 1 to 50, preferably from 10 to 18, and in which R ⁶ and R ⁸ independently of one another are phenylene or naphthylene.

Fibers made from such polyurethanes have different melting points, depending on the proportion of the repeating structural units of the formula VIII or IX; the higher the proportion of these structural units, the lower the melting point can be set.

All of these aliphatic, cycloaliphatic, aromatic, araliphatic or polyoxyalkylene radicals can be substituted with inert groups. These are to be understood as substituents that do not negatively influence the envisaged application.

Examples of such substituents are alkyl, alkoxy or halogen.

Alkyl radicals are to be understood as meaning branched and in particular straight-chain alkyl, for example alkyl having one to six carbon atoms, in particular methyl.

Alkoxy radicals are to be understood as meaning branched and in particular straight-chain alkoxy, for example alkoxy with one to six carbon atoms, in particular methoxy.

If any radicals are halogen, it is, for example, fluorine, bromine or, in particular, chlorine.

The matrix filaments used in the hybrid yarn used according to the invention can be constructed from thermoplastic polymers which usually have an intrinsic viscosity of at least 0.5 dl / g, preferably 0.6 to 1.5 dl / g. The intrinsic viscosity is measured in a solution of the thermoplastic polymer in dichloroacetic acid at 25 ° C.

If reinforcing filaments made of polyester are used in the hybrid yarn to be used according to the invention, these polyesters usually have an intrinsic viscosity of at least 0.5 dl / g, preferably 0.6 to 1.5 dl / g. The intrinsic viscosity is measured as described above.

The hybrid yarns used according to the invention usually have yarn titer of 2000 to 150 dtex, preferably 1100 to 150 dtex.

The individual fiber titer of the reinforcement or carrier filaments and the matrix or binder filaments usually ranges from 2 to 10 dtex, preferably 4 to 8 dtex.

The cross sections of the reinforcement or carrier filaments and the matrix or binder filaments can be any; for example elliptical, bi- or multilobal, ribbon-shaped or preferably round.

The thermoplastic polymers are prepared by processes known per se by polycondensation of the corresponding bifunctional monomer components. In the case of polyesters, dicarboxylic acids or dicarboxylic acid esters and the corresponding diol components are usually used. Such thermoplastic and optionally elastomeric polyesters, polyurethanes, polyamides and polyolefins are already known.

The reinforcing or carrier filaments used in the textile fabrics according to the invention are also known per se.

The mechanical properties of the hybrid yarns used according to the invention are dependent on the composition, such as the type and proportion of the reinforcing filaments or the matrix filaments, depending on the physical structure of the yarns, e.g. Degree of turbulence, can be varied within wide limits. The proportion of the matrix filaments is usually 3 to 50% by weight, based on the weight of the hybrid yarn.

The term "hybrid yarn" is to be understood in its broadest meaning within the scope of this description. Accordingly, this includes any combination containing reinforcing filaments and the matrix filaments defined above.

Examples of possible hybrid yarn types are filament yarns from different types of filaments which are interwoven with one another or combined with one another by means of another technology, such as for example twisting. All of these hybrid yarns are characterized by the presence of two or more types of filaments, at least one type of filament being a reinforcing filament and at least one type of filament being a matrix filament as defined above.

Hybrid yarns produced by intermingling or commingling techniques are particularly preferably used.

The production of the hybrid yarns used in accordance with the invention is described using the example of the preferred blow-mixed yarns. Other types of hybrid yarns can be produced in a manner known per se.

The interlacing of the hybrid yarns from reinforcement and matrix filaments of the first embodiment described above is preferably carried out by means of a special warm interlacing process, which is described in EP-B-0,455,193. In order to avoid filament breaks during swirling, the filaments are warmed to near the softening point before swirling (approx. 600 ° C for glass). The heating can be carried out by means of godets and / or a heating tube, while the low-melting thermoplastic single filaments made of polyester are fed to the superordinate intermingling nozzle without preheating. These smooth, high-yarn hybrid yarns are easy to weave.

The hybrid yarns can be produced from reinforcement and matrix filaments of the second embodiment described above by conventional intermingling techniques, for example by intermingling or commingling techniques, as described, for example, in chemical fibers / textile industry, (7/8) 1989, T 185-7 .

Such yarns can consist of reinforcement and matrix filaments from different or preferably from the same chemical substance classes.

The fabrics or scrims according to the invention can be processed in a simple manner by using elevated temperatures, if appropriate using pressure or negative pressure, for example by calendering, to form textile fabrics with predetermined gas and / or liquid permeability.

• a) Vorlage eines Gewebes oder Geleges enthaltend Hybridgarne gemäß der oben gegebenen Definition, und
• b) thermische Behandlung dieses Gewebes oder Geleges unter Bedingungen, so daß die Matrixfilamente aufschmelzen und sich ein textiles Flächengebilde mit vorbestimmter Gas- und/oder Flüssigkeitsdurchlässigkeit ausbildet.

The invention also relates to a method for the production of textile fabrics with predetermined gas and / or liquid permeability comprising the measures:

• a) presentation of a fabric or scrim containing hybrid yarns as defined above, and
• b) thermal treatment of this fabric or scrim under conditions so that the matrix filaments melt and a textile fabric with a predetermined gas and / or liquid permeability is formed.

The thermal treatment after step b) can e.g. by contact heating, by radiation, by convection (hot air blower), by ultrasound or by a combination of these measures.

Such a method is particularly preferred, in which in step a) fabrics or scrims are presented which contain hybrid yarns arranged in a predetermined pattern or combinations of reinforcing and hybrid yarns according to the definition given above.

In the context of this description, “textile fabrics with predetermined gas and / or liquid permeability” are to be understood as textile fabrics which are derived from the fabrics or scrims defined above by melting the matrix component. The property profile of such textile fabrics can be set differently depending on the intended use, for example by selecting the type of reinforcement and matrix filaments used, by the proportion of hybrid yarns in the preliminary fabric or scrim, by the proportion of matrix filaments in the hybrid yarns used, through the distribution of different yarn types in the fabric or scrim pre-products, as well as through the manufacturing conditions used in individual cases.

The gas and / or liquid permeability is reduced by melting the matrix filaments.

Such textile fabrics contain a woven fabric made of reinforcing filaments or at least one thread group of parallel reinforcing filaments and a matrix component made of thermoplastic polymer.

The matrix component in the textile fabrics can only make up a small proportion, for example 3% by weight, based on the weight of the textile fabric; however, the matrix component can also make up a high proportion, for example 70% by weight, preferably 3 to 50% by weight, based on the weight of the textile fabric.

The matrix components can be evenly distributed over the textile fabric or preferably in a predetermined pattern. Depending on the respective amount, the matrix component can embed the reinforcing filaments (which results in a particularly low gas or liquid permeability) or only fix them.

The invention also relates to textile fabrics with predetermined gas and / or liquid permeability containing a woven fabric made of reinforcing filaments or at least one thread bundle of parallel reinforcing filaments and a matrix component made of thermoplastic polymer, wherein reinforcing filaments and matrix components consist of one polymer class (single-variety combinations), preferably combinations Polyamide / polyamide, polyolefin / polyolefin and in particular made of polyester / polyester.

The gas and / or liquid permeability of the textile fabrics that can be produced according to the invention can be varied within wide limits.

Textile fabrics with a gas permeability of less than or equal to 80, preferably less than or equal to 30, in particular less than, are preferred equal to 12 dm ³ air per minute per square decimeter of fabric with a pressure drop of 500 Pa (measured according to DIN 53887).

The gas permeability is measured in accordance with DIN 53 887 on a fabric with a measuring area of 100 cm ² and with a pressure drop (measuring pressure) of 500 Pa.

For use as an airbag, textile fabrics of the type defined above are particularly preferred, which are additionally characterized by a bursting strength according to Mullen of greater than or equal to 3500 kPa, a maximum tensile force of greater than or equal to 1300 N, each 5 cm of fabric width, and a tear propagation resistance, measured according to the leg method , greater than or equal to 100 N, and a maximum tensile force elongation of greater than or equal to 20%.

• Berstfestigkeit nach Mullen: Federal Test Method Standard No: 191A, Method 5122
• Höchstzugkraft: nach DIN 53 857, Teil 1
• Weiterreißfestigkeit (Schenkelmethode): in Anlehnung an DIN 53 356 (Probengröße 150 * 200 mm geschlaucht; Auswertung nach DIN 53539, B)
• Höchstzugkraftdehnung: nach DIN 53 857, Teil 1.

The properties listed are determined as follows:

• Mullen bursting strength: Federal Test Method Standard No: 191A, Method 5122
• Maximum tensile force: according to DIN 53 857, part 1
• Tear resistance (leg method): based on DIN 53 356 (sample size 150 * 200 mm hose; evaluation according to DIN 53539, B)
• Maximum tensile force expansion: according to DIN 53 857, part 1.

Very particular preference is given to textile fabrics which contain the matrix component arranged in a predetermined pattern in different quantities, as a result of which different gas and / or liquid permeabilities are achieved in predetermined subregions of the textile fabric.

Particularly preferred textile fabrics are derived from fabrics or scrims which consist of the hybrid yarns defined above.

The textile fabrics usually have weights from 50 to 600 g / m ² , preferably from 50 to 300 g / m ² . The thickness of these fabrics is usually less than 1.5 mm, preferably less than or equal to 0.45 mm.

The basis weight of the fabrics according to the invention is measured in accordance with DIN 53 854; The thickness of the fabrics according to the invention is measured in accordance with DIN 53 855, part 1 (measuring area 10 cm ² ; measuring pressure 50 cN / cm ² ).

The textile fabrics according to the invention can be used in a large number of fields of application, for example as protective clothing, such as bullet, cut, stitch or saw-inhibiting clothing items or weather protection clothing or anti-G vests or diving clothing; as tent fabrics or tent floors; as linings for containers, such as silo, pool or container linings; as bags; as materials for making shoes; as packaging materials; as maritime textiles, such as textiles for the manufacture of inflatable boats, life jackets or life rafts; as a textile building material, such as textiles for the production of zeppelins; as a carrier material, such as a material for producing light conveyor belts; as geotextiles; for use in hydraulic engineering, such as rain catch tanks or landfill covers; as sails or tarpaulin, as filter materials or in particular for the production of airbags.

Another object of the present invention is the use of the textile fabrics according to the invention for the purposes mentioned above.

The following examples illustrate the invention without limiting it.

Example:

A plain weave type L1 / 1 with 36 threads / cm in warp and 22 threads / cm in weft was produced on a Dornier rapier weaving machine.

The chain consisted of yarns made of polyethylene terephthalate of the type dtex 315f100 VZ 120.

• Gewebe-Höchstzugkraft (gemessen nach DIN 53 857, Teil 1):
  • in Kettrichtung: 2854,4 (N/5 cm)
  • in Schußrichtung: 1932,2 (N/5 cm)
• Gewebe-Höchstzugkraftdehnung (gemessen nach DIN 53 857, Teil 1):
  • in Kettrichtung: 36,6 %
  • in Schußrichtung: 25,2 %
• Gewebebreite: 172 cm
• Gesamt-Kettfadenzahl: 6192

The weft consisted of hybrid yarns of the dtex 420f72 titre obtained by commingling two rovings of the dtex 280f48 type from polyethylene terephthalate and the type dtex 140f24 from isophthalic acid-modified polyethylene terephthalate. The proportion of repeating isophthalic acid units in the copolyester was 33 mol%, based on the total amount of component dicarboxylic acid.
The fabric had a basis weight of 234 g / m ² and had the following properties as raw fabric:

• Maximum fabric tensile force (measured according to DIN 53 857, part 1):
  • in warp direction: 2854.4 (N / 5 cm)
  • in weft direction: 1932.2 (N / 5 cm)
• Maximum fabric tensile strength (measured in accordance with DIN 53 857, Part 1):
  • in warp direction: 36.6%
  • in the weft direction: 25.2%
• Fabric width: 172 cm
• Total number of warp threads: 6192

Claims (33)

Fabrics or scrims containing at least two thread systems of parallel threads, at least one of these thread systems having more than 10 threads per centimeter and consisting of at least 10%, based on the thread system, of hybrid yarns containing reinforcing filaments and low-melting matrix filaments made of thermoplastic polymers. Fabric or scrim according to claim 1, characterized in that they have two thread systems with thread densities of at least 15 threads per centimeter and at least 10%, preferably at least 50%, of hybrid yarns containing reinforcing filaments and low-melting matrix filaments made of thermoplastic polymers. Fabric or scrim according to claim 2, characterized in that they consist of two thread systems, each consisting of at least 95% hybrid yarns containing reinforcing filaments and deep-melting matrix filaments made of thermoplastic polymers. Fabric or scrim according to claim 1, characterized in that in at least one thread system there is a combination of hybrid yarns containing reinforcing filaments and deep-melting matrix filaments and of yarns made from carrier filaments, or in at least one thread system a combination of different hybrid yarns containing reinforcing filaments and different proportions of deep-melting matrix filaments is present, wherein several of the hybrid yarns and the yarns from carrier filaments or several of the different hybrid yarns are each arranged in a predetermined pattern. Fabric or scrim according to claim 1, characterized in that the matrix filaments made of thermoplastic polymers have a melting point have at least 30 ° C below the melting point or the decomposition point of the reinforcing filaments. Fabric or scrim according to claim 1, characterized in that the reinforcing filaments have an initial modulus of greater than 50 GPa and are preferably made of glass, carbon or aromatic polyamide. Fabric or scrim according to claim 1, characterized in that the reinforcing filaments have an initial modulus of greater than 10 GPa and consist of polyester, in particular of polyethylene terephthalate. Woven or laid fabric according to claim 1, characterized in that the matrix filaments consist of polybutylene terephthalate. Fabric or scrim according to claim 1, characterized in that reinforcing filaments and matrix filaments consist of one polymer class. Fabric or scrim according to claim 9, characterized in that reinforcing filaments and matrix filaments consist of combinations of polyamide / polyamide, polyolefin / polyolefin and in particular of polyester / polyester. Tissue or scrim according to claim 1, characterized in that the matrix filaments consist of a modified polyethylene terephthalate containing the recurring structural units of the formulas I and II

-O-OC-Ar ¹ -CO-OR ¹ - (I),

and

-O-OC-R ² -CO-OR ³ - (II),

wherein Ar ^{1 represents} a divalent mono- or polynuclear aromatic radical, the free valences of which are in the para position or in a parallel or coaxial position with respect to one another, preferably 1,4-phenylene and / or 2,6-naphthylene, R ¹ and R ³ independently represent divalent aliphatic or cycloaliphatic radicals, in particular radicals of the formula -C _n H _2n -, in which n is an integer between 2 and 6, in particular ethylene, or a radical derived from cyclohexanedimethanol, and R ^{2 represents} a divalent aliphatic, cycloaliphatic or mononuclear or polynuclear aromatic radical, the free valences of which are in the meta position or in an angled position comparable to this position, preferably 1,3-phenylene. Fabric or scrim according to claim 11, characterized in that the matrix filaments consist of a modified polyethylene terephthalate which contains 40 to 95 mol% of the repeating structural units of the formula I and 60 to 5 mol% of the repeating structural units of the formula II, in which Ar ¹ 1, Is 4-phenylene and / or 2,6-naphthylene, R ¹ and R ^{3 are} ethylene and R ^{2 is} 1,3-phenylene. Fabric or scrim according to claim 1, characterized in that the matrix filaments consist of a thermoplastic and elastomeric polymer. Fabric or scrim according to claim 13, characterized in that the thermoplastic and elastomeric polymer is a polyester which contains the recurring structural units of the formulas III and IV

-O-OC-Ar ² -CO-OR ⁴ - (III),

and

-O-OC-Ar ³ -CO-OR ⁵ - (IV),

wherein Ar ² and Ar ³ independently of one another represent divalent aromatic radicals, preferably phenylene and / or naphthylene radicals, in particular 1,4-phenylene, R ^{4 represents} a divalent aliphatic or cycloaliphatic radical, in particular a radical of the formula -C _m H _2m -, in which m is an integer between 2 and 6 or a radical derived from cyclohexanedimethanol, in particular ethylene, and R ^{5 represents} the divalent radical of a polyalkylene ether, preferably represents a radical of the formula V.

- [C _o H _2o -O] _z -C _o H _2o - (V),

wherein o is an integer from two to four, in particular four, and z is an integer from 1 to 50, in particular an integer from 10 to 18. Fabric or scrim according to claim 14, characterized in that Ar ² and Ar ^{3 are} 1,4-phenylene, R ^{4 is} ethylene, o is four, and in which the proportion of the repeating structural units of the formula V, based on the proportion of the polyester molecule 5 is up to 60% by weight. Fabric or scrim according to claim 13, characterized in that the thermoplastic and elastomeric polymer is a polyurethane which contains the recurring structural units of the formulas VI and VII

- [O-OC-NH-R ⁶ -NH-CO-OR ⁷ ] - (VI),



- [O-OC-NH-R ⁸ -NH-CO-OR ⁹ ] - (VII),

wherein R ⁶ , R ⁷ and R ⁸ independently of one another represent a divalent aliphatic, cycloaliphatic, aromatic or araliphatic radical, R ⁶ and R ^{8 are} preferably divalent mono- or dinuclear aromatic radicals, in particular phenylene and / or naphthylene, R ^{7 is} preferably a radical of the formula -C _p H _2p -, in which p is an integer between 2 and 6 or a radical derived from cyclohexanedimethanol, in particular butane-1,4-diyl, R ^{9 represents} a radical of the formulas VIII and / or IX

- [C _q H _2q -O] _x -C _q H _2q - (VIII),



- [R ¹⁰ -O-OC-R ¹¹ -CO-O] _y -R ¹⁰ - (IX),

wherein q is an integer from two to four and x is an integer from 1 to 50, R ^{10 represents} a divalent aliphatic or cycloaliphatic radical or a radical of the formula VIII, R ^{11 is} a divalent aliphatic, cycloaliphatic, aromatic or araliphatic radical, and y represents an integer from 1 to 50. Tissue or scrim according to Claim 16, characterized in that R ⁷ denotes butane-1,4-diyl, R ^{9 is} a radical of the formula VIII according to Claim 16, in which q denotes an integer from two to four, in particular four, and x is an integer from 1 to 50, preferably from 10 to 18, and in which R ⁶ and R ⁸ independently of one another are phenylene or naphthylene. Process for the production of textile fabrics with predetermined gas permeability comprising the measures: a) presentation of a fabric or scrim containing hybrid yarns according to claim 1, and b) thermal treatment of this fabric or scrim under conditions so that the matrix filaments melt and a textile fabric with a predetermined gas permeability is formed. A method according to claim 18, characterized in that in step a) fabrics or scrims are presented which contain hybrid yarns arranged in a predetermined pattern according to claim 4. Textile fabric with predetermined gas and / or liquid permeability containing a woven fabric made of reinforcing filaments and a matrix component made of thermoplastic polymer or containing at least one thread bundle of parallel reinforcing filaments and a matrix component made of thermoplastic polymer, wherein reinforcing filaments and matrix components consist of a polymer class, preferably combinations of polyamide / Polyamide, polyolefin / polyolefin and in particular made of polyester / polyester. Textile fabric according to claim 20, characterized in that it has a gas permeability of less than or equal to 80, preferably less than or equal to 30, in particular less than or equal to 12 dm ³ air per minute per square decimeter of fabric at a pressure drop of 500 Pa (measured according to DIN 53887) . Textile fabric according to claim 20, characterized in that this has a bursting strength according to Mullen of greater than or equal to 3500 kPa, a maximum tensile force of greater than or equal to 1300 N, each 5 cm of fabric width Tear resistance, measured according to the leg method, of greater than or equal to 100 N, and has a maximum tensile strength elongation of greater than or equal to 20%. Textile fabric according to claim 20, characterized in that it contains the matrix component arranged in a predetermined pattern in different quantities, and thereby different gas and / or liquid permeabilities are achieved in predetermined partial areas of the fabric. Textile fabric according to claim 20, characterized in that the reinforcing filaments have an initial modulus of greater than 10 GPa and consist of polyester, in particular of polyethylene terephthalate, and that the matrix component consists of polybutylene terephthalate. Textile fabric according to Claim 20, characterized in that the reinforcing filaments have an initial modulus of greater than 10 GPa and consist of polyester, in particular polyethylene terephthalate, and that the matrix component consists of a modified polyethylene terephthalate containing the recurring structural units of the formulas I and II

-O-OC-Ar ¹ -CO-OR ¹ - (I),

and

-O-OC-R ² -CO-OR ³ - (II),

wherein Ar ¹ , R ¹ , R ² and R ^{3 have} the meaning defined in claim 11. Textile fabric according to Claim 25, characterized in that the matrix component consists of a modified polyethylene terephthalate which contains 40 to 95 mol% of the repeating structural units of the formula I and 60 to 5 mol% of the repeating structural units of the formula II, wherein Ar ^{1 is} 1,4-phenylene and / or 2,6-naphthylene, R ¹ and R ^{3 are} ethylene and R ^{2 is} 1,3-phenylene. Textile fabric according to claim 20, characterized in that the reinforcing filaments have an initial modulus of greater than 10 GPa and consist of polyester, in particular polyethylene terephthalate, and that the matrix component consists of a thermoplastic and elastomeric polyester. Textile fabric according to claim 27, characterized in that the thermoplastic and elastomeric polyester contains the recurring structural units of the formulas III and IV

-O-OC-Ar ² -CO-OR ⁴ - (III),

and

-O-OC-Ar ³ -CO-OR ⁵ - (IV),

wherein Ar ² , Ar ³ , R ⁴ and R ^{5 have} the meaning defined in claim 14. Textile fabric according to claim 28, characterized in that Ar ² and Ar ^{3 are} 1,4-phenylene, R ^{4 is} ethylene, R ^{5 represents} a radical of formula V according to claim 14

- [C _o H _2o -O] _z -C _o H _2o - (V),

in which o is four, z is an integer from 10 to 18 and in which the proportion of the repeating structural units of the formula V, based on the proportion of the polyester molecule, is 5 to 60% by weight. Use of the textile fabrics according to claim 20 as protective clothing, as tent fabrics or tent floors; as linings for containers, as bags, as materials for making shoes; as packaging materials; as maritime textiles, as a textile building material, as a carrier material, as geotextiles; for use in hydraulic engineering, as sails or tarpaulins, as filter materials or for the production of airbags. Use according to claim 30, characterized in that the martial textiles are textiles for the manufacture of inflatable boats, life jackets or life rafts. Use according to claim 30, characterized in that the linings for containers are silo, pool or container linings. Use according to claim 30, characterized in that the textile fabrics are used for the production of airbags.