EP2169110A1 - Fire-resistant hollow fibres with silicon-free soft grip apparatus - Google Patents

Abstract

Flame-resistant modified fibres (FRF) based on melt-spinnable polymers are provided with a silicone-free soft-feel finish. Independent claims are also included for (1) fibre fillers containing (FRF) (2) coverings filled with such fibre fillers (3) textile sheet materials containing (FRF) .

Description

The invention relates to a flame-retardant modified hollow fiber with a silicone-free soft-grip equipment, and a method for producing the same and their use for Füllfaserprodukte.

Fiber fillings can be used in many applications, such as apparel, cushions, furniture, insulation, quilts, filters, upholstery (e.g., in cars), sleeping bags, mattress pads, and mattresses. The hollow fibers used for these applications are generally hollow fibers which are flame-retardant with phosphorus-containing compounds. As hollow fibers polyester hollow fibers are preferably used.

The preparation of corresponding flame-retardant modified polyester fibers in which the polyester comprises fused phosphorus-containing chain links is known per se. It is at this point on the German patent applications or patents DE 22 36 037 . DE 22 42 002 . DE 23 28 00 343 . DE 23 46 787 . DE 24 54 189 directed.

The fibers described there were previously used as such only where it depends on the flame retardancy.

Furthermore, fiber fillings are provided with a so-called softening finish with a pleasant feel, improved fluffiness, improved surface smoothness, and improved recovery. For this softening equipment, according to the prior art, silicone-based softening is used, such as, for example, in US Pat WO 2004/007 347 (Trevira GmbH), US 3,271,189 (Hofmann ) and in U.S. 3,454,422 (Mead et al. ) disclosed.

However, it is known of such fibers with a silicone-containing softening finish that this silicone-containing softening finish severely impairs the flame retardant properties.

The object of the present invention is therefore to provide flame-retardant hollow fibers with a soft-grip finish which does not impair the flame-retardant properties of the hollow fibers.

It has been found that in flame-retardant polyester hollow fibers provided with the silicone-free softening finish according to the invention, on the one hand, the flame-retardant properties of the hollow fibers are not impaired by the applied soft-grip finish and, on the other hand, the desired softening is obtained.

The present invention therefore provides flame-retardant modified fibers based on melt-spinnable polymers, in particular based on polyesters, characterized in that these fibers are provided with a soft-grip finish which is silicone-free.

The fibers of melt-spinnable polymers according to the invention are preferably fibers based on polyesters. Suitable polyester materials are in principle all known types suitable for fiber production. Such polyesters consist predominantly of building blocks derived from aromatic dicarboxylic acids and from aliphatic diols. Common aromatic dicarboxylic acid building blocks are the divalent radicals of benzenedicarboxylic acids, in particular terephthalic acid and isophthalic acid. Common diols have 2 to 4 carbon atoms, with the ethylene glycol being particularly suitable. Particularly advantageous are fibers which consist of at least 85 mol% of polyethylene terephthalate. The remaining 15 mol% are made up of dicarboxylic acid units and glycol units which act as so-called modifying agents and which allow the person skilled in the art to influence the physical and chemical properties of the filaments produced in a targeted manner. Examples of such dicarboxylic acid units are residues of isophthalic acid or of aliphatic dicarboxylic acids, such as glutaric acid, adipic acid and sebacic acid. Examples of modifying diol radicals are those of longer-chain diols, for example of propanediol or butanediol, of di- or triethylene glycol, or, if present in a small amount, of polyglycol having a molecular weight of about 500 to 2,000. Particularly preferred are polyesters containing at least 95 mol% of polyethylene terephthalate (PET), in particular PET not modified with dicarboxylic acid units and / or glycol units.

The flame retardant modification of the polyester fibers is achieved by using flame retardant modified polyesters. Such flame-retardant modified polyesters are known. They contain additions of halogen compounds, in particular bromine compounds, or, what is particularly advantageous, they contain phosphorus compounds which are condensed in the polyester chain.

For the purposes of the invention, these condensed-in phosphorus-containing chain links are understood to be chain links which are arranged in the linear chain of the polymer molecule (longest chain), but also in any side chains and branches that may be present.

worin R Alkylen oder Polymethylen mit 2 bis 6 Kohlenstoffatomen oder Phenyl und R¹ Alkyl mit 1 bis 6 Kohlenstoffatomen, Aryl oder Aralkyl bedeutet. Vorzugsweise bedeuten in der Formel (I) R Ethylen und R¹ Methyl, Ethyl, Phenyl, oder o-, m- oder p-Methylphenyl, insbesondere Methyl. Derartige Polyester werden z.B. in der DE-A-39 40 713 beschrieben. Die erfindungsgemäß verwendeten Polyester haben vorzugsweise ein Molekulargewicht entsprechend einer intrinsischen Viskosität (IV), gemessen in einer Lösung von 1 g Polymer in 100 ml Dichloressigsäure bei 25°C, von 0,45 bis 0,85.Particularly preferred are flame-retardant modified polyesters which contain condensed in the chain assemblies of the formula (I)

wherein R is alkylene or polymethylene having 2 to 6 carbon atoms or phenyl and R ^{1 is} alkyl having 1 to 6 carbon atoms, aryl or aralkyl. Preferably in the formula (I) R is ethylene and R ^{1 is} methyl, ethyl, phenyl, or o-, m- or p-methylphenyl, in particular methyl. Such polyesters are, for example, in the DE-A-39 40 713 described. The polyesters used in the invention preferably have a molecular weight corresponding to an intrinsic viscosity (IV), measured in a solution of 1 g of polymer in 100 ml of dichloroacetic acid at 25 ° C, from 0.45 to 0.85.

The silicone-free softener finish of the present invention is a blend comprising at least one polyether and at least one Fatty acid condensation product. According to the invention, this mixture preferably has a mixing ratio (weight) of polyether: fatty acid condensation product of 10: 1 to 1: 1, in particular of 5: 1 to 2: 1, particularly preferably of 4: 1.

wobei die Reste

• R³, R⁴ gleich oder verschieden sein können und ausgewählt werden aus Wasserstoff, geradkettigen und/oder verzweigten Alkyl- und /oder Alkenylgruppen, sowie aromatischen und/oder heteroaromatischen Gruppen,
• R² gleich oder verschieden sein können und ausgewählt werden aus geradkettigen und/oder verzweigten Alkyl- und /oder Alkenylgruppen, sowie aromatischen und/oder heteroaromatischen Gruppen und
• n eine Zahl von mindestens 1, vorzugsweise mindestens 2, bedeuten.

Suitable polyethers for the softening equipment of the present invention are compounds having the general formula

where the radicals

• R ³ , R ^{4 may be} identical or different and are selected from hydrogen, straight-chain and / or branched alkyl and / or alkenyl groups, and also aromatic and / or heteroaromatic groups,
• R ^{2 may be the} same or different and are selected from straight-chain and / or branched alkyl and / or alkenyl groups, as well as aromatic and / or heteroaromatic groups and
• n is a number of at least 1, preferably at least 2.

Preferred radicals R ² are straight-chain or branched alkyl groups, in particular ethyl (polyethylene glycol) or propyl groups (propylene glycol). The end groups R ³ , R ⁴ are usually hydrogen, but may also be substituted by the same groups as mentioned above for R ³ , R ⁴ .

Preferred compounds of the formula (II) are nonionic polyethers. It is further preferred if the polyethers are miscible with water and have a pH in the range from 6 to 9, in particular from 7 to 8, particularly preferably from 7.5 as 10% solution (weight percent). It is further preferred if the dynamic viscosity of the polyethers (measured as 10% strength solution in water) at 20 ° C. (HTC51) is preferably between 50 and 80 mPas, in particular between 60 and 70 mPas, particularly preferred at 65 mPas ,

Such polyethers are commercially available, for example under the trade name ^Duron® FF 1751, a product of CHT R. Beitlich GmbH.

Fatty acid condensation products of the invention suitable for softening equipment are compounds of fatty acids having the general formula

R ⁵ -COOH,

where R ⁵ denotes straight-chain or branched, alkyl or alkenyl groups having 6 to 30 carbon atoms, preferably 6 to 26 carbon atoms,
with aliphatic or aromatic, mono- or polyfunctional alcohols or amines.

Preferred fatty acid condensation products according to the invention are fatty acid condensation products, in particular cationic fatty acid condensation products, which are completely miscible with water and have a pH in the range from 1 to 6, preferably 2 to 5, particularly preferably 3, as the 10% solution (weight percent) to 4, have. Their dynamic viscosity (measured as 10% by weight solution in water) at 20 ° C. is preferably between 80 and 120 mPas, preferably between 90 and 110 mPas, particularly preferably about 100 mPas.

One such commercially available fatty acid condensation product is ^Duron® FF 1995, a product of CHT R. Beitlich GmbH.

Particularly preferred is a softening finish comprising (i) non-ionic polyethers whose pH (measured as 10% strength by weight solution in water at 20 ° C.) is between 7 and 8 and whose dynamic viscosity of the polyethers (measured as 10 wt .-% - solution in water at 20 ° C) is between 50 and 80 mPas and (ii) cationic fatty acid condensation products whose pH (measured as 10 wt .-% solution in water at 20 ° C) in the range of 2 to 5 and their dynamic viscosity (measured as 10% by weight solution in water) at 20 ° C between 80 and 120 mPas and wherein the mixing ratio (parts by weight) of nonionic polyether (i) to cationic fatty acid condensation product (ii) is 5: 1 to 2: 1.

Very particular preference is given to the abovementioned mixture of (i) nonionic polyether and (ii) cationic fatty acid condensation product to those in which the polyethers (i) are different polyethers selected from the group of polyethylene glycol, polypropylene glycol or mixtures of polyethylene glycol and polypropylene glycol, include.

With the use according to the invention of this silicone-free soft-grip finish on the flame-retardant fibers, it is possible to produce fiber products, in particular for the filling fiber sector, which have both soft feel and flame-retardant properties.

Silicone-free means that silicon-containing material is contained as little as possible so that the flame retardant properties according to the invention are not impaired. This is the case for amounts of no more than about 10 ppm of silicone-containing material relative to the finished hollow fiber, preferably less than about 1 ppm, more preferably less than about 0.1 ppm.

The fibers may have round, oval and other suitable cross-sections or other shapes, such as dumbbell, kidney-shaped, triangular or trilobal or multilobal cross-sections. Hollow fibers are preferably used.

Polyester fibers generally have titer values in the range of 0.9 to 16 dtex. Polyester hollow fibers having the above values are preferably used, preferably with titres of 0.9 to 17 dtex, more preferably 4 to 13 dtex. If the polyester hollow fibers according to the invention are to be used as staple fibers, they have a cut length (staple length) of 1 to 150 mm, preferably 8 to 100 mm and particularly preferably 24 to 80 mm.

In particular embodiments of the invention, the polyester fibers consist of a Titer mixture and / or a mixture of fibers with different staple length.

If the polyester fibers according to the invention are used for textile applications or as filler fiber packing, texturing is advantageous, in particular crimping.

According to the invention, the degree of crimping is 2 crimps (crimps) per cm (Bg) or more, preferably 3 sheets per cm or more.

The number of sheets per cm must also be in a certain ratio to the so-called crimp K1. K1 preferably has values of at least 15%, preferably at least 18%. Accordingly, the ratio of curling to number of sheets per cm is preferably in the range of 5 ≦ K1 / Bg ≦ 6 at a number of sheets per cm Bg of 3.0.

wobei L_k die Länge der gekräuselten Stapelfaser im entspannten freiliegenden Zustand ist und L_v die Länge der gleichen, jedoch gestreckten Faser, d.h. die Faser liegt dann praktisch geradlinig ohne Kräuselung vor. Die Streckung erfolgt unter Anwendung der sogenannten Entkräuselungskraft. Diese wird in Vorversuchen mit Hilfe einer an das Kraft-Dehnungsdiagramm der jeweiligen Faser angelegten Tangente ermittelt.Circling in the context of the invention means the following ratio: $$\mathrm{K}\mathrm{1}\mathrm{=}\frac{\mathrm{lv}\mathrm{-}\mathrm{lk}}{\mathrm{lv}}$$

where L _{k is} the length of the crimped staple fiber in the relaxed, exposed state and L _{v is} the length of the same but stretched fiber, ie, the fiber is then practically straight without crimping. The stretching is carried out using the so-called Entkräuselungskraft. This is determined in preliminary tests by means of a tangent applied to the force-strain diagram of the respective fiber.

The flame retardant fibers of the invention may additionally comprise other additives commonly used in the art. These include in particular antioxidants, stabilizers (eg UV stabilizers), matting agents (eg TiO ₂ zinc sulfide or zinc oxide), pigments (eg TiO ₂ ), additional flame retardants, antistatic agents, dyes, fillers (eg calcium carbonate), antimicrobial agents, bioactive agents, optical Brighteners, extenders and other processing aids to understand.

Such additives may be added to the polymer at any time during polymer preparation or applied to the fibers with the finish.

Fiber fabrication is accomplished by spinning polymers into filaments, optionally with lubricants, and then processing into fibers, drawing and crimping the fibers, and optionally applying an antistatic agent to the fibers. In the case of the production of staple fibers, the fibers are cut and then pressed into so-called flake bales and packaged.

Fabrication of the fibers is accomplished using conventional methods and equipment as are preferred in the art in the context of polyester fibers. For example, numerous methods of spinning in US 3,816,486 . U.S. 4,639,347 . GB 1 254 826 and JP 11-189938 described.

The spinning speed is preferably 800 meters per minute or more, and is typically 1600 meters per minute or less. The spinning temperature is typically 255 ° C or more and 305 ° C or less. More preferably, spinning is carried out at about 280 ° C.

The spinneret is a conventional spinneret of the type used in conventional polyesters, with hole size, location and number depending on the desired fiber and spin line.

Quenching of the melt-spun polyester filaments in this manner may be carried out in a conventional manner using air or other fluids as described in the art (e.g., nitrogen). Cross-flow, radial, asymmetric or other cooling methods can be used. It is preferred to blow with air for quenching.

After cooling, conventional spin finishes can be applied using standard techniques.

The fiber filaments thus produced are first deposited in cans for further processing.

According to a preferred method, the melt-spun fiber filaments are taken up on a spinning-cable cylinder and subsequently a plurality of spinning-wire cylinders are assembled and a large tow is produced from the fiber-filaments. Thereafter, the fiber tows can be drawn using conventional techniques, preferably at 10 to 110 m / min. The draw ratios are preferably from 1.25 to 4, more preferably from 2.5 to 3.5, most preferably 3.2. The temperature during the drawing is in the range of the glass transition temperature of the polyester cable to be stretched and is preferably 40 ° C. to 80 ° C. and is particularly preferably 69 ° C. The aftertreatment is carried out at about 150 ° to 165 ° C to ensure good drying. The stretching can be carried out optionally using a two-stage stretching process (see, for example, the US 3,816,486 ). Before and during drawing, one or more finishes may be applied using conventional techniques.

Preferably, the silicone-free soft-grip equipment according to the invention is applied between the stretching and the crimping. The application is carried out by conventional techniques, in particular by spraying or by means of an applicator roll. The amount applied is between 0.4 and 0.5% of the fiber weight and is preferably 0.46%.

For the crimping of the fibers thus stretched, conventional methods of mechanical crimping can be used with known crimping machines. Preferred is a mechanical device for staple fiber crimping with steam assist, such as a stuffer box. However, crimped fibers can also be used according to other methods, for example also three-dimensionally crimped fibers. To carry out the crimping, the cable is first heated to a temperature in the range of 60 ° to 100 ° C., preferably 70 ° to 85 ° C., particularly preferably about 83 ° C., and with a pressure of the cable entry rollers of 1.0 to 2, 0 bar, more preferably at about 1.5 bar, a pressure in the crimping chamber of 0.5 to 1.0 bar, particularly preferably 0.8 bar, with steam at between 1.0 and 2.0 kg / min., especially preferably 1.5 kg / min, treated.

Using conventional methods, another finish can be applied in the crimper.

The fibers are relaxed at 150 ° to 165 ° C in the oven and / or fixed. The preparation does not need its own fixation step.

Optionally, antistatic finish may be applied to the fibers after relaxation.

Furthermore, if desired, the fibers can be made pillar free.

To make staple fibers, the textured fibers are taken up, followed by cutting and possibly hardening and depositing in pressed bales as a flake. The staple fibers of the present invention are preferably cut on a relaxation downstream mechanical cutter. For the production of cable types can be dispensed with the cutting. These cable types are placed in uncut form in the bale and pressed.

Another object is the use of the fiber products according to the invention as fiber fillers or in textile fabrics.

The use of the fiber products of the present invention as fibrous fillers includes fillings for filled covers, e.g. Pillows, duvets, quilts and the like, as well as for mattresses and sleeping bags, insulation and upholstery, for example for furniture and in the automotive sector, as well as filters.

Inventive textile fabrics are, for example, clothing, the upper and lower webs of the above-mentioned covers, as well as mattress pads.

EXAMPLE

The invention will be explained in more detail with reference to the following example:

A staple fiber with a hollow profile is spun from the melt in the usual way for fibers from the flame-retardant raw material, cooled by blowing with air, provided with conventional staple fiber preparation and stored in cans for processing on the strip line.

The spun goods are collected as a fiber cable via an inlet rake and fed by a first septet, consisting of seven rotating rollers, passed through a dip bath, where it is tempered and again provided with preparation. The spun goods are transported by another septet. The stretching takes place on the sixth or seventh roll of this septet or between this and a further septet running faster by the factor of stretching. Subsequently, the fiber is crimped in a stuffer box, fixed in the oven or dried and optionally cut. Between drawing and crimping, the addition of a silicone-free softening equipment by spraying or by application roller.

The following textile technological values are determined on the fibers produced: <u> Table 1: </ u> Fineness / dtex: 6.0 Tear strength / cN / tex: 40 Elongation at break /% 36 Thermal shrinkage (200 ° C) /%: 4 ripple: K1 /%: 18 Bg / cm: 4

Claims (29)

Flame-retardant modified fiber based on melt-spinnable polymers, characterized in that the fiber is provided with a soft-grip finish which is silicone-free. Flame-retardant modified fiber according to claim 1, characterized in that the melt-spinnable polymers are polyesters. Flame-retardant modified fiber according to claim 1 or 2, characterized in that the silicone-free softening finish is a softening finish comprising at least one polyether and at least one fatty acid condensation product. Flame retardant modified fiber according to claim 3, characterized in that the softening equipment comprises at least one polyether and at least one fatty acid condensation product and the mixing ratio (weight) of polyether: fatty acid condensation product is 10: 1 to 1: 1. Flame retardant modified fiber according to claim 3 or 4, characterized in that it is in the polyether one or more compounds having the general formula

where the radicals R ³ , R ^{4 may be} identical or different and are selected from hydrogen, straight-chain and / or branched alkyl and / or alkenyl groups, and also aromatic and / or heteroaromatic groups, R ^{2 may be the} same or different and are selected from straight-chain and / or branched alkyl and / or alkenyl groups, as well as aromatic and / or heteroaromatic groups and n is a number of at least 1, preferably at least 2, is. Flame retardant modified fiber according to claim 5, characterized in that it is the polyether to polyethylene glycol and / or propylene glycol. Flame retardant modified fiber according to claim 3 or 4, characterized in that it is the fatty acid condensation product to one or more condensation compounds of fatty acids having the general formula

R ⁵ -COOH,

where R ⁵ denotes straight-chain or branched, alkyl or alkenyl groups having 6 to 30 carbon atoms, preferably 6 to 26 carbon atoms, with aliphatic or aromatic, mono- or polyfunctional alcohols or amines. Flame retardant modified fiber according to claim 1 to 7, characterized in that it is a polyester hollow fiber in the fiber. Flame retardant modified fiber according to any one of claims 1 to 8, characterized in that it is a polyester staple fiber in the fiber. Flame retardant modified fiber according to any one of claims 1 to 9, characterized in that the polyester fiber consists predominantly of building blocks derived from aromatic dicarboxylic acids and aliphatic diols. Flame-retardant modified fiber according to claim 10, characterized in that the aromatic dicarboxylic acids are divalent radicals of benzenedicarboxylic acids, in particular radicals of terephthalic acid and of isophthalic acid. Flame retardant modified fiber according to claim 11, characterized in that the fibers consist of at least 85 mol% of polyethylene terephthalate. Flame-retardant modified fiber according to one of claims 10 to 12, characterized in that the aliphatic diols are those having 2 to 4 carbon atoms, in particular ethylene glycol. Flame-retardant modified fiber according to any one of claims 10 to 13, characterized in that the fibers consist of at most 15 mol% of dicarboxylic acid units and diol units, in particular glycol units. Flame-retardant modified fiber according to claim 14, characterized in that the dicarboxylic acid units are isophthalic acid residues or aliphatic dicarboxylic acids. Flame retardant modified fiber according to claim 15, characterized in that the aliphatic dicarboxylic acids are selected from glutaric acid, adipic acid and sebacic acid. Flame retardant modified fiber according to claim 2 to 16, characterized in that the flame retardancy on the basis of the polyester by additions of halogen compounds, in particular bromine compounds, or by phosphorus compounds which are condensed in the polyester chain, is achieved. Flame retardant modified fiber according to claim 17, characterized in that the flame-retardant modified polyester in the chain contains fused assemblies of the formula (I)

where R is alkylene or polymethylene having 2 to 6 carbon atoms or phenyl and R ^{1 is} alkyl having 1 to 6 carbon atoms, aryl or aralkyl, Flame-retardant modified fiber according to claim 18, characterized in that the fused into the chain of the flame-retardant modified polyester assemblies can be arranged in the linear chain of the polymer molecule (longest chain), but also in any existing side chains and branches Flame retardant modified fiber according to one of the preceding claims 1 to 19, characterized in that the fiber is textured. Flame retardant modified fiber according to claim 20, characterized in that the fiber is crimped, preferably upsetting crimped. Flame-retardant modified fiber according to claim 21, characterized in that the crimp K1 is at least 15%, preferably at least 18%. Flame-retardant modified fiber according to one of the preceding Claims 1 to 22, characterized in that the fibers have titres values in the range from 0.9 to 16 dtex, preferably from 0.9 to 17 dtex, particularly preferably from 4 to 13 dtex. Flame retardant modified fiber according to one of the preceding claims 1 to 23, characterized in that the fibers are present as staple fibers and have a staple length of 1 to 150 mm, preferably from 8 to 100 mm, particularly preferably from 24 to 80 mm. Fiber fillers containing the flame retardant modified fibers according to claims 1 to 24. Filled covers filled with the fiber fillers according to claim 25. Filled covers according to claim 26, wherein the filled covers preferably include pillows, quilts and quilts, as well as mattresses and sleeping bags, insulating material and upholstery, for example for furniture and in the automotive sector, as well as filters. Textile fabrics containing the flame-retardant modified fibers according to claims 1 to 24. Textile fabrics according to claim 28, wherein the textile surfaces preferably comprise the top or bottom sheets of the filled covers according to claims 26 or 27, as well as clothing and mattress pads.