EP2200721A2

EP2200721A2 - Yarns, fibres or filaments and use thereof, in particular in ropes

Info

Publication number: EP2200721A2
Application number: EP08839787A
Authority: EP
Inventors: Franck Bouquerel; Caroll Vergelati; Florence Clement
Original assignee: Rhodia Operations SAS
Current assignee: Rhodia Operations SAS
Priority date: 2007-10-16
Filing date: 2008-10-10
Publication date: 2010-06-30
Also published as: WO2009050114A2; US20110034098A1; AR068883A1; WO2009050114A3; FR2922223A1; FR2922223B1; CN101896233A; TW200928026A

Abstract

The invention relates to yarns, fibres or filaments, in particular based on polyamide, which can be used to produce ropes. More specifically, the invention relates to climbing ropes containing said yarns, fibres or filaments and having good mechanical properties, particularly under conditions of high relative humidity.

Description

SON. FIBERS OR FILAMENTS AND THEIR USE IN PARTICULAR

IN STRINGS

The present invention relates to son, fibers or filaments, in particular based on polyamide, used especially for making ropes. It relates more particularly climbing ropes comprising these son, fibers or filaments, which have good mechanical properties, especially in high relative humidity conditions. The properties that must present spun articles are different according to their use. These include, for example, toughness, elongation at break, fatigue strength, transparency, gloss, whiteness, dyeability, shrinkage, retention capacity, water, fire resistance, stability and longevity to heat. A property that may be required, especially for applications in so-called technical wire fields, is the breaking strength, as well as the damping capacity during an impact.

This is the case for example ropes, ropes, ropes, which are used in many areas such as the maritime domain, the climbing field, etc. They can for example be used to moor boats and ships, for example pleasure boats.

[0004] These ropes, ropes, ropes undergo significant mechanical stresses during their use, due for example to the movements of the sea, the manipulation of the rope by the users, etc. In the field of climbing ropes for example, the rope must not only withstand the possible falls of the climber, but it must also dampen these falls, especially during the phase of sudden tension of the rope, to preserve the climber from the damage resulting from the fall. Standards exist which evaluate these properties, in particular the EN 892 standard. The measurement of the resistance properties for the EN 892 standard is based in particular on the number of drops before breaking, which must be greater than a minimum value. The minimum requirement in terms of number of falls before breaking the standard may be 4 or more; it depends in particular on the nature of the rope and its use (single rope, double rope). Today climbing ropes made from polyamide 6 son meet these standards. However, the measurement conditions of these standards are the standard conditions of air humidity (65 +/- 5%) and temperature (25 ° C). The ropes can be used in very variable humidity conditions, for example very dry conditions (such as 30% relative humidity), for example in the desert, under very humid conditions (such as 90% relative humidity), for example after an intense rain event. Now it has been shown that some known strings in the field of climbing polyamide 6 have only a number of falls before breakage of 2 or 3, when they have been previously soaked in water for one hour , while this number of falls before rupture is 10 under standard conditions of humidity (65 +/- 5%) and temperature (25 ⁰ C). It is therefore sought to improve the breaking strength properties and in particular the damping capacity during a shock, including ropes climbing ropes, particularly wet conditions.

For this purpose the invention proposes, in a first object, son, fibers or filaments based on thermoplastic polymer obtained from a composition comprising:

a thermoplastic polymer matrix

a novolac resin.

In a second object, the invention provides a method of preparing these son, fibers, or filaments. In a third object, the invention provides an article comprising the son, fibers and / or filaments of the invention, in particular climbing ropes.

In a fourth object, the invention provides the use of the article in high humidity conditions. Finally, in a final object, the invention proposes the use of a novolak resin in the field of climbing ropes.

The invention therefore relates, in a first object, son, fibers or filaments based on thermoplastic polymer obtained from a composition comprising: - a polymeric matrix

a novolac resin.

The son, fibers, filaments of the invention are based on thermoplastic polymer. By way of example, mention may be made of thermoplastic (co) polymer suitable in the context of the invention: polyolefins, polyesters, polyalkylene oxides, polyoxyalkylenes, polyhaloalkylenes, poly (alkylene phthalate or terephthalate) poly (phenyl or phenylene), poly (phenylene oxide or sulfide), polyvinyl acetates, polyvinyl alcohols, polyvinyl halides, polyvinyl polyvinylidene halides, polyvinyl nitriles, polyamides, polyimides, polycarbonates, polymers of acrylic or methacrylic acid, polyacrylates or methacrylates, natural polymers such as cellulose and its derivatives, synthetic polymers such as synthetic elastomers , or thermoplastic copolymers comprising at least one monomer identical to any one of the monomers included in the abovementioned polymers, as well as mixtures and / or alloys of all these (co) polymers. Other preferred thermoplastic polymers of the invention include semicrystalline or amorphous polyamides, such as aliphatic polyamides, semi-aromatic polyamides and, more generally, linear polyamides obtained by polycondensation between an aliphatic or aromatic saturated diacid, and a saturated aromatic or aliphatic primary diamine, the polyamides obtained by condensation of a lactam, an amino acid or linear polyamides obtained by condensation of a mixture of these different monomers.

More specifically, these copolyamides may be, for example, hexamethylene polyadipamide, polyphthalamides obtained from terephthalic acid and / or isophthalic acid such as the polyamide marketed under the trade name AMODEL, copolyamides obtained from adipic acid, hexamethylene diamine and caprolactam. The thermoplastic polymer may be a polyester, such as polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), copolymers and mixtures thereof. More preferably still, the thermoplastic polymer is selected from the group of (co) polyamides comprising: polyamide 6, polyamide 6.6, polyamide 4, polyamide 11, polyamide 12, polyamides 4-6, 6-10, 6-12, 6-36, 12-12, their copolymers and mixtures. The son, fibers and filaments of the invention may be based on a mixture of thermoplastic polymers or thermoplastic copolymers. The son, fibers or filaments of the invention are obtained from a composition comprising a novolak resin. Novolac resins are polyhydroxy compounds, for example condensation products of phenolic compounds with aldehydes. These condensation reactions are generally catalyzed by an acid.

The phenol compounds may be chosen alone or in a mixture from phenol, cresol, xylenol, naphthol, alkyphenols, such as butylphenol, terbutylphenol or isooctylphenol; or any other substituted phenol. The most frequently used aldehyde is formaldehyde.

However, others may be used, such as acetaldehyde, paraformaldehyde, butyraldehyde, crotonaldehyde, and glycoxal.

According to a particular embodiment of the invention, the resin is a condensation product of phenol and formaldehyde.

Advantageously, the novolak resin has the following formula

with R and R 'are alkyl groups, t is between 1 and 20, preferably between 8 and 13.

The resins used advantageously have a molecular weight between 500 and 3000 g / mol, preferably between 800 and 2000 g / mol.

As novolac commercial resin, there may be mentioned Durez® products, Vulkadur® or Rhenosin®.

The composition from which the yarns, fibers or filaments of the invention are obtained comprises between 0.1 and 20% by weight, preferably between 1 and 10% by weight, of novolak resin.

The son, fibers, and filaments of the invention may comprise additives such as reinforcing fillers, flame retardants, stabilizers for

UV, heat, mattifiers such as titanium dioxide, bioactive agents etc. The overall title of the son of the invention can be chosen throughout the range of usual son titles, for example between 200 dtex and 3000 dtex.

According to one particular embodiment of the invention, the yarns, fibers, filaments of the invention are yarns which have an overall count of between 700 and

2500 dtex. The title strand of the son of the invention can be chosen throughout the range of the usual son of titles. Strand titer is usually greater than or equal to 0.3 dtex. It is usually less than the equivalent in dtex with a diameter of 800 microns in the case of large diameter monofilaments.

According to a particular embodiment of the invention, the yarns, fibers, filaments of the invention are yarns which have a strand titer of between 3 and 10 dtex. The invention also relates to a process for preparing the son, fibers and filaments of the invention, by spinning the composition comprising the thermoplastic polymer matrix and the novolak resin. The composition may be prepared according to any method known to those skilled in the art.

The composition can be achieved by introducing the novolak resin into the molten polymer in a mixing device, for example upstream of a spinning device. It may be for example an introduction into the molten stream of the matrix, or else by means of a master batch ("master-batch" in English).

The son, fibers or filaments are made according to the usual spinning techniques from a composition comprising the thermoplastic polymer matrix and the novolak resin. The spinning can be carried out immediately after the polymerization of the matrix, the latter being in molten form. It can be made from a granule comprising the composition.

The son, fibers, filaments according to the invention may be subjected to all the treatments that may be performed in subsequent steps in the spinning step. They can in particular be relaxed or stretched, textured, curled, heated, twisted, dyed, sized, cut ... These complementary operations can be performed continuously and be integrated after the spinning device or be performed discontinuously. The list of operations subsequent to spinning has no limiting effect.

By spinning the composition, it is possible to obtain, for example, continuous multifilament yarns, short or long fibers, monofilaments, yarns of fibers, plies, ribbons, cables, etc.

The invention also relates, in a third object, an article comprising the son, fibers and / or filaments of the invention. The article may be a rope, rope or rope comprising at least threads, fibers, filaments described above, including multifilament yarns. Such articles can be obtained in particular from a single type of yarn, fibers, filaments or on the contrary from a mixture of yarns, fibers, filaments of different types. The rope, rope or rope comprises at least in part threads, fibers, filaments according to the invention. For a given type of yarn, fibers, filaments - for example yarns, fibers, filaments containing no novolak resin -, yarns, fibers or filaments of different natures can be used in the rope, rope, rope of the invention. The rope, rope or rope advantageously comprises at least 50% by weight of yarns, fibers, filaments of the invention.

The rope, rope or rope is preferably a climbing rope. Climbing ropes undergo significant mechanical stress. Climbing ropes generally consist of a core or core of ropes surrounded by a braided tubular sheath. The soul and the sheath are generally made of threads. There may be connections between the wires of the soul and the wires of the sheath. In a climbing rope, the son, fibers, filaments of the invention are advantageously present in the core of the rope, as opposed to the sheath. In the climbing rope of the invention, advantageously at least 50% by weight of the son, fibers, filaments of the core consist of son, fibers, filaments of the invention. Preferably the yarns, fibers, filaments of the invention are present both in the core and in the sheath of the rope. The rope of the invention not only has a significant resistance to the possible falls of the climber during its use, but also it allows to dampen these falls to preserve the climber of significant damage caused by the fall, especially in conditions of use of the rope at high humidity levels. Thus the invention also relates to the use of the rope of the invention under relative humidity conditions greater than or equal to 80%, preferably greater than or equal to 90%.

The invention also relates to the use of the rope of the invention in mooring or anchoring devices for boats, ships, floating docks, light pontoons, anchor buoys, navigation or tracking.

Finally, the invention relates to the use of a novolak resin as described above in the field of climbing ropes. The article of the invention may also be a paper machine felt. Typically these felts comprise fibers and monofilament fabrics. The felt may be produced from the blend of fibers of the invention and conventional fibers. The felt may also be produced from fabrics comprising monofilaments of the invention and conventional monofilaments. These felts are usually used in wet conditions.

The article of the invention may also be an airbag fabric generally obtained from multifilaments, or a textile article. The article of the invention may finally be a reinforcing article of tires. These items may for example be ropes. They can be obtained from multifilaments or monofilaments of the invention. They can also be obtained from mono or multifilament mixtures according to the invention and conventional. Other details or advantages of the invention will appear more clearly in view of the examples given below.

Damping capacity tests during a shock

The EN892 standard is a specific standard that evaluates the usage property of climbing ropes. In this standard, the ropes are preconditioned (72h to 65% RH) then subjected to a succession of falls under defined conditions of rope mass, height, length of the rope, and waiting time between 2 falls. Several quantities are measured among which:

- the impact force or maximum force perceived by the climber during the first fall, which must be less than a maximum value,

- the maximum elongation during the first fall, which must be less than a maximum value, - the number of falls before breaking the rope, which must be greater than a minimum value.

The force of impact perceived by the climber is, under the laws of mechanics (Force = Mass x Acceleration) a direct image of the acceleration seen by the climber. Imposing a maximum force amounts to imposing maximum acceleration.

The underlying physical property in this test is a property of damping or dissipation of energy. A "good" rope must absorb as quickly as possible the kinetic energy of the fall. Beyond the test performed according to EN892, necessarily performed on strings, it is possible to characterize the property of damping or dissipation of energy with many other methods. For example, the evaluation in dynamic mechanical tests of the elastic modulus G 'and the viscous module G "and their G7G' ratio, called tanδ, is often used to quantify this ability to dissipate energy. being this time possible on any type of material, whether the finished product (the rope), the constituent unitary material of the rope (the multi-filament or the monofilament) or any other piece obtained from of the same polymer formulation (an injected part for example).

EXAMPLES

Examples 1 to 4: Preparation of the Polyamide 6 and Novolac Resin Compositions The materials used are:

polyamide 6 granules with a viscosity index of 215 ml / g, measured in 90% formic acid (according to the ISO 307 standard)

pellets of phenol-formaldehyde novolac resin sold by Rhein Chemie under the reference Rhenosin® PR95

The polyamide 6 is pre-dried in a vacuum oven in order to reduce its water content to a value of approximately 500 ppm.

The mixture of polyamide 6 pellets and novolak resin pellets is made on a Leistritz 34 co-rotating twin-screw extruder.

A classic, relatively shearless profile is used on this extruder. The extrusion temperature is about 270 to 280 ° C.

The extrusion takes place without any notable difficulty. The extrusion conditions are perfectly stable and in total, 4 batches of 10kg each of granules are produced: Table 1

Examples 5 to 8: Spinning and Drawing of the Compositions The dtex-containing, multi-filament multifilament yarns comprising 12 strands (unit title after stretching approximately 7dtex) are made from the granules of Examples 1 to 4 on a laboratory spinning / drawing position FOURNE .

This spinning is carried out using a single-screw extruder, a title pump and a die, the spinning temperature is 265-270 ° C and the winding speed 300m / min.

This spinning step takes place under perfectly stable conditions. The speed of call can be maintained without difficulties and no breakage of strands is perceptible. This shows that the phenol-formaldehyde resin is perfectly compatible with the PA6 matrix in a spinning process.

In a second step, a step of stretching in recovery is carried out, by passing on heating rollers, then a relaxation and a winding. The winding is done at about 400m / min.

The call speed of the last rollers is adjusted to obtain a wire having an elongation at break of about 20%. This corresponds to a draw ratio of 4.35.

It should be noted that the drawing of these different threads took place under good conditions. The draw ratio of 4.35 of the reference yarns of Example 1 can be maintained at the same level on the additive systems of the yarns of Examples 2 to 4, which shows that the phenol-formaldehyde resin, which is approximately 5% additive, is compatible with a stretching process. The following table summarizes the torque analysis results. This is the average of 10 break values. They were measured on a FRANK machine in a laboratory conditioned to textile standards (65% RH).

Table 2

Examples 9 and 10: Evaluation of the Amortization Capacity of the Compositions Comprising Polyamide 6 and Novola Solvent

Plate moldings 100 x 100 x 1 mm are produced from the granules of Examples 1 and 4 on a DEMAG H200-80 press, which respectively corresponds to Examples 9 and 10. The temperature of the sheath is of the order of 285 mm. at 290 ° C.

The injection of these two samples takes place without any particular difficulty.

The evaluation of the damping capacity of the compositions of Example 1 and of Example 4, which respectively corresponds to Examples 9 and 10, is carried out by measuring the ratio between the viscous modulus G "and the elastic modulus. G 'called G "/ G' = tanδ. This measurement was performed on a Rheometrics brand RSA2 dynamic measuring machine (DMA).

DMA evaluations are carried out on specimens cut from the previous plates. A sinusoidal stress applied in 3-point bending with double embedding (frequency 1 Hz and amplitude 0.02%) and the analysis by DMA is carried out between -50 and + 100 ° C (raised to + 2.5 ° C / min). The DMA evaluations are carried out under 3 different hygrometric equilibrium conditions of the test pieces, at respective values of 50%, 75% and 95% RH. These hygrometric equilibria are obtained at the end of accelerated preconditionings, carried out at 70 ° C. The conditioning times required to reach equilibrium were estimated by following the water recovery. They are at least 96h at 50% RH, 48h at 75% RH and 24h at 95% RH.

Table 3 and Figure 1 specify the values of the dissipation coefficient tanδ measured with this method of DMA at the temperature of 25 ° C, corresponding to the typical temperature of stress during the impact of the climbing rope:

Table 3 and Figure 1 shows that the damping capacity (tanδ factor) is improved at 25 ° C between 50 and 95% RH for the add-on system according to the invention.

Table 3

Examples 11 to 14: Preparation of Polyamide 6.6 and Novolac Resin Compositions

The materials used are:

polyamide 6.6 granules with a viscosity index of 140 ml / g, measured in 90% formic acid (according to ISO 307) - pellets of phenol-formaldehyde novolac resin sold by Rhein

Chemie under the reference Rhenosin® PR95

The polyamide 6.6 is pre-dried in a vacuum oven in order to reduce its water content to a value of about 0.1 to 0.2% by weight.

The mixture of the polyamide 6.6 pellets and the novolac resin pellets is made on a Leistritz 34 co-rotating twin-screw extruder. A classic, relatively shearless profile is used on this extruder. The extrusion temperature is about 280 to 295 ° C depending on the area.

The extrusion takes place without any notable difficulty. The extrusion conditions are perfectly stable and in total, 4 batches of 10kg each of granules are produced:

Table 4

Examples 15 to 18: Evaluation of the Absorption Capacity of the Compositions Comprising Polyamide 6.6 and Novolac Resin

Plate moldings 100 × 100 × 1 mm are produced from the granules of Examples 1 1 to 14 on a DEMAG H200-80 press, which respectively corresponds to Examples 15 to 18. The temperature of the sheath is of the order of 280 to 290 ° C depending on the area.

The injection of these 4 samples takes place without any particular difficulty.

The evaluation of the damping capacity of these compositions is carried out under the same conditions as for the preceding examples Nos. 9 and 10, that is to say with the DMA technique on the RSA2 apparatus.

The DMA evaluations are carried out under 2 different conditions of hygrometric equilibrium of the test pieces, at respective values of 0 and 50% RH. The value 0% RH corresponds to a sample taken directly from the press followed by conditioning in an inert atmosphere before evaluation. The hygrometric equilibrium for the value 50% RH is obtained at the end of an accelerated preconditioning, carried out at 70 ° C. The conditioning time required to reach equilibrium was estimated by following the water recovery. It is about 75 hrs at 50% RH. Table 5 and Figure 2 specify the values of the dissipation coefficient tanδ measured with this method of DMA at a temperature of 25 ° C, corresponding to the typical temperature of loading during the impact of the climbing rope:

Table 5 and Figure 2 shows that the damping capacity (the tanδ factor) is improved at 25 ° C between 0 and 50% RH for the additive system according to the invention.

Table 5

Examples 19 to 21: spinning and stretching the compositions

Global title multifilament dtex 84 and having 12 strands (unit title after stretching about 7dtex) are made from the following formulations on a FOURNE laboratory spinning / stretching position.

Table 6

PA66 granules and Rhenosin® PR95 pellets are added directly to the spinning position.

This spinning is carried out using a single-screw extruder, a title pump and a die, the spinning temperature is 280-290 ° C and the winding speed 300m / min. This spinning step takes place under perfectly stable conditions. The speed of call can be maintained without difficulties and no breakage of strands is perceptible. This shows that the phenol-formaldehyde resin is perfectly compatible with the PA6.6 matrix in a spinning process.

The call speed of the last rollers is adjusted to obtain a wire having an elongation at break of about 20%.

It should be noted that the drawing of these different threads took place in good conditions. The draw ratio of the reference wires (example 19) is 4.76. It can be maintained at the same level on the 1% additive system (Example 20), which shows that the phenol-formaldehyde resin is compatible with a drawing process.

The following table summarizes the torque analysis results. This is the average of 10 break values. They were measured on a FRANK machine in a laboratory conditioned to textile standards (65% RH).

Table 7

Claims

1. Yarns, fibers or filaments based on thermoplastic polymer obtained from a composition comprising: - a thermoplastic polymer matrix, - a novolak resin.

2. Yarns, fibers or filaments according to claim 1, characterized in that the polymeric matrix is polyamide.

3. Yarns, fibers or filaments according to claim 1 or 2, characterized in that the novolac resin is a condensation product of phenol and formaldehyde.

4. Yarns, fibers or filaments according to one of the preceding claims, characterized in that the novolak resin has the following formula

5. Yarns, fibers or filaments according to one of the preceding claims, characterized in that the composition comprises between 0.1 and 20% by weight, preferably between 1 and 10% by weight, novolac resin.

6. Process for preparing the son, fibers, filaments according to one of claims 1 to 5 by spinning the composition comprising the thermoplastic polymer matrix and the novolak resin.

7. Method according to claim 6, characterized in that the spinning is a melt spinning of the composition.

8. Article comprising yarns, fibers and / or filaments according to one of claims 1 to 5.

9. Article according to claim 8, characterized in that it is a rope, a rope or a rope.

10. Article according to claim 9, characterized in that it is a climbing rope.

1. Article according to claim 8, characterized in that it is tire reinforcing articles.

12. Article according to claim 8, characterized in that it is tissues for airbag.

13. Article according to claim 8, characterized in that it is a felt machine for paper.

14. Article according to claim 8, characterized in that it is a textile article.

15. Use of the article according to one of claims 8 to 14 in relative humidity conditions greater than or equal to 80%, preferably greater than or equal to 90%.

16. Use of the article according to claim 9 in mooring or anchoring devices for boats, ships, floating wharves, light pontoons, anchor buoys, navigation or tracking.

17. Use of a novolac resin in the field of climbing ropes.