FR3124808A1 - TEXTILE ELEMENT WITH WATER-REPELLENT TREATMENT, METHOD FOR PREPARATION, AND ITS USES - Google Patents

Abstract

The present invention relates to a rope with water-repellent treatment, its method of preparation, and its uses, in particular for outdoor sports. (no figure)

Description

TEXTILE ELEMENT WITH WATER-REPELLENT TREATMENT, METHOD FOR PREPARATION, AND ITS USES

The present invention relates to a textile element, in particular a rope or a strap, with water-repellent treatment, its method of preparation, and its uses, in particular for outdoor sports.

Climbing or mountaineering ropes are an integral part of the mountaineer's and rock climber's equipment, and are even one of their most important elements. Indeed, the different phases of climbing or mountaineering such as ascent, descent or even protection, all require the use of this equipment. Equipped routes, but also chocks, harnesses, and many other mountaineering products can only be used when combined with climbing ropes.

The first climbing ropes were made of cotton, then they were developed using hemp. From the 1950s, they were made of polyamide fibers, especially nylon, with excellent properties in many aspects such as tension, durability and abrasion resistance. However, the warps of polyamide fibers, especially nylon, contain hydrophilic amide bonds, which makes polyamide woven ropes highly hydrophilic. Thus, the weight of these polyamide climbing ropes increases sharply, up to 2 or 3 times, in contact with water. In addition, always in humid conditions, especially after having been wet and frozen, their resistance to wear, their durability, and their flexibility decrease.

All this makes their use difficult, unpleasant and even potentially dangerous in harsh weather conditions and/or environments.

Ropes treated with fluorinated products have been developed to make them waterproof. However, it has now been proven that such fluorinated products have a negative impact on the environment and health.

There is therefore a need to find an alternative to the textile elements, in particular the ropes and the straps, of the prior art.

Thus, one of the aims of the invention is to provide textile elements, in particular a rope or a strap whose water intake is greatly reduced compared to untreated textile elements, while being free of products dangerous for the environment and the health of the user.

Another object of the invention is to provide a process for the preparation of such textile elements, which can be implemented using biosourced starting materials and so-called “green” solvents.

Thus, according to a first aspect, the invention relates to a textile element, in particular a rope or a strap, consisting of or comprising fibers of at least one polyamide functionalized with at least one aldehyde of the following formula (I):

H-C(=O)-X(I);

in which X is a group chosen from:

• linear or branched C ₁ -C ₁₆ alkyls, in particular cyclohexanyl;
• C ₃ -C ₁₆ cycloalkyls;
• linear or branched C ₂ -C ₁₆ alkenyls;
• linear or branched C ₂ -C ₁₆ alkynyls; And
• C ₃ -C ₁₆ cycloalkenyls;

said group X being optionally substituted by at least one group R _a independently chosen from:

• linear or branched C ₁ -C ₁₆ alkyls,
• linear or branched C ₁ -C ₁₆ O-alkyls,
• aryls, in particular phenyl, optionally substituted with at least one R _b group independently chosen from linear or branched C ₁ -C ₁₆ alkyls; And
• phosphates, phosphonates, and phosphinates, in particular phosphates

Without wishing to be restricted to any theory, the at least one aldehyde of formula (I) is capable of reacting with the terminal –NH ₂ functions of the polyamide to form covalent bonds of the –N=CHX type, which make it possible to increase very significantly the hydrophobicity of the textile element thus functionalized.

According to a particular embodiment, said fibers are at least partly braided, in particular braided.

According to a particular embodiment, the textile element, in particular a cord or a strap, according to the invention is made up of or comprises a core surrounded by a sheath, the core and/or the sheath being made up of or comprising said fibers of polyamide.

According to a more particular embodiment, the textile element, in particular a rope or a strap, according to the invention consists of or comprises a core surrounded by a sheath, it being specified that:

• the core and the sheath are made of or include polyamide fibers; Or
• the core consists of or includes polyamide fibers, the sheath being in particular devoid of polyamide fibers; Or
• the sheath consists of or includes polyamide fibers, the core being in particular devoid of polyamide fibers.

According to a particular embodiment, the textile element according to the invention is a rope, for example a mountaineering rope or a climbing rope, a cord, a strap, a lace, in particular a shoe lace, or any device consisting of or comprising at least one rope and/or at least one strap, such as for example a harness or a chock. According to a particular embodiment, the polyamide is a 6-6 polyamide.

According to a particular embodiment, said polyamide fibers are functionalized with at least one aldehyde of formula (I _a ) below:

HC(=O)-X (I _a );

in which X is a group chosen from:

• linear or branched C ₁ -C ₉ alkyls;
• C ₃ -C ₉ cycloalkyls;
• linear or branched C ₂ -C ₉ alkenyls;
• linear or branched C ₂ -C ₉ alkynyls; And
• C ₃ -C ₉ cycloalkenyls;

said group X being optionally substituted by at least one group R _a independently chosen from:

• methyl,
• O-methyl,

and at least one aldehyde of formula (I _b ) below:

HC(=O)-X (I _b );

in which X is a group X ₁ chosen from:

• linear or branched C ₁₀ -C ₁₆ alkyls;
• linear or branched C ₁₀ -C ₁₆ alkenyls; And
• linear or branched C ₁₀ -C ₁₆ alkynyls;

said group X ₁ being optionally substituted by at least one group R _a independently chosen from:

• linear or branched C ₁ -C ₁₆ alkyls,
• linear or branched C ₁ -C ₁₆ O-alkyls,
• aryls optionally substituted with at least one R _b group independently chosen from linear or branched C ₁ -C ₁₆ alkyls; And
• phosphates, phosphonates, and phosphinates, in particular phosphates;

or a group X ₁ chosen from:

• linear or branched C ₂ -C ₁₆ alkyls;
• C ₃ -C ₁₆ cycloalkyls;
• linear or branched C ₂ -C ₁₆ alkenyls;
• linear or branched C ₂ -C ₁₆ alkynyls; And
• C ₃ -C ₁₆ cycloalkenyls;

said group X ₁ being substituted by at least one group R _a independently chosen from aryls optionally substituted by at least one group R _b independently chosen from linear or branched C ₁ -C ₁₆ alkyls.

According to a particular embodiment, said polyamide fibers are functionalized with at least one aldehyde of formula (I _a ) below:

HC(=O)-X (I _a );

in which X is a group chosen from:

• linear or branched C ₁ -C ₉ alkyls;
• linear or branched C ₂ -C ₉ alkenyls;
• linear or branched C ₂ -C ₉ alkynyls; And

said group X being optionally substituted by at least one group R _a independently chosen from:

• methyl,
• O-methyl,

and at least one aldehyde of formula (I _b ) below:

HC(=O)-X (I _b );

in which X is a group X ₁ chosen from:

• linear or branched C ₁₀ -C ₁₆ alkyls;
• linear or branched C ₁₀ -C ₁₆ alkenyls; And
• linear or branched C ₁₀ -C ₁₆ alkynyls;

said group X ₁ being optionally substituted by at least one group R _a independently chosen from:

• linear or branched C ₁ -C ₁₆ alkyls,
• linear or branched C ₁ -C ₁₆ O-alkyls,
• aryls optionally substituted with at least one R _b group independently chosen from linear or branched C ₁ -C ₁₆ alkyls; And
• phosphates, phosphonates, and phosphinates, in particular phosphates.

According to a particular embodiment, said polyamide fibers are functionalized with at least one aldehyde chosen from the aldehydes of the following formula:

.

According to a particular embodiment, said polyamide fibers are functionalized with at least citronellal.

According to another aspect, the invention also relates to a method for preparing a textile element, in particular a cord or a strap, in particular a textile element, in particular a cord or a strap consisting of or comprising fibers of at least one polyamide functionalized with at least one aldehyde of formula (I) as defined above, said method comprising a step (i) of treating a textile element, in particular a rope or a strap, consisting of or comprising fibers of au at least one polyamide with a composition A comprising:

• an aldehyde of formula (I) as defined previously;
• a supercritical fluid.

All the embodiments mentioned above with regard to the textile element of the invention can also be applied here, alone or in combination.

According to a particular embodiment, the aldehyde of formula (I) is present at 0.1 to 50%, in particular from 1 to 20%, more particularly from 2 to 10%, for example from 4 to 8% , or 5 to 7%, by weight relative to said textile element.

According to a particular embodiment, step (i) of processing comprises the following sub-steps:

• supply and optionally bringing into contact, within a closed reactor, the textile element, in particular rope or strap, with the aldehyde of formula (I);
• introduction of a liquid or gaseous composition, for example a liquid or gaseous composition of CO ₂ , intended for the preparation of the supercritical fluid, and heating of the said composition in order to obtain a supercritical fluid loaded with aldehyde of formula (I) , in particular homogeneously;
• impregnation of the textile element using the aldehyde-laden supercritical fluid of formula (I);
• depressurization of the reactor and recovery of the functionalized textile element.

According to a particular embodiment, step (i) is preceded by a step (o) of pretreatment of the textile element using a supercritical fluid.

This step (o) is likely to allow, if necessary, the desizing and/or the drying of the textile element before step (i).

According to a particular embodiment, step (i) is followed by a step (ii) of post-treatment of the textile element using a supercritical fluid.

This stage (o) is capable of making it possible, if necessary, to remove the excess of compound of formula (I) and optionally of formula (II) which could be present after stage (i).

According to a particular embodiment, the supercritical fluid of step (o), of step (i), and/or of step (ii), is supercritical carbon dioxide, the supercritical CO ₂ being in particular generated in situ by heating under pressure of liquid CO ₂ .

According to a particular embodiment, the process of the invention is a process in which:

• the temperature applied during steps (o), (i) and/or (ii) is between 80° C. and 140° C., preferably between 90° C. and 120° C.; and or
• the pressure applied during steps (o), (i) and/or (ii) is between 80 bar and 350 bar, preferably between 225 bar and 320 bar; and or
• the temperature and pressure conditions applied during steps (o), (i) and/or (ii) are maintained for a period varying from 5 minutes to 10 hours, more particularly from 10 minutes to 5 hours.

According to a particular embodiment, the method of the invention is a method in which the pressure applied during steps (o), (i) and/or (ii) is between 80 bar and 350 bar, in particular between 100 or 200 bar and 350 bar, preferably between 225 bar and 320 bar.

According to a particular embodiment, the process of the invention is a process in which:

• the pressure applied during step (o) is between 80 bar and 350 bar, in particular between 80 or 100 bar and 320 bar, preferably between 80 or 100 bar and 225 bar;
• the pressure applied during steps (i) and/or (ii) is between 200 bar and 350 bar, preferably between 225 bar and 320 bar.

According to a particular embodiment, the process of the invention is a process in which:

• the temperature applied during step (i) is between 90°C and 120°C, preferably between 100°C and 110°C; and or
• the pressure applied during step (i) is between 225 bar and 320 bar, preferably between 240 bar and 280 bar; and or
• the temperature and pressure conditions applied during step (i) are maintained for a period varying from 30 minutes to 8 hours, more particularly from 1 to 5 hours.

According to a particular embodiment, the process of the invention is a process in which:

• the temperature applied during steps (o) and/or (ii) is between 80° C. and 110° C., preferably between 90° C. and 110° C.; and or
• the pressure applied during steps (o) and/or (ii) is between 240 bar and 350 bar, preferably between 280 bar and 320 bar; and or
• the temperature and pressure conditions applied during steps (o) and/or (ii) are maintained for a period varying from 5 minutes to 2 hours, more particularly from 10 minutes to 30 minutes or 1 hour.

According to a particular embodiment, steps (o) and (i), or (i) and (ii), or (o), (i) and (ii), are carried out within the same reactor.

According to another aspect, the invention also relates to a textile element, in particular a rope or a strap, capable of being obtained by the method as defined above.

According to another aspect, the invention also relates to the use of a textile element, in particular a rope or a strap as defined previously for the practice of hiking or mountaineering or any other sport of outdoors (kiting, paragliding), or for lacing shoes, especially walking, hiking or climbing shoes.

All the embodiments mentioned above with regard to the textile element or the method of the invention can also be applied here, alone or in combination.

Definitions

As used herein, the term "about" refers to an interval of values within ±10% of a specific value. By way of example, the expression “approximately 20” includes values of 20 ± 10%, i.e. values from 18 to 22.

Within the meaning of the present description, the percentages refer to percentages by mass relative to the total mass of the formulation, unless otherwise indicated.

As understood here, value ranges in the form of "x-y" or "from x to y" or "between x and y" include the x and y bounds as well as the integers between these bounds. By way of example, "1-5", or "from 1 to 5" or "between 1 and 5" designates the integers 1, 2, 3, 4 and 5. Preferred embodiments include each integer taken individually in the range of values, as well as any sub-combination of these integers. By way of example, preferred values for "1-5" may include the integers 1, 2, 3, 4, 5, 1-2, 1-3, 1-4, 1-5, 2-3, 2 -4, 2-5, etc.

As used herein, the term "alkyl" particularly denotes a straight or branched chain alkyl group having the number of carbon atoms indicated before said term, especially 1 to 12 carbon atoms, such as methyl, ethyl , propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isoamyl, neopentyl, 1-ethylpropyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, hexyl, octyl, etc. Thus, an expression such as "C1-C16 alkyl" denotes an alkyl radical containing from 1 to 16 carbon atoms. These include a C1-C12 alkyl, designating an alkyl radical containing 1 to 12 carbon atoms.

As used here, the term "alkenyl" designates in particular a group with a carbon chain corresponding to a chain of an alkyl group as defined previously, in particular of 1 to 12 carbon atoms, which carries at least one unsaturation, at i.e. a covalent double bond between two carbon atoms. This unsaturation can be located at any position of the carbon chain. The group "alkenyl" also covers carbon chains carrying more than one unsaturation, for example two unsaturations, in particular two conjugated unsaturations.

As used here, the term “alkynyl” designates in particular a group with a carbon chain corresponding to a chain of an alkyl group as defined previously, in particular of 1 to 12 carbon atoms, which carries at least one unsaturation, at namely a triple covalent bond between two carbon atoms. This unsaturation can be located at any position of the carbon chain. The group "alkynyl" also covers carbon chains carrying more than one unsaturation, for example two unsaturations, in particular two conjugated unsaturations.

As used here, the term “cycloalkye” designates in particular a group whose carbon chain, corresponding to an alkyl group chain as defined above, forms one or more rings, in particular one or two rings. It is for example a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc…, in particular cyclohexyl. This "cycloalkye" can be bridged.

As used here, the term "cycloalkene" designates in particular a cycloalkyl group as defined above bearing at least one insertion, in particular one or two unsaturations (namely covalent double bond between two carbon atoms).

FIGURES

There illustrates a drop of water on sample 2 of the examples, according to the invention, obtained by a process according to the invention.

EXAMPLES

Materials and methods

A lace (core in UHMWPE and sheath in PA 6-6) and a rope (core and cover in PA6-6) were treated by the method of the invention. These are commercial items, for example marketed by Simond or Salomon.

The lace and the rope were treated in a supercritical CO ₂ medium (CO2SC) containing an aldehyde of formula (I), for example citronellal.

The treatment was carried out using batch supercritical CO ₂ treatment equipment (for example SEPAREX SFE-1L, France, or AGECOM). It is in particular a cylindrical reactor.

The shoelace and rope were first treated with only SCCO2 at 300 bar, 100°C for 15 min, then with the reagent(s) in SCCO2 at 260 bar, 105°C for 3 hours.

The at least one aldehyde of formula (I) is, for example, present at a level of 6 to 7% by weight with respect to the cord or the lace.

A water uptake test was then carried out on the samples obtained.

This test is done for example by immersing a fraction of lace or rope (10-20cm for example) in a beaker of water (100-500ml depending on the size of the sample), for 1 minute, then weighing after sketchy drainage (no formation/fall of a drop of water when the sample is suspended vertically).

The percentage of water uptake ∆m% was calculated as follows, for each sample:

∆m% = (m _wet -m _dry )/m _dry .

In addition, the drop angle of a drop of deionized water (DI water) was observed and measured, confirming the development of surface hydrophobicity (cf. ).

Results

The results are recorded in the following table:

Sample # Nature ∆m% 1 Lace (Reference excluding invention) 27.09 2 Lace + citronellal 2.55 4 Rope (Reference excluding invention) 52.57 5 Rope + citronellal 10.26

These results show the very significant effect of the treatment of the invention on commercial ropes and laces, in terms of reduced water intake.

Claims (9)

Textile element, in particular a rope or a strap, consisting of or comprising fibers of at least one polyamide functionalized with at least one aldehyde of the following formula (I):
H-C(=O)-X(I);
in which X is a group chosen from:

• linear or branched C ₁ -C ₁₆ alkyls;
• C ₃ -C ₁₆ cycloalkyls;
• linear or branched C ₂ -C ₁₆ alkenyls;
• linear or branched C ₂ -C ₁₆ alkynyls; And
• C ₃ -C ₁₆ cycloalkenyls;

said group X being optionally substituted by at least one group R_Toindependently chosen from:

• linear or branched C ₁ -C ₁₆ alkyls,
• linear or branched C ₁ -C ₁₆ O-alkyls,
• aryls optionally substituted with at least one R _b group independently chosen from linear or branched C ₁ -C ₁₆ alkyls; And
• phosphates, phosphonates, and phosphinates, in particular phosphates.

Textile element according to claim 1:

• wherein said fibers are at least partly braided; and or
• which consists of or comprises a core surrounded by a sheath, the core and/or the sheath being made of or comprising said polyamide fibers; and or
• which is a mountaineering rope, strap or shoelace; and or
• wherein the polyamide is polyamide 6-6.

Process for preparing a textile element according to any one of claims 1 to 2, said process comprising a step (i) of treating a textile element consisting of or comprising fibers of at least one polyamide with a composition A including:

• an aldehyde of formula (I) as defined in claim 1;
• a supercritical fluid.

Process according to Claim 3, in which the aldehyde of formula (I) is present in the amount of 0.1 to 50%, in particular of 1 to 20%, more particularly of 2 to 10%, for example of 4 to 8 %, or 5 to 7%, by weight relative to said textile element. A method according to any of claims 3 to 4, wherein processing step (i) comprises the following sub-steps:

• supply and possibly contacting, within a closed reactor, of the textile element, of the aldehyde of formula (I));
• introduction of a liquid or gaseous composition, for example a liquid or gaseous composition of CO ₂ , intended for the preparation of the supercritical fluid, and heating of the said composition in order to obtain a supercritical fluid loaded with aldehyde of formula (I) , in particular homogeneously;
• impregnation of the textile element using the aldehyde-laden supercritical fluid of formula (I);
• depressurization of the reactor and recovery of the functionalized textile element.

A method according to any of claims 3 to 5, wherein:

• step (i) is preceded by a step (o) of pretreatment of the textile element using a supercritical fluid; and or
• step (i) is followed by a step (ii) of post-treatment of the textile element using a supercritical fluid.

A method according to claim 6, wherein the supercritical fluid of step (o), step (i), and/or step (ii), is supercritical carbon dioxide, the supercritical CO ₂ being in particular generated in situ by heating under pressure of liquid CO ₂ . A method according to any of claims 3 to 7, wherein:

• the temperature applied during steps (o), (i) and/or (ii) is between 80° C. and 140° C., preferably between 90° C. and 120° C.; and or
• the pressure applied during steps (o), (i) and/or (ii) is between 200 bar and 350 bar, preferably between 225 bar and 320 bar; and or
• the temperature and pressure conditions applied during steps (o), (i) and/or (ii) are maintained for a period varying from 5 minutes to 10 hours, more particularly from 10 minutes to 5 hours.

Use of a textile element according to any one of claims 1 to 2 for the practice of hiking or mountaineering or any other outdoor sport, or for lacing shoes, in particular walking shoes, hiking or climbing.