FR2948132A1 - ASSOCIATION OF NATURAL CATIONIC AND ANIONIC PRODUCTS AS BINDER FOR TEXTILE SUPPORT - Google Patents

Abstract

The present invention relates to the use of a mixture of at least two polymers and / or molecules of natural organic origin, one anionic and the other cationic, respectively, as a binder for textile support, as well as a method of binder deposit based on such a mixture to achieve a textile finishing or to consolidate a textile support.

Description

ASSOCIATION OF NATURAL CATIONIC AND ANIONIC PRODUCTS AS BINDER FOR TEXTILE SUPPORT

TECHNICAL FIELD The present invention relates to a combination of organic products, all derived from natural and renewable resources, for which binder properties for textile substrates have been demonstrated.

More specifically, in the context of the present invention, the binder is the combination of polymers and / or molecules, at least one cationic and the other anionic.

With a relatively simple process, these polymers and / or molecules can serve as a chemical binder for any type of textile support, whatever the structure and nature of the textile fibers used in the support.

STATE OF THE PRIOR ART

The textile industry is defined as encompassing the entire process from 20 fibers to the finished product. In this technical field, two main sectors of activity are defined, namely the long fibers (for example wool) and the short fibers (for example cotton).

A textile support or textile structure is defined as an assembly of textile fibers, whatever the assembly technique used. The nonwoven in which the fibers are randomly assembled are distinguished, the woven in which the fibers are an interweaving of warp yarns and weft yarns, and the knit where the fibers are interlaced in stitches. The nonwoven fabric is distinguished from paper by the greater length of its fibers (about 5 mm) and especially by the absence of hydrogen bonds between the fibers.

In other words, a nonwoven is a manufactured sheet, consisting of directionally or randomly oriented webs or webs of fibers bound by friction and / or cohesion and / or adhesion, excluding paper and the products obtained. by weaving, knitting, tufting, stitching incorporating binding yarns or filaments or felts by wet pressing, whether or not needled. The textile field also encompasses composite materials. A composite material is an assembly of at least two immiscible materials, but having good compatibility, thus constituting a new material that has properties that the elements alone do not possess. This possibility explains the increasing use of composite materials in different industrial sectors. Nevertheless, the exact description of a composite depends on the field of use and the expected mechanical performance.

In general, a composite material consists of a fibrous framework, called reinforcement, which provides the mechanical strength and a protection, called matrix, which is generally a plastic material (thermoplastic or thermosetting resin) and which ensures the cohesion of the structure and the retransmission of the forces towards the fibrous reinforcement. There are today a large number of composite materials that are typically classified into three families, depending on the nature of the matrix: - organic matrix composites (CMO), which are by far the most important volumes today on an industrial scale; - ceramic matrix composites (CMC) reserved for high-tech applications and working at high temperatures such as space, nuclear and military, as well as braking (ceramic brakes); - metal matrix composites (CMM).

The reinforcement is the skeleton supporting the mechanical forces. It can be in many forms: short fibers (mat) or continuous fibers (fabrics or multidirectional textures) depending on the intended application. Fibers generally have good tensile strength but low compressive strength. Among the most used fibers include glass fibers, carbon fibers, aramid fibers, silicon carbide fibers. For natural composites, there is a growing interest in plant fibers, such as hemp or flax. These fibers have good mechanical properties for a modest price, and are particularly ecological since they are natural products.

The resin remains synthetic (thermo-fusible polyolefin fibers or powders, polyamide, etc.). Many composites are also based on thermosetting polymers, which makes them difficult to recycle. These technological solutions therefore go against sustainable development.

In the field of textile, one can also mention the braids, ropes and structures mentioned above (non-woven, fabrics or knits) which have a three-dimensional structure (3D).

In general, the fibers used in the field of textiles can be of natural, synthetic or artificial origins. Another classification of the fibers divides them into organic and mineral fibers, respectively: mineral fibers, such as glass fibers and asbestos; - organic fibers: • of natural animal origin (such as silk or wool) or vegetable origin (such as cotton, linen or hemp); • of synthetic origin (polyamide, polyester, ...) • of artificial origin (viscose, cellulose acetate).

Textile supports have many applications, in particular in the following fields: - clothing, furniture; - transport (automobile, air, rail), more specifically for the interior trim or for the development of panels for the bodywork; - manufacture of panels for the building; - molding of packaging and transport elements; - agrotextile, namely the manufacture of flexible materials intended for example for the revegetation of soils or the fight against erosion; In the textile industry, in general, a binder (or resin) is defined as a product (liquid or solid) which assembles elements on the fibers constituting the textile: for example, immobilization of powder on fibers, fibers on fibers, molecules on fibers, microcapsules on fibers, ... Thus binders are used for textile finishing processes, such as: - pigment-based prints or dyes; - textile coating; immobilization of microcapsules on fibers; immobilization of biocidal (antimicrobial, anti-insect, etc.) actives on fibers; Immobilization of odorant molecules on fibers.

For these applications, the commercial binders used are acrylic, polyurethane or PVC binders.

Moreover, in the nonwoven industry in particular, the fibers are carded and transformed into a sheet. The sheet is consolidated by various techniques: - either thermally, by adding a binder (powder or fiber) which melts and glues the fibers together; - by needling (mechanical bonding); or by adding a chemical binder (or adhesive) which bonds the fibers together (chemical impregnation); or using a combination of several of these techniques.

In the non-woven industry, the most common bonding for consolidating fiber webs involves commercial products derived from petroleum chemistry, such as polypropylene powders or two-component fibers of which one component melts at a higher temperature. moderate temperature and resins (eg epoxy resins).

Of course, from an environmental point of view, these solutions for binding, based on petroleum resources, are considered unsatisfactory. Thus, it has been envisaged to create chemically related structures of natural and biodegradable origin. In the literature, two main categories of technical solutions of plant origin have been reported: thermoplastics, available in powder form, such as starch modified by a chemical functionalization, or else polylactic acid (PLA for Polylactic Acid) or Polyhydroxyalkanoates (PHA) which are entirely synthetic molecules but based on vegetable raw materials; thermosets, such as epoxidized vegetable oils.

However, the use of these binders requires the removal of powders, two-component fibers, or the projection or impregnation of the resins on the textile support, and the heating of the support at an elevated temperature.

There is therefore a clear need to identify new technical solutions that can be used for the treatment of textile structures by binders, in particular for textile finishing or chemical bonding of nonwovens, which do not have the drawbacks of those of the prior art. mentioned above.

SUMMARY OF THE INVENTION

Thus, the present invention relates to a binder for textile structures characterized in that this binder is exclusively of natural organic origin.

In the context of the invention, a structure or a textile support is defined as above, namely an arrangement of textile fibers, regardless of the method of manufacture of the structure (woven, knitted, nonwoven, braided textile surfaces , ..., whether 2D or 3D) and whatever the nature of the textile fibers.

Furthermore, a satisfactory binding function is defined as: a mechanical consolidation of the textile support, and / or an immobilization of elements (powder, molecules, microcapsules) on the fibers constituting the textile. Advantageously, this binding function persists over time and withstands various factors, in particular water and / or detergents, and abrasion. Various tests are known to those skilled in the art to test these properties, in particular: - the washing standard in the field of clothing articles = washing method 20 and domestic drying NF EN 26330; - the standard for evaluating the resistance to friction of textiles = NF EN ISO 105-X12 standard (crockmeter test).

Characteristically according to the invention, the binder is of natural organic origin, in other words derived from renewable resources, preferably of plant origin.

More specifically, the binder according to the invention is characterized by the presence of at least two polymers and / or molecules of natural origin, one anionic and the other cationic respectively. The term organic origin indicates that the polymers and / or molecules contain carbon.

The terms of vegetable origin or derived from renewable resources indicate that the polymers and / or molecules may, in their natural state, be in anionic or cationic form, or may be slightly modified, in particular so as to graft these functions. ionic. Advantageously, it is the combination of cationic and anionic polymers. However, a possible alternative to the implementation of anionic polymers is the use of anionic molecules.

In the context of the invention, the term "polymer" is understood to mean a macromolecule composed of monomers of low molecular weight, linked together in a chain or in a network.

Advantageously, the anionic or cationic polymers used have molar masses of between 103 and 106 Da. Typically, the polymers have a molecular weight of the order of 103 to 105 Da for the anionic lignosulfonates and 3.104 to 105 Da for the cationic starches.

Thanks to their network structure and intermolecular ionic bonds between the negative charges of the anion and the positive charges of the cation, the high molecular weight polymers used in the composition of the binder therefore serve to stiffen the textile support. bonding the fibers together and / or immobilizing elements (powder, molecules, microcapsules) on the fibers constituting the textile. They play perfectly their role of binder for textile supports.

It can be envisaged that the same polymer is both carrier of the anionic and cationic function, which is particularly the case of proteins such as albumin or collagen under conditions close to their isoelectric point. However, the intramolecular bonds being weaker than the intermolecular bonds, such polymers are advantageously used in anionic or cationic form, in association with a polymer and / or a molecule carrying the complementary charge.

As regards the cationic polymer, it is advantageously a starch derivative, in particular functionalized by quaternary ammonium functions. Starch is a complex carbohydrate main constituent of cereals and potatoes.

Such cationic starch derivatives are commercially available, in particular: Celquat H100 or Polyquaternium 4 (National Starch), a hydroxyethyl cellulose dimethyl diallylammonium (cationic) copolymer (CAS No. 92183-41-0); Celquat L200 (National Starch) or polyquaternium 4, a cationic cellulosic polymer; Celquat SC240C (National Starch) or polyquaternium-10 (CAS No. 53568-66-4), an ethoxylated and quaternized hydroxyethyl cellulose; - C * Bond HR 05949 (Cargill Industrial Starches), a cationic starch with a nitrogen content of 0.1% dry matter (CAS no .: 56780-58-6); - Cationamyl 9865 (AGRANA STÂRKE GMBH), a potato starch with a nitrogen content of 0.27-0.32% (CAS RN: 56780-58-6); - VECTOR SC 20157 (ROQUETTE), a cationic polymer derived from starch (CAS No. 56780 58 6).

In a preferred manner, the anionic polymer is a negatively charged lignin derivative. Lignin is a group of compounds found mainly in the pectocellulosic walls of certain plant cells, including wood. A preferred derivative of lignin is lignosulfonate (CAS RN: 8062-15-5), resulting from the production of pulp using bisulphite and carrying anionic sulfonate functions.

Thus, calcium lignosulfonate (CAS No: 8061-52-7), sodium lignosulfonate (CAS No: 8061-51-6), potassium lignosulfonate (CAS No: 37314-65-1), and ammonium lignosulfonate (CAS No. 8061-53-8) may be used in the context of the present invention.

Some of these polymers are commercially available, including the following sodium lignosulfonates: - Arbo N18 (TEMBEC), with a molar mass greater than 30,000, with a high degree of sulfonation (16% sulfur), resistant to 250 ° C without losing its surfactant and dispersant power; REAX 81A (Mead Westvaco), of medium degree of sulfonation, with about 5% sulfur; - REAX 85A (Mead Westvaco), low degree of sulfonation, and high molecular weight; Diwatex XP-9 (Borregaard LignoTech), of low degree of sulfonation, with about 3.5% sulfur; - Ultrazine Na (Borregaard LignoTech), high molecular weight; - Lignosol SD 60 (Borregaard LignoTech).

Alternatively, other types of anionic polymers may be used, such as sodium alginate from algae, cellulose oxide resulting from the oxidation of cellulose or anionic starch from of the chemical modification of the native starch.

In addition, the anionic component of the binder according to the invention may be an anionic molecule of natural origin, advantageously having a molar mass of between 100 and 1000 Da. In a preferred manner, it is a soluble fatty acid salt derived from natural products of both plant and animal origin. By way of example, such an anionic molecule may be sodium oleate or sodium lauryl sulphate.

It appears that the present invention is not limited to the combination of an anionic polymer or molecule and a cationic polymer, but that one or more polymers and / or anionic molecules may be associated with one or more cationic polymers. , the essential condition in the context of the invention being that all of these polymers and / or molecules is of natural origin.

Particularly preferred combinations within the scope of the invention have been defined: Arbo N18 + VECTOR SC 20157; - Arbo N18 + C * Bond HR 05949; Arbo N18 + Cationamyl 9865; - Arbo N18 + Cationamyl 9865 + C * Bond HR 05949; - Arbo N18 + Celquat H100; - Sodium oleate + VECTOR SC 20157; - Sodium lauryl sulphate + VECTOR SC 20157; - Sodium Oleate + C * Bond HR 05949.

In order to optimize the binder function, the best polymer mass ratios and / or anionic molecule / cationic polymers, especially cationic starch / sodium lignosulfonate are between 1/10 and 10/1, advantageously between 20/80 and 80/20.

It should be noted that the ideal ratio is not the stoichiometric ratio (number of cations / number of anions = 1). Unexpectedly, this ratio is in a wide range around 1, which makes it possible to obtain binders with different viscosity and appearance: fluid emulsions or suspensions, crystalline precipitates, oils, gums or gels. This working range around 1 is probably related to the spatial structure of the products used, their deformability in aqueous solution and the steric hindrance around the ionic charges that will be associated.

According to another preferred feature of the invention, particularly because of the intended applications such as agrotextile, the polymers and / or constituent molecules of the binder are advantageously biodegradable. By biodegradable is meant that, by the action of microorganisms under aerobic conditions, the decomposition of an organic compound into CO2, water and mineral salts provides a new biomass. A product is said to be biodegradable if it can be decomposed by living organisms in the biological environment (soil, fresh water, salt water, compost, activated sludge, etc.). Biodegradation results in a gradual simplification of the chemical structure of the organic compound: cleavage of the polymer chains and obtaining low molecular weight oligomers available for the synthesis of cellular constituents (biomass).

One of the methods for measuring the biodegradation of textiles is the standard NF EN ISO 11721-1 (June 2001): Determination of the resistance to microorganisms of textiles containing cellulose - Landfill tests - Part 1: Evaluation of a treatment rot-proof. This standard is used both to show the resistance of a textile to soil germs and to measure its biodegradation.

Thus, to the knowledge of the Applicant, it is the first time that a mixture of anionic and cationic polymers and / or molecules of exclusively natural origin is proposed for use as a binder for textile substrates.

The invention also relates to a method of depositing a binder as defined above on a textile support. This can be done for textile finishing, namely the assembly of elements on the fibers constituting the textile (immobilization of powder on fibers, fibers on fibers, molecules on fibers, microcapsules on fibers, etc. ) or for the consolidation of a nonwoven textile support.

More specifically, such a process comprises the following steps: application, on the textile support, of a mixture containing: at least two polymers and / or molecules of natural origin, the anionic and the cationic respectively ; At least one solvent; elimination of at least one solvent In preferred embodiments of the invention, the polymers and / or anionic and cationic molecules of natural origin are defined as above.

To be applied on the textile support, the anionic and cationic polymers and / or molecules are advantageously formulated in a liquid medium, using at least one solvent. A true or colloidal solution is thus obtained. Advantageously, the mixture is in the form of a solution. According to a preferred embodiment, the solvent is water, optionally supplemented with an alcohol. The alcohol may be either a light alcohol (defined as having not more than 3 carbon atoms), or a heavy alcohol (defined as having at least 4 carbon atoms), optionally in a mixture. A preferred light alcohol is ethanol. An example of an advantageous heavy alcohol is glycerol (Teb = 290 ° C.), derived from the saponification of animal or vegetable fats. Glycerol is also a by-product of the trans-esterification of vegetable oils in the production of methyl esters of vegetable oils which serve as fuels under the name of biodiesel or diester.

Of course, the dispersion of the cationic and anionic polymers and / or molecules in the solvent depends on the respective nature of these polymers and / or molecules and the solvent, but also on the concentration of polymers and / or molecules and the mass ratio between the polymers and / or molecules in the presence.

If these parameters can be determined case by case by those skilled in the art, it has been demonstrated, in the context of the present invention, that the polymers and / or molecules constituting the binder advantageously represent at most 20% by weight. of the mixture. This is the mass ratio between the dry matter of the binder and the total material of the mixture (binder + solvent in particular).

Moreover and as already mentioned, the mass ratio between polymers and / or anionic and cationic molecules, respectively, is advantageously between 1/10 and 10/1, and more particularly between 20/80 and 80/20.

Preferably, the application of the mixture on the textile support is carried out by spraying, in practice using a device equipped with one or more nozzles for projecting the mixture in the form of droplets. Alternatively, this deposition can be achieved by the two other techniques conventionally used in the textile field, namely by padding or immersion in a full bath. Alternatively, this deposition can be carried out by spraying with the aid of separate mixtures. solution in a solvent, or in the solid state. Thus, each polymer and / or molecule can be deposited independently.

Suitably, the application is carried out in a mass ratio between the dry matter of the binder mixture and the fibers of the textile support between 0.1 and 20%, ideally between 2% and 5%.

In the context of spraying which requires relatively fluid solutions, it turns out that the concentration and the ratio between the polymers and / or ionic molecules are particularly critical to obtain a final sprayable mixture: In fact, it has been observed that in case of over- or under-dosing of one of these polymers or molecules, non-soluble, non-manipulable products are obtained with formation of powder, gel, gum or excessive thickening of the solution.

The next step is to fix or activate the binder on the textile support. In the context of the present invention, this is achieved by simple partial or total elimination of all or part of the solvents in the presence.

In practice, the elimination is carried out by simple drying at a temperature adapted to the fibers and the products. The preferred temperature range is between 100 and 120 ° C. In the case where the solvent is water, this drying can also be carried out at ambient temperature. However, and in order to increase the elimination rate, it is possible to dispose the treated textile in an oven, between two heated plates of a press or in a drying ream. The use of moderate temperatures in the treatment of the textile constitutes a significant difference, with the prior art which imposed the heating of the support at an elevated temperature, higher than 150 ° C.

The spray application technique has the advantage of decreasing the amount of solvent in the presence and especially of facilitating its removal due to its dispersion in droplets.

According to this method, it is therefore necessary to find a compromise in terms of the concentration of the polymers and / or molecules, allowing on the one hand spraying (and therefore a limited concentration) and on the other hand a rapid elimination of the solvent (and therefore advantageously a high concentration).

In a particular embodiment and as already mentioned, the mixture of at least two polymers and / or anionic and cationic molecules, respectively, is produced in situ, that is to say directly on the textile support. In practice, this can be achieved by formulating each type of ionic polymer and / or molecule in a solvent and spraying each solution either consecutively or simultaneously but from separate nozzles.

EXAMPLES OF EMBODIMENT The invention and the advantages which result therefrom will emerge more clearly from the following exemplary embodiments, in support of the appended figures. These examples are however in no way limiting.

LEGENDS OF THE FIGURES FIG. 1 illustrates, in industrial trials, the influence of different spray mixtures on the mechanical properties of a rolled nonwoven of 600 g / m 2 in the production direction (A) or in the cross direction (B). Figure 2 illustrates, in laboratory tests, the influence of different spray mixtures on the mechanical properties of a rolled nonwoven calender in production (A) or cross-direction (B) direction. FIG. 3 illustrates, in laboratory tests, the influence of different spray mixtures on the mechanical properties of a rolled non-rolled non-woven fabric in the production (A) or cross-direction (B) direction. FIG. 4 illustrates, in laboratory tests, the influence of different spray mixtures on the mechanical properties of a non-rolled nonwoven fabric in the production (A) or cross-direction (B) direction. FIG. 5 illustrates, in laboratory tests, the influence of different spray mixtures on the mechanical properties of a non-rolled non-rolled non-rolled nonwoven in the production (A) or cross-direction (B) direction.

1 / GENERAL PROTOCOL FOR THE PREPARATION OF THE MIXTURE

The general protocol for obtaining a binder based on sodium lignosulfonate and cationic starch in water is as follows: Arbo N18 lignosulfonate (anionic polymer), which is in solid form, is solubilized in the cold water or possibly warmed at 40 ° C to accelerate the dissolution.

The cationic starch, C * Bond HR 05949, Cationamyl 9865 or Celquat H100 being in the form of powdered solids, is solubilized in water at 95 ° C. (to accelerate the dissolution), using a powerful stirrer of the Ultra type. Turrax at 6000 rpm until the solution is translucent, while maintaining the temperature at about 95 ° C.

Both solutions are mixed by pouring the Arbo N18 lignosulfonate solution into the cationic starch solution. The liquid medium thickens and then becomes fluid and can become a mixture of gum in water in the mass ratios of cationic starch / lignosulfonate. 2 / MIXING AN ANIONIC AND A CATIONIC:

Various combinations of Arbo N18 lignosulfonate (anionic polymer) and a cationic starch have been obtained at low (about 1%) or medium (about 5%) concentrations: Arbo N18 (N18) + Cationamyl 9865 (C98) Arbo N18 (N18) ) + Celquat H100 (H100) Arbo N18 (N18) + Vector SC 20157 (Vector)

Table 1 below summarizes the various tests carried out and indicates the percentages of the constituents of the binder in dry matter: Composition N18 H100 C98 Vector Total dry matter Cationamyl 9865 / Arbo N18 1.36% 4.32% 5.70% Celquat H100 / Arbo N18 0.25% 0.80% 1.05% Vector SC 20157` / Arbo N18 0.36% 0.71% 1.07% All these binders are sprayable at room temperature.

30 3 / MIXING AN ANIONIC AND A CATIONIC WITH HIGH CONCENTRATION:

A mixture of Arbo N18 lignosulfonate (anionic polymer) and a cationic starch was obtained in high concentration (10%): Arbo N18 (N18) + Cationamyl 9865 (C98)

Table 2 below summarizes the test carried out and indicates the percentages of the constituents of the binder, in dry matter: Composition N18 C98 Total dry matter Cationamyl 9865 / Arbo N18 2.39% 7.58% 10.0% This binder is sprayable at room temperature.

4 / MIXTURE OF ANIONIC AND TWO CATIONICS: Various combinations of Arbo N18 lignosulfonate (anionic polymer) and two cationic starches were obtained at average (about 5%) and at a high concentration (10%): Arbo N18 (N18 ) + Cationamyl 9865 (C98) 1/3 + C * Bond HR 05949 (HR) 2/3 Arbo N18 (N18) + Cationamyl 9865 (C98) 2/3 + C * Bond HR 05949 (HR) 1/3 The Table 3 below summarizes the different tests carried out and indicates the percentages of the constituents of the binder, in dry matter: Composition N18 C98 HR Total dry matter C Bond HR 05949 2/3 + Cationamyl 1,10% 1,16% 2,62 % 4,90% 9865 1/3 / ArboNl8 C Bond HR 05949 1/3 + Cationamyl 1.22% 2.57% 1.46% 5.20% 9865 2/3 / Arbo N18 C Bond HR 05949 2/3 + Cationamyl 2.25% 2.37% 5.35% 10.0% 9865 1/3 / Arbo N18 All these binders can be sprayed at room temperature.

5 / INDUSTRIAL MIXING OF MIXTURES:

This example describes industrial testing of lignosulfonate binders and cationic starch sprays on hemp nonwovens. The water removal conditions and the properties of the reinforced support (especially the mechanical strength) are indicated. The fibrous supports used for the spray treatments are nonwovens of needled hemp fiber. Control nonwovens are raw needled hemp nonwovens, having undergone the same treatment (heating / calendering) as sprayed nonwovens.

The binders are sprayed with a hand sprayer (gun type for addition of fluid liquids) on each side of the sample at a rate of about 2% dry matter. The feed speed of the nonwoven into the oven and the temperature are adjusted to dry the sample under good conditions without decomposition (120 ° C for 45 seconds).

The industrial tests are carried out with binders 3, 1 'and 2' of average concentration (approximately 5%).

Table 4 below summarizes the tests carried out and indicates the percentages of the constituents of the binder in dry matter: No. Composition N18 C98 HR Total dry matter 1 Cationamyl 9865 / Arbo N18 1.36% 4.32% 5.7% 1 Cationamyl 9865 / Arbo N18 1.60% 5.20% 6.80% 2 C Bond HR 05949 + Cationamyl 1.10% 1.16% 2.62% 4.9% 9865 / Arbo N18 2 'C Bond HR 05949 + Cationamyl 1.43% 1.4% 3.9% 6.7% 9865 / Arbo N18 3 C Bond HR 05949 + Cationamyl 1.22% 2.57% 1.46% 5.2% 9865 / Arbo Nl8 Binders 3, 1 'and 2' were used in this Example 5. Binders 1, 2 and 3 were used in Example 6 below.

The impregnated and dried nonwoven is calendered (or not) at the outlet of the oven, at 90 ° C so as not to alter the nonwoven fabric.

To characterize the effectiveness of the various binders, tensile tests were carried out on the various samples made industrially.

Experimental conditions: - Size of the test specimens: 5X20 cm (one specimen in the production direction and one specimen in the cross direction); - Parameters of the test: Fraction speed 50 mm / min; - Initial gap between the jaws: 100 mm.

For each binder sprayed, the results are expressed in - Maximum tensile strength (Fm); - Maximum stretch reversible to traction (cm); - Resistance to breaking (Fr); - Elongation at break (Er), in production direction and in cross direction.

These results, expressed in terms of gain (A in%) relative to the non-sprayed nonwoven, are shown in FIG.

The samples of 600 g / m2 thus obtained were studied and compared. The following conclusions can be drawn: The binder 1 '(anionic + cationic) is the least effective; The binder 2 '(one anionic + two cationic with [HR]> [C98]) improves all the properties of the nonwoven, while the binder 3 (solution 3 = one anionic + two cationic with [HR] <C98 ]) only improves properties in the elongation direction; In addition, the binder 2 'is sprayed at 1.8% (in dry matter), against 2.4% and 2.5% for the other binders 3 and 1', respectively (Figure 1).

6 / COMPLEMENTARY LABORATORY TESTS:

These laboratory tests made it possible to prepare comparable samples comparable to the industrial samples of Example 5, and thus to confirm the industrial results. The conditions of elimination of the water, the properties of the reinforced support (in particular the mechanical resistance) are indicated.

The sprays were carried out on the same nonwoven needles hemp of 600 g / cm 2, rolled or not, used in Example 5.

The binders are sprayed with a hand sprayer (gun type for fluid addition) on each side of the sample. The feed speed of the nonwoven into the oven and the temperature are adjusted to dry the sample under good conditions (120 ° C for 45 seconds). The samples are calendered or not at 90 ° C so as not to alter the nonwoven.

The binders 1, 2 and 3 (see Table 4) are sprayed on each side with 2% (+/- 0.1%) in total dry matter relative to the mass of fibers.

The tensile tests are carried out on these samples under conditions similar to those of Example 5.

The results, presented in FIGS. 2 to 5, are expressed in: Maximum tensile strength (Fm), denoted Rmax; 15 - Maximum stretch reversible to traction (cm).

The figures show the change in% of the mechanical characteristics provided by the binder with respect to the control supports (non-woven raw calendered or not).

In general, the maximum strength Fm (Rmax in the figures) is significantly improved (from 30 to 120%).

The corresponding maximum reversible tensile elongation (cm) is little modified or negative. If we consider the AFm (Rmax), in both machine and through directions, we observe that: - The binder 3 is the most suitable for the calendered-retted sample; The binder 2 is the most suitable for the calendered-non-rusty sample; The binder 2 is the most suitable for the non-calendered-retted sample; The binder 3 is the most suitable for the non-calendered-non-rusty sample.

7 / MODIFICATION OF THE SOLVENT:

A mixture of Arbo N18 lignosulfonate (anionic polymer) and a cationic starch (Vector SC 20157) was made at a low concentration (about 1%) in the presence of a heavy alcohol.

Thus, a heavy alcohol, in this case glycerol, is added in the binder formulation at a level of 1% relative to the solids. Glycerol is placed in the solution of Vector SC 20157. The Vector SC 20157 + Glycerol solution is then added to the lignosulfonate: Arbo N18 (N18) + Vector SC 20157 (Vector) + Glycerol

Table 5 summarizes the test carried out and indicates the percentages of the constituents of the binder, in dry matter: Composition N18 Vector Glycerol Total dry matter Vector SC 20157 "/ Arbo N18e 0.36% 0.71% 0.01% 1.08 The binder is sprayable at room temperature, resulting in a softer feel.

8 / RESISTANCE TO WASHING AND FRICTION:

Tests of resistance to washing and rubbing of a binder applied to cotton fabric were carried out.

The binder whose composition is shown in Table 6 below is applied by coating on a 130 g / m 2 cotton fabric. Composition N18 Vector Total Dry Tissue Vector SC 20157 "/ Arbo N18e 0.36% 0.71% 1.07% The fabric is dried in an oven at 120 ° C for 45 seconds 25 A - Wash Resistance Test:

A test piece of the fabric prepared above is washed. The fabric is washed twice at 40 ° C. in the presence of ECE laundry without perborate according to standard NF EN 26330.

On leaving the washes, the sample is dried. A small portion of the binder placed in excess on the cotton was removed at the washings. The majority of the binder remained on the fabric after washing. The binder placed on cotton by coating is resistant after 2 washes.

B - Friction resistance test:

The test is carried out on a specimen of the fabric prepared above according to standard NF EN ISO 105-X12 (crockmeter test).

The binder must not generate powder during the various manipulations of the textile (during manufacture, storage, installation or during use). In order to verify this property, an abrasion resistance test is done on the crockmeter. The abrasive medium is cotton.

The test piece is fixed on the cylindrical part of the apparatus and then deposited on the abrasive cotton support. The crank is then actuated. Under the effect of the weight, there is friction between the specimen and the support in white abrasive cotton (tests carried out with 150 fast return trips). No trace of binder, which is brown in color, is observed on the white abrasive medium; the coated fabric test piece is intact. The results are satisfactory, the binder placed on cotton by coating is resistant after 150 round trips.

20 9 / EARTH BIODEGRADATION TESTS:

One of the methods for measuring the biodegradation of textiles is the standard NF EN ISO 11721-1 (June 2001): Determination of the resistance to microorganisms in textiles containing cellulose - Landfill tests - Part 1: Evaluation of a 25 rotproof treatment.

The binder whose composition is shown in Table 7 below is sprayed onto a white cotton fabric of 130 g / m 2. The impregnation rate is 8.0% dry matter. Composition N18 Vector Total Dry Tissue Vector SC 20157 "/ Arbo N18e 0.36% 0.71% 1.07% The fabric is dried in an oven at 120 ° C for 45 seconds.

The treated fabric and the untreated fabric are buried in the soil for 8 and 15 days. The tissues are taken out of the ground, cleaned and weighed.

The observations are shown in Table 8: Samples Mass Change Mass Change Comments to 15 after 8 days after 15 days landfill days Cotton treated - 5.1% compared to - 7.4% compared to The binder is very much the mass of tissue the mass of degraded fabric. Cotton is treated as a low-severity starting point. Cotton no - 3.9% compared to - 10.7% versus cotton is highly treated the mass of tissue not to the mass of degraded tissue. starting untreated starting treatment After 15 days of burial, the binder placed on the cotton was degraded largely in the soil, under the conditions of the test. The treated cotton has not deteriorated much: the cotton begins to degrade when the totality of the binder disappeared after 15 days. The binder has behaved as a biodegradation retarding agent. In contrast, untreated cotton began to degrade (10% weight loss).

It is clear that the technical solution proposed in the context of the invention has many advantages, in particular: - economic solution (heating only to dry, and not to melt or polymerize) and ecological with the absence of use of products from oil and the possibility of exclusive use of vegetable raw materials, prepared in water; maintaining the biodegradation of the final textile product: the addition of the binder according to the invention does not inhibit the natural chain of biodegradation in soil, formation of humus and biomass; - Easy process: application of the binder by simple spraying or coating, followed by drying; - mechanical performance in line with expectations, especially when the textile is a non-woven fabric; - solid fixation of the binder to the fibers preventing its elimination by the rain (case of the agrotextiles), by the moisture (case of use in the transport) or by the laundry (case of textiles for clothing and furniture).

Claims (21)

REVENDICATIONS1. Use of a mixture of at least two polymers and / or molecules of natural organic origin, one anionic and the other cationic respectively, as binder for textile support. 2. Use according to claim 1, characterized in that the polymers and / or molecules of natural origin are biodegradable. 3. Use according to claim 1 or 2, characterized in that the anionic polymer is a lignin derivative, preferably lignosulfonate, and more preferably sodium lignosulfonate. 4. Use according to claim 1 or 2, characterized in that the anionic molecule is a fatty acid salt, preferably an oleate or a lauryl sulphate. 5. Use according to one of the preceding claims, characterized in that the cationic polymer is a starch derivative. 6. Use according to one of the preceding claims, characterized in that the mass ratio between polymers and / or anionic and cationic molecules is between 1/10 and 10/1, preferably between 20/80 and 80/20. 7. A process for depositing a binder on a textile support comprising the following steps: - application, on the textile support, of a mixture containing: • at least two polymers and / or molecules of natural organic origin, one anionic and the other cationic respectively; At least one solvent; - Elimination of at least one solvent. 8. Method according to claim 7, characterized in that the polymers and / or molecules of natural origin are biodegradable. 9. The method of claim 7 or 8, characterized in that the anionic polymer is a lignin derivative, preferably lignosulfonate. 10. Process according to claim 7 or 8, characterized in that the anionic molecule is a fatty acid salt, advantageously an oleate or a lauryl sulphate. 11. Method according to one of claims 7 to 10, characterized in that the cationic polymer is a starch derivative. 12. Method according to one of claims 7 to 11, characterized in that the mass ratio between polymers and / or anionic and cationic molecules is between 1/10 and 10/1, preferably between 20/80 and 80/20. 13. Method according to one of claims 7 to 12 characterized in that the mixture is in the form of a solution. 14. Process according to one of Claims 7 to 13, characterized in that the solvent is an aqueous solvent. 15. The method of claim 14 characterized in that the solvent consists of water. 20 16. The method of claim 14 characterized in that the solvent is water added with at least one alcohol. 17. Method according to one of claims 7 to 16 characterized in that the polymers and / or molecules represent at most 20% by weight of the dry matter mixture. 18. Method according to one of claims 7 to 17 characterized in that the application of the mixture on the textile support is carried out by spraying. 19. Method according to one of claims 7 to 18 characterized in that the application 30 is carried out in a mass ratio between the dry material of the mixture and the fibers of the textile support between 0.1 and 20%, preferably between 2 and 5%. 20. Method according to one of claims 7 to 19 characterized in that the removal of the solvent is carried out by drying, preferably at a temperature between 100 and 120 ° C. 10 25 21. Method according to one of claims 7 to 20 characterized in that the polymers and / or anionic and cationic molecules are applied to the textile support with the aid of separate mixtures, preferably in solution in a solvent or in the state solid.