FR2834523A1 - Production of polymer-based treatment agent for improving the antistatic and hydrophilic properties of textiles involves reacting polyisocyanate with ethoxylated fatty amine - Google Patents

Abstract

A method for the production of a polymer-based treatment agent (A), especially for improving the antistatic properties of textile substrates, in which the polymer is obtained by reaction of polyisocyanate(s) (B) with ethoxylated fatty amine(s) (C). Independent claims are also included for the following (1) a treatment agent prepared as above, especially for improving the antistatic and/or hydrophilic properties of textiles (2) methods for the antistatic treatment of textiles by (M1) impregnation or padding with the addition of 2.5-100 g/l of (A) to a treatment bath, or by (M2) a draining process with the addition to the treatment bath of 0.2-12% (A) based on the material to be treated (3) treated textile substrates comprising fibers coated with (A).

Description

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 The subject of the invention is a method for manufacturing a treatment agent, in particular intended to improve the antistatic power of a textile support.

 The accumulation of electrostatic charges on the surface of the clothing fibers can cause abrupt and unpleasant discharges of these charges when they are brought into contact with an electrically conductive element.

 It is therefore desirable to treat these clothes to increase their antistatic power.

 Many treatment agents are currently used in the textile field. For example, the sodium or potassium salts of formic acid are inexpensive anionic treatment agents, but the effectiveness of which is low.

 The diethanolamine or triethanolamine salts of the derivatives of the reaction of phosphorus pentoxide with alcohols, such as, for example, diethanolamine diisobutyl phosphate, are also used. These products are effective and applicable by padding or spraying. Anionic, they do not naturally rise in the fibers and are not suitable for applications by exhaustion.

 There is therefore a need for treating agents capable of improving the antistatic power of textile substrates, which are effective and can be applied by exhaustion, padding or spraying.

 The present invention aims to satisfy this need.

 More particularly, the invention relates to a method for manufacturing a treatment agent, in particular for improving the antistatic power of a textile support, said treatment agent comprising at least one polymer. This process is remarkable in that said polymer is produced by reacting at least one polyisocyanate and at least one oxyethylenated fatty amine.

 It has been unexpectedly observed that a polymer-based treatment agent obtained by reacting a polyisocyanate or polyisocyanate mixture with an oxyethylenated fatty amine or a mixture of oxyethylenated fatty amines improves the antistatic power of treated textile substrates, without degrading their degree of white.

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 The invention also relates to - an agent for treating textile substrates comprising a polymer obtained according to a process according to the invention; processes for treatment by impregnation, padding or exhaustion of a textile support to improve its antistatic power; a treated textile support comprising fibers coated with a treatment agent according to the invention.

où - R est une chaîne grasse saturée ou insaturée, avec un nombre d'atomes de carbone compris entre 6 et 40, - x est compris entre 1 et 50 inclus, - y est compris entre 1 et 50 inclus

ou pour formule

Preferably, the oxyethylenated fatty amines used according to the process of the invention have the formula:

where - R is a saturated or unsaturated fatty chain, with a number of carbon atoms between 6 and 40, - x is between 1 and 50 inclusive, - is between 1 and 50 inclusive

or for formula

où - Ri est une chaîne grasse saturée ou insaturée avec un nombre d'atomes de carbone compris entre 6 et 40, - R2 est un atome d'hydrogène (H) ou une chaîne grasse saturée ou insaturée avec un nombre d'atomes de carbone compris entre 6 et 40, - z est compris entre 1 et 50 inclus.

where - Ri is a saturated or unsaturated fatty chain with a carbon number of between 6 and 40, - R2 is a hydrogen atom (H) or a saturated or unsaturated fatty chain with a number of carbon atoms between 6 and 40, - z is between 1 and 50 inclusive.

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 Preferably, at least one of said fatty chains R, R 1 and R 2 comprises from 2 to 14 carbon atoms, that is to say are chains of Copra, oleic or tallow.

 More preferably, the oxyethylenated amine comprises between 10 and 30 units of ethylene oxide.

dans laquelle d a une valeur comprise entre 2,4 et 2,8 ; - le triphényl méthane triisocyanate, de formule :

- les polyisocyanates préparés par condensation d'un diisocyanate sur un polyol dans des conditions telles qu'il y ait plus de 2 groupes-N=C=O libres. Un exemple choisi dans cette classe de polyisocyanates est le produit de réaction de 3 moles de toluène diisocyanate sur une mole de triméthylol propane et dont la structure uréthane idéalisée est : Polyisocyanates comprising a plurality of isocyanate groups N = C = O attached to an aliphatic or aromatic structure and which can be used according to the invention are, for example: poly (phenylene isocyanate), of formula:

wherein da is between 2.4 and 2.8; triphenyl methane triisocyanate, of formula:

polyisocyanates prepared by condensation of a diisocyanate on a polyol under conditions such that there are more than 2 free N = C = O groups. An example chosen in this class of polyisocyanates is the reaction product of 3 moles of toluene diisocyanate on one mole of trimethylolpropane and whose idealized urethane structure is:

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- des polyisocyanates préparés par condensation d'un diisocyanate sur l'eau avec formation de cycles isocyanurates, - les polyisocyanates préparés par condensation d'un diisocyanate sur l'eau avec formation de groupes biuret. Un exemple de cette classe de polyisocyanates est le produit de condensation avec l'eau de 3 moles de 1-6 hexaméthylène diisocyanate et dont la structure biuret idéalisée est :

polyisocyanates prepared by condensation of a diisocyanate on water with formation of isocyanurate rings; polyisocyanates prepared by condensation of a diisocyanate on water with formation of biuret groups. An example of this class of polyisocyanates is the condensation product with water of 3 moles of 1-6 hexamethylene diisocyanate and whose idealized biuret structure is:

The above list of polyisocyanates that can be used in the invention is not limiting. On the other hand, the polyisocyanates can be used alone or as a mixture.

 In order to prepare, according to the invention, a treatment agent, a polyisocyanate or a mixture of polyisocyanates is dosed on the one hand and an oxyethylenated fatty amine or a mixture of oxyethylenated fatty amines on the other hand, so that the molar ratio OH-groups of oxyethylenated amines and isocyanate-N = C = O groups of the polyisocyanates is between 0.1 and 10, preferably between 0.5 and 2 moles of -OH per mole of-N = C = 0.

 The polysocyanates and oxyethylenated amines thus measured are then mixed and brought to a temperature of between 80 and 110 C.

 Optionally, it is also possible to add to the mixture a solvent, such as toluene for example, and optionally a catalyst for the reaction between the polysisocyanates and the oxyethylenated amines, for example tin salts.

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 After about 2 hours, a more or less viscous cationic polymer, soluble in water, is obtained.

 Preferably, the polymer is diluted in water so that the resulting treating agent has a solids content of 10 to 75% by weight, preferably a solids content of 20 to 30% by weight.

 The possible excesses of polyisocyanates are hydrolysed during dilution in water. The possible excesses of oxyethylenated amines do not modify the properties of the polymer.

 The treatment agent according to the invention makes it possible to treat textile substrates such as a fabric, a knit or a nonwoven, comprising, for example, fibers made of cotton, wool, polyester, nylon, acrylic, viscose, or a mixture of fibers of these different materials.

 The treatment agent according to the invention may be applied to the fibers of a textile support by impregnation or padding. The treatment agent is then added to the treatment bath in an amount of between 2.5 and 100 g per liter of treatment bath, preferably between 5 and 75 g per liter of treatment bath. The impregnated support can then be expressed in the headscarf. It is then dried at a temperature of between 100 ° C. and 180 ° C.

 Advantageously, the treatment agent according to the invention is cationic and is therefore applicable by exhaustion on a textile support. For an application by exhaustion, the doses of treatment agent to be added in the treatment bath are between 0.2 and 12%, preferably between 0.5 and 8%, as a percentage by weight relative to the mass of the support. treat.

 The treatment agent according to the invention can also be introduced into printing pastes or into coating formulas, or else be sprayed onto the textile support.

 The examples below are indicative and not limiting in order to illustrate the properties of treatment agents A, B and C according to the invention.

 To measure the antistatic power of a textile support, a difference in electrostatic charges is established between two points of this support spaced 10 cm apart. It is then measured using a voltmeter "static-Voltemeter Rotschild R1019"

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 the time required for this charge difference to decrease by half. This duration, called the half discharge time and expressed in seconds, provides a measure of the antistatic power of this medium.

 A zero value for the half-discharge time means that this time is less than the measurement capacity of the voltmeter used.

 To measure the hydrophilic power of a textile support, a capillary-mounted water height is measured on a sample of this support placed vertically above the water and whose base soaks in this water.

 The sample has a width of 2 cm and a height of 20 cm.

 The water depth, expressed in mm, is measured from the surface of the water in which the sample soaks, after 2 minutes of soaking.

 Agent A is obtained by reacting phenylene polyisocyanate with oleyl amine having 15 ethylene oxide units.

 In a 2-liter flask equipped with a stirrer, a thermometer and a reflux condenser, are introduced 500 g of toluene and 100 g of oleyl amine having 15 units of ethylene oxide. After having removed the traces of water by azeotropic distillation of the water-toluene mixture, 7.15 g of phenylene polyisocyanate are introduced. The molar ratio in this example is two moles of OH for one mole of -N = C = O. The mixture is heated at 100-110 C for 3 hours, then the toluene is removed by vacuum distillation of 40 mm Hg, at 170 C.

 At the end of the reaction, the product of the reaction is cooled and then diluted in water to reach a solids content of 22%. Agent A is the result of dilution.

 Agent B is obtained by reaction of phenylene polyisocyanate with oleyl amine having 15 ethylene oxide units.

 In a 2-liter flask equipped with a stirrer, a thermometer and a reflux condenser, are introduced 500 g of toluene and 100 g of oleyl amine having 15 units of ethylene oxide. After having removed the traces of water by azeotropic distillation of the water-toluene mixture, 14.3 g of phenylene polyisocyanate are introduced. The molar ratio in this example is one mole of -OH for one mole of -N = C = O. The mixture is heated at 100-110 C for 3 hours, then the toluene is removed by vacuum distillation 40 mm of mercury at 170 C.

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 At the end of the reaction, the product of the reaction is cooled and then diluted in water to reach a solids content of 22%. Agent B is the result of dilution.

 Agent C is obtained by reacting the phenylene polyisocyanate with a tallow amine having 25 ethylene oxide units.

 In a 2-liter flask equipped with a stirrer and a thermometer, 100 g of tallow amine having 25 ethylene oxide units are introduced. After removing the traces of water by distillation, 8.85 g of phenylene polyisocyanate are introduced. The molar ratio in this example is 0.9 mole of -OH for one mole of -N = C = O. The mixture is heated at 100-110 C for 3 hours.

 At the end of the reaction, the product of the reaction is cooled and then diluted in water to reach a solids content of 22%. Agent C is the result of dilution.

 For each example of Table 1 below, a polyester fabric (PES 100%) weighing 145 g / m 2 is impregnated in different padding baths. The fabric is then expressed and dried at 120 ° C., and then the antistatic power of this fabric is measured.

 The amounts of agent are given in grams per liter of pad bath.

TABLE 1

<Tb>
<tb> EXAMPLE <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 4 <SEP> 5 <SEP> 6 <SEP> control <SEP> 1
<tb> agent <SEP> A <SEP> 20 <SEP> 40 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> tissue
<tb> agent <SEP> B <SEP> 0 <SEP> 0 <SEP> 20 <SEP> 40 <SEP> 0 <SEP> 0 <SEP> no
<tb> agent <SEP> C <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 20 <SEP> 40 <SEP> processed
<tb> time <SEP> of <SEP> 1/2 <SEP> discharge <SEP> 2s <SEP> 0 <SEP> 3s <SEP> 0 <SEP> 1s <SEP> 0 <SEP>><SEP> 1 <SEP> hour
<Tb>

The values obtained in Table 1 show the high antistatic power of the treated supports by means of agents according to the invention.

 For each example of Table 2 below, an acrylic fabric 100% weight 145 glum 2 is treated by exhaustion in various treatment baths.

 The bath ratio is 1/10. The temperature of the bath is 40 C.

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i Le temps de traitement est d'une demi-heure. In a depletion application, the term "bath ratio" is used to refer to the ratio of the weight of material to be treated to the volume of bath in which this material will be treated. For example, per 10 kg of material to be treated in a bath of 100 liters, the bath ratio is 1 to 10 or 1/10.

i The treatment time is half an hour.

 The amounts of agent are expressed as a percentage by weight relative to the mass of the treated fabric.

 The fabric is then dried at 120 ° C., and then the antistatic power of this fabric is measured.

TABLE 2

<Tb>
<tb> EXAMPLE <SEP> 7 <SEP> 8 <SEP> 9 <SEP> 10 <SEP> 11 <SEP> 12 <SEP> 13 <SEP> 14 <SEP> 15 <SEP> Control <SEP> 2
<tb> agent <SEP> A <SEP> 4 <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> Fabric
<tb> in <SEP>%
<tb> agent <SEP> B <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 2 <SEP> 4 <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> no
<tb> in <SEP>%
<tb> agent <SEP> C <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 2 <SEP> 4 <SEP> 10 <SEP> processed
<tb> in <SEP>%
<tb> Time
<tb> of <SEP> Y2 <SEP> 10s <SEP> 0 <SEP> 0 <SEP> 8s <SEP> 0 <SEP> 0 <SEP> 12s <SEP> 1s <SEP> 0 <SEP>> 1 <SEP> hour
<tb> discharge
<Tb>

The values obtained in Table 2 show that the agents according to the invention confer strong antistatic powers on a textile support, even when they are applied by exhaustion.

 For examples 16 and 17, polyester fabrics (PES 100%) with a basis weight of 145 g / m 2 are impregnated in a padding bath containing 30 g and 50 g, respectively, of agent A per liter of bath.

 The tissues are then expressed and dried at 120 ° C. Then the antistatic power of these tissues is measured.

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 The tissues are then dipped in a water bath at 20 ° C. for 5 minutes, then expressed and dried at 120 ° C. The antistatic power of the tissues (half-discharge time 2) is measured again.

 The fabrics are then washed at 40 ° C. in a washing bath, with 5 g of soap per liter of the washing bath, for 30 minutes.

 The tissues are then rinsed, expressed and dried at 120 C.

 The antistatic power of the tissues is measured again (half-discharge time 3).

TABLE 3

<Tb>
<tb> EXAMPLE <SEP> 16 <SEP> 17 <SEP> Control <SEP> 3
<tb> agent <SEP> A <SEP> in <SEP> g / l <SEP> of <SEP> bath <SEP> 30 <SEP> 50 <SEP> Tissue <SEP> no <SEP> processed
<tb> time <SEP> of <SEP> 1/2 <SEP> discharge <SEP> 1 <SEP> 0 <SEP> 0 <SEP>><SEP> 1 <SEP> hour
<tb><SEP> antistatic <SEP> power after
<tb> soaking <SEP> 2s <SEP> Os <SEP>><SEP> 1 <SEP> hour
<tb> time <SEP> of <SEP> 1/2 <SEP> discharge <SEP> 2
<tb><SEP> antistatic <SEP> power after
<tb> wash <SEP> to <SEP> 400C <SEP> 10s <SEP> 3s <SEP>><SEP> 1 <SEP> hour
<tb> time <SEP> of <SEP> 1/2 <SEP> discharge <SEP> 3
<Tb>

By way of comparison, the same polyester fabric treated, according to the prior art, by means of a bath containing an antistatic agent based on sodium salts of formic acid, at the same dose, no longer has antistatic power after soaking.

 The values obtained in Table 3 show the high antistatic power imparted to a textile support by the agents according to the invention, but also the permanence of this power after prolonged soaking in water or after washing.

 For Example No. 18, 100% polyester / viscose and 100% acrylic fabrics are impregnated in a padding bath containing only 10 g of Agent A per liter of padding bath. The tissues are then expressed and dried at 120 ° C., and then the hydrophilic power of the tissue is measured.

 The hydrophilic powers obtained are presented below:

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<Tb>
<tb> tissue <SEP> of <SEP> cotton <SEP> (100%) <SEP> no <SEP> treated <SEP>: <SEP> 15 <SEP> mm
<tb> tissue <SEP> of <SEP> cotton <SEP> (100%) <SEP> treated <SEP>: <SEP> 40 <SEP> mm
<tb> tissue <SEP> of <SEP> polyester / viscose <SEP> no <SEP> treated <SEP>: <SEP> 20 <SEP> mm
<tb> fabric <SEP> of <SEP> polyester / viscose <SEP> treated <SEP>: <SEP> 50 <SEP> mm
<tb> tissue <SEP> in <SEP> acrylic <SEP> (100%) <SEP> no <SEP> treated <SEP>: <SEP> 8 <SEP> mm
<tb> tissue <SEP> in <SEP> acrylic <SEP> (100%) <SEP> treated <SEP>: <SEP> 70 <SEP> mm
<Tb>

After drying, there is therefore a high degree of hydrophilicity of the treated textile supports by means of agents according to the invention. These agents advantageously make it possible to improve the hydrophilicity of the supports very clearly.

 The improvement of the hydrophilic power makes it possible to reduce the surface electrical resistance of the fibers, in particular synthetic fibers. It is thus the improvement of the hydrophilic power of the fabric which could be at the origin of the improvement of the antistatic power.

 Of course, the present invention is not limited to the embodiments described and shown, provided by way of illustrative and non-limiting examples. In particular, the field of application of the present invention is not limited to the field of clothing alone.

Claims (16)

 1. A method of manufacturing a treatment agent, in particular for improving the antistatic power of a textile support, said treatment agent comprising at least one polymer, characterized in that said polymer is produced by reaction of at least one a polyisocyanate and at least one oxyethylenated fatty amine. 2. Method according to claim 1, characterized in that said oxyethylenated fatty amine has the formula

 where - R is a saturated or unsaturated fatty chain, with a number of carbon atoms of between 6 and 40, - x is between 1 and 50 inclusive, - is between 1 and 50 inclusive or for formula

 where - Ri is a saturated or unsaturated fatty chain with a carbon number of between 6 and 40, - R2 is a hydrogen atom (H) or a saturated or unsaturated fatty chain with a number of carbon atoms between 6 and 40, - z is between 1 and 50 inclusive. 3. Method according to claim 2, characterized in that at least one of said fatty chains R, R 1 and R 2 comprises from 2 to 14 carbon atoms. <Desc / Clms Page number 12>  4. Method according to any one of the preceding claims, characterized in that said oxyethylenated amine comprises between 10 and 30 ethylene oxide units. 5. Method according to any one of the preceding claims, characterized in that said polyisocyanate is selected from the group consisting of: - poly (phenylene isocyanate), - triphenyl methane triisocyanate, - polyisocyanates prepared by condensation of a diisocyanate on a polyol under conditions such that there are more than 2 free N = C = O groups, - the polyisocyanates prepared by condensation of a diisocyanate on water with the formation of isocyanurate rings, - the polyisocyanates prepared by condensation of a diisocyanate on water with formation of biuret groups. 6. Process according to any one of the preceding claims, characterized in that said polyisocyanate and said oxyethylenated fatty amine are dosed so that the molar ratio of the OH groups of said oxyethylenated amine and N = C = O of said polyisocyanate. between 0.1 and 10 moles of OH per mole of N = C = O. 7. Process according to claim 6, characterized in that said molar ratio is between 0.5 and 2 moles of OH per mole of -N = C = O. 8. Treatment agent of a textile support, in particular to improve the antistatic and / or hydrophilic, characterized in that it comprises a polymer obtained by a process according to any one of the preceding claims. 9. Treatment agent according to claim 8, characterized in that it has a solids content of 10 to 75% by weight. 10. Treatment agent according to claim 9, characterized in that it has a solids content of between 20 and 30% by weight. <Desc / Clms Page number 13> 11. Process for treating, by impregnation or padding, a textile support to improve its antistatic power, characterized in that it comprises a step of adding to a treatment bath a treatment agent according to the invention. any one of claims 8 to 10 in an amount of between 2.5 and 100 g per liter of said treatment bath. 12. The method of claim 11, characterized in that said amount is between 5 and 75 g per liter of said treatment bath. 13. Process for the treatment, by exhaustion, of a textile support to improve its antistatic power, characterized in that it comprises a step of adding to a treatment bath a treatment agent in accordance with any one of claims 8 to 10 in an amount of between 0.2 and 12%, by weight percentage relative to the mass of the support to be treated. 14. The method of claim 13, characterized in that said amount is between 0.5 and 8% relative to the mass of the support to be treated. 15. Support textile treated, especially to increase the antistatic power, characterized in that it comprises fibers coated with a treating agent according to any one of claims 8 to 10.  16. Textile carrier according to claim 15, characterized in that said fibers are cotton, wool, polyester, nylon, acrylic, or viscose.