ITVA20070077A1 - TREATMENT FOR WOOL - Google Patents

Description

Description of the industrial invention entitled:

TREATMENT FOR WOOL

SECTOR OF THE INVENTION

The present invention refers to a treatment for wool, wool fibers or animal hair (hereinafter "wool") to impart dimensional stability, to reduce the formation of pilling and hairiness on its surface and the damage caused by use. and from washes.

According to the present invention, the aforementioned characteristics can be obtained by means of a process which comprises treating the wool with an aqueous solution comprising a cationic polyurethane having filming characteristics and a formulation containing a water-dispersible polyisocyanic crosslinker.

STATE OF THE ART

On most woolen textile materials, before or after weaving or knitting, resins are applied to obtain dimensional stability, to reduce the formation of pitting and to improve durability after washing.

One of the most common methods of increasing the dimensional stability of wool is to combine chlorination and the application of a polymer.

Many resins have been proposed for the above purposes.

For example, the use of a cationic polyurethane as an anti-shrinking agent for keratin fibers is known from JP 2004115950.

WO 0066830 describes the use of aqueous preparations comprising a bisulfite masked polyisocyanic prepolymer for the anti-felting treatment of wool.

US 4,985,040 refers to a treatment for woolen textile material comprising the application of a polyamide-epichlorohydrin resin and a polyurethane.

Additionally, various enzymatic treatments have been used to reduce shrinkage of the wool.

DETAILED DESCRIPTION

The present invention relates to a wool treatment which comprises: i) preparing an aqueous composition containing a cationic polyurethane, a water-dispersible non-ionic non-ionic polyisocyanate and an ethoxylated phosphate alcohol having one or more phosphoric groups in acid form; ii) impregnating the wool with the aqueous composition obtained; iii) drying the wool.

The treatment according to the invention imparts shrinkage resistance and dimensional stability, reduces the formation of pellets and the damage caused by use and washing.

The aqueous composition useful for impregnating the wool typically comprises from 0.5 to 5% of cationic polyurethane, from 0.3 to 3% of non-ionic water-dispersible non-ionic polyisocyanate and from 0.03 to 0.3% of alcohol ethoxylate phosphate. having one or more phosphoric groups in acid form, on the weight of the goods to be treated.

The aqueous composition can advantageously contain from 0.05 to 0.5% of a non-ionic surfactant on the weight of the goods to be treated; preferably the surfactant is an ethoxylated fatty alcohol.

Normally 5 to 100 I of aqueous composition are used per kilogram of wool.

Step ii) takes place immediately after the preparation of the aqueous composition, preferably within eight hours of preparation, since the water-dispersible non-ionic non-ionic polyisocyanate reacts slowly with water even at room temperature.

The wool to be treated can be in the form of combed ribbon, fiber, yarn, fabric or knit.

The treatment of the invention can also be carried out on bows or on garments made of wool.

The best results are obtained by treating the wool in the form of yarn or knit.

When wool in the form of yarn is used as a substrate, the treatment can advantageously be carried out on cones or skeins.

Wool can comprise up to 50% by weight of other fibers, such as viscose, polyester, polyamide fibers.

Impregnation can take place by immersion, spray, roller deposition, and so on.

Preferably, the impregnation of the wool is carried out in the aqueous composition according to the invention at 20-60 ° C, for from 10 to 60 minutes, until exhaustion.

The pH of the aqueous composition during impregnation is adjusted to about 4-6; acetic acid is preferably used to adjust the pH to about 5.

After impregnation, i.e. the saturation of the material, the wool is advantageously centrifuged and dried, in the conditions deemed suitable by the expert in the field.

The cationic polyurethanes suitable for the preparation of the aqueous composition of the invention are commercially available, for example they are marketed by Cesalpinia Chemicals under the brand name Rolflex CN 24. They are normally marketed in the form of aqueous dispersions at 20-40% by weight.

Suitable polyurethanes are those obtained from: a) reaction of one or more organic diisocyanates with a mixture of an alkyldiethanolamine and a substantially linear polyol to obtain a prepolymer having free isocyanic groups; b) cationization of amino groups; c) extension of the cationic polyisocyanate thus obtained with water or amines.

The prepolymer preparation can be carried out using the reagents and molar ratios defined in EP 98752.

Usable cationic polyurethanes normally have a molecular weight of 2,000-100,000 daltons.

As organic diisocyanates, both aromatic, aliphatic and cycloaliphatic diisocyanates can be used; preferably the organic diisocyanates are aliphatic or cycloaliphatic and more preferably they are 4-4 'dicyclohexyl-methane-diisocyanate, 1-isocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane (or isophorondisocyanate), hexamethylene diisocyanate and their mixtures.

The polyols useful for the preparation of the cationic polyurethane of the invention are polyalkylene ether glycols or polyesters polyols. Polyalkylene glycol ethers are preferred,

The most useful polyalkylene ether glycols are those having a molecular weight of from 50 to 5,000 and preferably from about 500 to about 4,000.

Examples of polyalkylene ether glycols are, among others, polypropylene ether glycol, polytetramethylene ether glycol and their mixtures.

Particularly preferred is polytetramethylene ether glycol.

Alkyldiethanolamines useful for the preparation of cationic polyurethane are, for example, methyl-, ethyl-, isopropyl-, n-butyl-, t-butylcyclohexyl-, n-hexyl-diethanoalline and their mixtures.

The cationization is carried out by adding an organic or inorganic acid or by quatification with alkylating agents, as described for example in US 3,480,592 and US 3,388,087.

The extension of the cationic polyurethane obtained from step b) is preferably carried out in water.

The cationic polyurethanes useful for the treatment of the invention are filming polymers, capable of generating a film of medium softness with an elongation at break of between 400 and 1000%, determined according to the ASTM D882-02 method.

In the practice of the invention, a commercially available aqueous dispersion of a polyurethane suitable for the purpose is diluted in water, possibly in the presence of a non-ionic surfactant, and added to the bath where the impregnation takes place (for example in a dyeing machine) .

Subsequently, the water-dispersible non-ionic non-ionic polyisocyanate and the alcohol ethoxylated phosphate in acid form are added to the bath in the form of a previously prepared composition which includes both (Composition II), preferably immediately after it has been diluted with da 2 to 20 parts of water.

Composition II comprises I) from 30 to 99% by weight of one or more non-blocked nonionic water-dispersible polyisocyanates obtained by reaction of polyisocyanates of aliphatic or cycloaliphatic nature containing from 3 to 10 isocyanic groups per molecule with polyols; II) from 1 to 20% by weight, and preferably from 5 to 15% by weight, of one or more ethoxylated phosphate alcohols in acid form III) from 0 to 50% by weight, and preferably from 5 to 30% by weight, of a non-reactive organic solvent miscible with water.

The freshly diluted Composition II can also be added to the aqueous bath before adding the cationic polyurethane; or its individual components I) and II) can be added separately to the bath.

Preferably, the non-ionic water-dispersible non-blocked polyisocyanates are prepared using as polyols 1,3- or 1,2-diols non-ionic containing only one polyethoxylated and / or polypropoxylated alkoxy-terminated chain; said polyols are for example sold by Th. Goldschmidt AG under the brands Tegomer ® D-3403 and Tegomer ® D-3123 ,.

The usable nonionic water-dispersible polyisocyanates contain from 1 to 25% by weight, preferably from 3 to 15% by weight, of polyoxyethylene and / or polyoxypropylene chains deriving from the aforementioned nonionic 1,3-and / or 1,2-diols or other ethoxylated and / or propoxylated alcohols, such as for example the ethoxylated and / or propoxylated derivatives of methanol, nbutanol, cyclohexanol, 3-methyl-3-hydroxymethyloxyethane, ethylene glycol, propylene glycol, glycerol and trimethylolpropane, or mixtures thereof.

Examples of aliphatic or cycloaliphatic polyisocyanates containing from 3 to 10 isocyanic groups that can be used for the preparation of non-ionic water-dispersible non-ionic polyisocyanates are the compounds obtained from the trimerization, biuretization, urethanization or alloophanation of polyisocyanates, such as hexamethylene diisocyanate, phytophorondiisocyanate, 4'-dicyclohexylmethane diisocyanate and their mixtures.

Phosphate ethoxylated alcohols in useful acid form have the following general formula:

wherein R is a saturated or unsaturated, linear or branched alkyl group having from 4 to 20, preferably 12 to 15, carbon atoms, s is a number between 2 and 20, preferably 4 to 10 and t is 1 or 2.

Acid form phosphate ethoxylated alcohols are commercially available.

Composition II can be prepared by adding one or more ethoxylated phosphate alcohols in acid form to a non-ionic water-dispersible non-blocked polyisocyanate, optionally dissolved in a suitable non-reactive solvent, or by preparing the non-ionic water-dispersible non-blocking polyisocyanate in the presence of either plus ethoxylated phosphate alcohols in acid form.

The treatment according to the invention optionally comprises a pre-treatment step with a commercial formulation based on protease, which can be performed on the wool before step i).

The protease-based pre-treatment is carried out at pH about 8 in an aqueous bath containing the protease at 40-60 ° for about 30 minutes.

Protease pretreatment is believed to improve the absorption of polyurethane and Composition II on wool. The best results have been obtained using in the pre-treatment a bath containing Deterlam SI, a formulation based on protease marketed by Lamberti SpA.

EXAMPLE 1

A. Preparation of the cationic polyurethane diluted in water.

600 g DI Rolflex CN 24, a film-forming cationic polyurethane dispersion sold by Cesalpinia Chemicals having an active content equal to 30%, is diluted in 442 g of water containing 20 g of ethoxylated isotridecyl alcohol at room temperature under stirring and then with about 3 parts of water (Composition A).

B. Preparation of the mixture of non-blocked nonionic water-dispersible polyisocyanate and alcohol ethoxylate phosphate in acid form diluted in water.

In a reactor equipped with stirrer, thermometer and coolant, 82.458 g (135 milliequivalents) of Tegomer ® D-3403, ethoxylated diol with a molecular weight equal to 1220 g / mol and 100 g of C12 alcohol are charged in a nitrogen atmosphere at room temperature. -C15 ethoxylate 6 moles phosphate in acid form (% P = 7.1; N ° of acidity = 200-210). The mixture is distilled under vacuum to reduce the residual water content to values below 0.05%, measured by Karl Fisher titration.

At a temperature of 40 ° C in a nitrogen atmosphere, 817.542 g (4406 milliequivalents) of Tolonate® HDT LV2, hexamethylene diisocyanate isocyanation product, having a content of isocyanic groups equal to 23.0 ± 1%, are added under stirring, 100% solid content, marketed by RHODIA.

The mixture is then brought to 90 ° C and kept at a temperature of 85 - 90 ° C for about an hour, until the percentage value of isocyanic groups equal to 18% is reached (determined by titration according to the ASTM D2572 method).

A clear yellow liquid composition is obtained having a Brookfield viscosity at 25 ° C equal to 3200 mPa * s. ; 1600 g of this composition are mixed with 40 g of dipropylene glycoledimethyl ether, marketed by DOW Chemicals as Proglyde® DMM. A composition (Composition II) having a Brookfield viscosity at 25 ° C equal to 550 mPa * s is obtained.

200 g of Composition II are diluted with 2000 g of water at room temperature, obtaining Composition B.

Treatment on hanks.

In an OBEM dyeing cabinet, skeins of wool, title 2/30, previously treated with 55-60% sodium dichloroisocyanurate (Basolan DC, BASF) at 4% on the weight of the goods and dyed with reactive dyes were placed.

Once the machine has been filled with water and the circulation of the pumps has been activated, the pH is adjusted to about 8 using industrial ammonium hydroxide (30%).

Subsequently, through the "expansion tank" placed in recirculation, 4 g / l of Deterlam SI are introduced into the cabinet.

The temperature is raised to 40 ° C and it is treated for 30 minutes. This is followed by a bath drain and thorough rinsing.

When the bath is new, the pH is again adjusted to about 5.

Through the expansion tank, 8% of the weight of the goods of Composition A is added. The product is then loaded into the tank and waits for 5 minutes for it to disperse evenly.

Composition B is then added to the bath, at a rate of 2% on the weight of the goods.

Wait another 5 minutes, then proceed to raise the temperature to 40 ° C and then treat for 40 minutes. Finally the bath is unloaded and the goods, without any rinses, are centrifuged and dried at 80-90 ° C.

With the yarn of the skeins treated in this way, drapes are knitted which are tested according to the IWS TM 31 method, test 5x5 A (simulation of 50 machine washes) and the percentage of the area of the cloth itself is measured.

The total return of the treated material was 1%. The same untreated material has a return of -46% already after 1x5A (10 washes).

Application on spool yarn.

In an OBEM vertical dyeing machine, 100% wool bobbins are placed in the laboratory, pre-treated with 4% Basolan DC and dyed with reactive dyes.

When the bath is new, the pH is adjusted to about 5 again.

Through the expansion tank, 8% of the weight of the goods of Composition A is added. The product is then loaded into the tank and waits for 5 minutes for it to disperse evenly.

Composition B is then added, at a rate of 2% on the weight of the goods.

Wait another 5 minutes, then proceed to raise the temperature to 40 ° C and then treat for 40 minutes.

Finally the bath is unloaded and the goods, without any rinses, are centrifuged and dried at 80-90 ° C.

With the yarn of the packages thus treated, drapes are knitted which are tested according to the IWS TM 31 method, test 5x5 A (simulation of 50 machine washes) and the percentage of the area of the cloth itself is measured.

The total return of the treated material was -17.22% for the yarn outside the package and -14.34% for the yarn inside. The same untreated material has a shrinkage of about -30% already after 1x5A (10 washes).

Application on knitted fabric.

In a laboratory dyeing machine, type linitest, woolen sheets, 2/30 count, previously treated with 2.8% BASOLAN DC and dyed with premetallized dyes, were placed.

Once the machine has been loaded with water and the circulation of the bath activated, the pH is adjusted to about 8 using industrial ammonium hydroxide (30%).

Subsequently, 4 g / l of Deterlam SI are introduced.

The temperature is raised to 40 ° C and it is treated for 30 minutes, followed by a drain of the bath and a thorough rinsing.

When the bath is new, the pH is again adjusted to about 5.

15% of the weight of the composition A product is added. The product is then loaded into the tubs and it is waited for 5 minutes for it to disperse homogeneously.

Composition B is then added, at a rate of 5% on the weight of the goods.

Wait another 5 minutes, then proceed to raise the temperature to 40 ° C and then treat for 40 minutes.

Finally the bath is unloaded and the goods, without any rinses, are centrifuged and dried at 80-90 ° C.

The drapes obtained are tested according to the IWS TM 31 method, test 5x5 A, and have a return of -8.5%

The same untreated material has a shrinkage of about -40% already after 1x5A (10 washes).

Claims (6)

CLAIMS 1. A wool treatment comprising: i) preparing an aqueous composition containing a cationic polyurethane, a water-dispersible non-ionic non-ionic polyisocyanate and an ethoxylated phosphate alcohol having one or more phosphoric groups in acid form; ii) impregnating the wool with the aqueous composition obtained; iii) drying the wool. 2. Treatment for wool according to claim 1 wherein the aqueous composition comprises 0.5 to 5% cationic polyurethane, 0.3 to 3% water-dispersible nonionic non-blocked polyisocyanate and 0.03 to 0.3% of alcohol ethoxylate phosphate having one or more phosphoric groups in acid form, on the weight of the goods to be treated. 3. Treatment for wool according to claim 2 wherein step ii) is carried out at 20-60 ° C, for 10 to 60 minutes, until exhaustion, at a pH of the aqueous composition comprised between 4 and 6. 4. Treatment for wool according to claim 3 wherein the polyurethane is a filming polymer, capable of generating a film with an elongation at break between 400 and 1000% determined according to the ASTM D882-02 method, and is obtained by: a) reaction of one or more organic diisocyanates with a mixture of an alkyldiethanolamine and a substantially linear polyol to obtain a prepolymer having free isocyanic groups; b) cationization of amino groups; c) extension of the cationic polyisocyanate thus obtained with water or amines. A wool treatment according to any one of the preceding claims wherein the non-ionic water-dispersible non-blocked polyisocyanate and the ethoxylated phosphate alcohol in acid form are added to the bath in the form of a composition (Composition II) comprising both. 6. Treatment for wool according to claim 5 wherein Composition II comprises I) from 30 to 99% by weight of one or more water-dispersible nonionic non-blocked polyisocyanates obtained by reaction of aliphatic or cycloaliphatic polyisocyanates containing from 3 to 10 groups isocyanic per molecule with polyols; II) from 1 to 20% by weight, and preferably from 5 to 15% by weight, of one or more ethoxylated phosphate alcohols in acid form III) from 0 to 50% by weight, and preferably from 5 to 30% by weight, of a non-reactive organic solvent miscible with water.