PT1957705E - Process for finishing textiles - Google Patents

Description

ΡΕ1957705 1

DESCRIPTION " PROCESS FOR TEXTEIS FINISHING " The present invention relates to a process for the finishing of a cellulose-based textile as well as to a finished cellulose-based textile in accordance with this process.

Textile cross-linking finishes are currently used to give cellulose fabrics permanent ironing properties and resistance to wrinkling or crease recovery, dimensional stability to household washes, as well as ease of maintenance (easy ironing or ironing) among other properties. Most of these crosslinking textile finishes contain free or combined formaldehyde, which is released either in the finishing shop or when finished fabrics are used in this manner. However, formaldehyde is now considered to be a harmful product, the exposure rates of which are limited to very low levels by certain national regulations.

US Pat. No. 3,304,312 discloses 4,5-dihydroxy or 4,5-dialkoxy derivatives of 2-imidazolidinones as non-formaldehyde textile finishing agents 2 ΡΕ1957705 suitable for imparting resistance to wrinkling. The impregnated material is subjected to drying and curing operations at a temperature within the range of 82 ° C to 232 ° C.

These compounds are widely used in Finishing-Drying and Hardening, or Filling-Drying-Hardening finishing processes, in which a cellulose-containing fabric is impregnated with a bath containing this non-formaldehyde crosslinking agent, a catalyst and additives. The impregnated fabric is dried and hardened at elevated temperatures; the drying and hardening steps may be consecutive or simultaneous. In cases where the fabric is first dried, set temperatures are set at 120 ° C to 230 ° C (US 4,295,846).

Unfortunately, fabrics finished in accordance with this prior art have low tear strength, show a strong tendency to yellow, and may give an unpleasant smell to the amine.

In addition to the ease of maintaining properties of the finished fabrics, it is possible to increase the concentration of these non-formaldehyde crosslinking agents, but at the expense of whiteness and tear strength. The malodor the amine is also potentiated. It is known to the artisan, as described in Textile Chemist and Colorist 1982 (Cooke et al. (14 (5), 3 ΡΕ1957705 100-106, 1982), that the required acidity conditions (pH 3 to 5) catalyze the etherification of the cellulose, but also cause an undesirable side reaction where dialkylhydantoins are formed, thereby reducing the efficiency of the crosslinking agent (resin attachment degrees of between 50 and 70% are generally observed).

Surprisingly, it has now been discovered that non-formaldehyde crosslinking agents under extreme acidity conditions can be applied to a cellulose-based fabric in a wet hardening process (a combination of impregnation, padding, soft drying, low temperature hardening and washing ) to provide good maintainability properties. The finished fabrics in accordance with this invention have an excellent level of whiteness, a very high tear resistance, and no unpleasant smell to the amine.

This invention provides a free-formaldehyde crosslinking finishing process for cellulosic fabrics or cellulose-containing fabrics.

The compounds used in this invention have the general formula (I)

X

Rb OR4

4 ΡΕ1957705

Both the cis and trans isomer, or mixtures thereof, wherein X is O or S, preferably 0, R 1, R 2 are identical or different and are a linear or branched C 1 -C 20 alkyl, preferably a straight or branched C 2 -C 20 alkyl, preferably a C 1 -C 8 alkyl, substituted by one or more functional groups such as hydroxyl, amino, carboxyl, amide, ester, (R 3 and R 4 may form part of the same cyclic structure): and are H or a linear or branched C 1 -C 20 alkyl, preferably C 1 -C 20 alkyl, Optionally substituted by one or more functional groups such as hydroxyl, amino, carboxyl, amide, ester, ether, and halogen (fluorine, chlorine, bromine and iodine) or groups such as 5 ΡΕ1957705 n is 1 to 20, preferably 1 to 6, more preferably 2, and R 5 is H or a linear C 1 -C 4 alkyl or ram preferably H.

Most preferably, R1 and R2 are methyl and R3 and R4 are H or methyl or - (CH2) 20H.

Preferred compounds of the invention are 1,3-dimethyl-4,5-dihydroxy-2-imidazolidinone (also called DMeD-HEU, DiMetili-HydroxyethyleneUne) and their etherified derivatives. To partially or completely etherify DMeD-HEU, the preferred alcohols are methanol or DEG (diethyleneglycol), or mixtures thereof.

These products are generally marketed and sold, for example under the trade name Arkofix NZF New (Clariant), or may be prepared by various techniques known to the person skilled in the art as described, among other possible processes, in US 3 304 312 , US 4 295 846, EP 0 141 755, or US 5 707 404. The process is generally a condensation of glyoxal and disubstituted urea, followed or not by an etherification step with one or more alcohol or polyol.

The process of this invention is characterized by the following steps: a) impregnation of a cellulose-containing tissue with a bath containing a non-formaldehyde crosslinking agent of formula (I) and a catalyst or a mixture of catalysts in (b) drying at a temperature of from 130 ° C or lower to a residual moisture of from 3 to 30%, and (c) drying at a temperature of 50 ° C or lower.

Thereafter, the fabric is washed, neutralized and dried by means of operations known in the art.

Optionally, an additional top finishing step may complete the present process.

Detailed description of the invention

A cellulose-containing fabric is impregnated with a bath containing a non-formaldehyde crosslinking agent of formula (I) and a catalyst, or a mixture of catalysts. The concentration of the finishing agent of formula (I) in the bath, calculated as solid, is generally governed by the desired effect. As a rule, there is between 30 and 500 g / l, preferably between 100 and 300 g / l, more preferably between 120 and 240 g / l. 7 ΡΕ1957705

Suitable catalysts for this process are a single acid or combinations of organic and inorganic acids or acid donors. Crosslinking of the cellulose is acid catalyzed; the pH of the bath is adjusted to 3 or less, preferably to 2 or less, and most preferably to 0.8-1.5.

Typical catalysts include acids, such as hydrochloric, sulfuric, fluoroboric, phosphoric, nitric, acetic, glycolic, maleic, lactic, citric, tartaric, muriatic and oxalic acids; metal salts, such as magnesium chloride, nitrate, fluoroborate or fluorosilicate; chloride, nitrate, fluoroborate, or zinc fluorosilicate; ammonium chloride; zirconium oxychloride; potassium or sodium bisulfate; amine hydrochlorides, such as 2-amino-2-methyl-1-propanol hydrochloride; and the like and mixtures thereof. Preferred are hydrochloric acid, sulfuric acid, phosphoric acid or ammonium chloride.

Optionally, additives may be added to the bath. Conventional additives such as wetting agents, lubricants, softeners, bulking agents, water repellents, flame retardants, soil absorption inhibitors, mold inhibitors, wetting agents, fluorescent optical brighteners, antimicrobial, anti-fungal, anti-fungal, insect repellents, anti-dust mites, anti-mold), and the like can be used in the treatment bath in conventional amounts provided that the stability of the bath is compatible with the very low pH range of the invention. These auxiliaries can not, however, interfere with the convenient operation of the finishing resin, can not themselves have a deleterious effect on the fabric, and will desirably be free of formaldehyde. Preferred are wetting agents, lubricants and softeners. The impregnated fabric is dried at a temperature below 130 ° C, preferably below 100 ° C, and more preferably between 60 and 90 ° C to a residual moisture of between 3 and 30%, preferably between 5 and 15% and more preferably between 6 and 10%. The fabric maintained at this moisture, whether wrapped in plastic wrap or by any other means, is hardened at low temperature, below 50øC, preferably below 40øC, to avoid damage to the fibers for 5 to 30 hrs, preferably for 15 to 25 h. During this hardening stage, the fabric is preferably maintained in rotation to prevent migration and excessive local concentration of the catalyst, which could damage the fabric. 9 ΡΕ1957705

Upon curing, the fabric is washed and neutralized with any conventional method generally used by the skilled person. Neutralization can be achieved for example with a base such as caustic soda, or simply by rinsing.

After the wash and neutralization step, the fabric is dried. Optionally, but preferably, the fabric will be subjected to an upper finish with a bath containing additives. This step may be subsequent to drying, or the fabric may be filler after washing in a wet-on-wet process and then dried.

Conventional additives may be used, such as wetting agents, lubricants, softeners, bulking agents, water repellents, flame retardants, soil absorption inhibitors, mold inhibitors, wetting agents, fluorescent optical brighteners, biocides (anti-microbial, anti-bacterial, anti-fungal, anti fungal, insect repellents, anti-dust mites, anti-mold) and the like in the top finishing bath in conventional amounts, provided the bath is stable. However, such auxiliaries can not interfere with the convenient operation of the finishing resin, can not themselves have a deleterious effect on the fabric, and will desirably be free of formaldehyde. 10 ΡΕ1957705

The finished non-formaldehyde fabrics in accordance with the disclosed process have easy-to-maintain properties and, in addition, have improved tear strength, higher whiteness (no yellowing) and do not detract from any unpleasant smell to the amine.

The following examples will explain the present invention in more detail. parameter Permanent Iron AATCC method 124 Tear strength NF G07-149 Tensile strength NF GO7-001

Degree of fixation The degree of fixation is obtained by determining the nitrogen (% of N) of the fabric before and after washing by analyzing the elements.

Degree of fixation = 100 x% of N fabric washed /% of N finished fabric

Example 1:

Wet toughening with a DMeDHEU crosslinking agent 11 ΡΕ1957705

A 100% cotton 1/1 bleached fabric (116 g / m2, 40x27.5 yarn / cm) was impregnated in a bath in accordance with recipe # 1. The material was squeezed to a moisture absorption of 65%, and then dried with hot air at 70 ° C to a residual moisture of 7-8%. The material was wrapped in a plastic bag and allowed to stand at 35 ° C for 24 hours (cure). It was then promptly washed, neutralized, rinsed with water at 30øC for 5 minutes, then squeezed and dried at 120øC. After drying, the material was impregnated and squeezed with recipe A to a moisture absorption of 60%, and dried at 130 ° C (topcoat).

Comparative Example 1:

Drying-cure-drying air with a drying agent

DMeDHEU-based crosslinking The fabric of Example 1 is impregnated into a bath in accordance with recipe # 2. The material was squeezed to a moisture absorption of 65% and then dried and hardened at 150 ° C (effective time at 150 ° C: 60 seconds).

The details of the recipes are shown in Table ΡΕ1957705 12

Table 1

Products / Reagents: 1 A 2 Sandozin MRN liq conc (commercial wetting agent) g / 1 0.3 0.3 0.3 Arkofix NZF New liq (DMeDHEU * commercial crosslinking agent) g / 1 440 440 MCI liq catalyst (commercial organic and organic acid blend) g / l 110 NKD liq catalyst (commercially available magnesium chloride catalyst with organic acid *) g / 1 Sandolube SVN ZP liq (commercial nonionic polyethylene softener *) g / 1 40 20 40 Sandoperm MEW liq (nonionic silicone microemulsion *) g / 1 30 10 30 Sandoperm RPU liq (commercial polyurethane softener *) g / 1 30 bath pH 1.2 4.2 3.9 * provided by Clariant

Results: 0 = untreated tissue ΡΕ1957705 13

Table 2

Example 0 1 ex comp 1 Permanent Ironing (5x washes at 60øC, drum drying) 1.8 3.4 3.2 Tear resistance Elmendorf (weft) cN 1059 1483 958 Tensile strength (tensile) of N 57 , 2 36.4 37.5 Degree of attachment o O - 45 64

These results clearly demonstrate a surprising increase in tear resistance when the fabric is treated by the present wet hardening process.

Example 2:

Wet toughening with a DMeDHEU-based crosslinking agent

A bleached 100% cotton poplin (120 g / m2) was impregnated with a bath in accordance with recipe # 3. The material was squeezed to a moisture absorption of 75%, and then dried with hot air at 90 ° C to a residual moisture of 9%. The material was wrapped in a plastic bag and allowed to stand at 20 ° C for 22 hours. It was then promptly rinsed, neutralized with caustic soda, rinsed with water for 10 minutes, acidified with acetic acid, rinsed again and then squeezed and dried at 120 ° C. After drying, the material was impregnated and squeezed with recipe B to a moisture absorption of 75%, and dried at 120 ° C.

Comparative Example 2:

Filling-drying-cure with a DMeDHEU-based cross-linking agent The fabric of example 2 is impregnated in a bath in accordance with recipe # 4. The material was squeezed to a moisture absorption of 75% and then dried for 45 seconds at 120 ° C and cured for 30 seconds at 160 ° C.

Comparative Example 3: The finished material of Comparative Example 2 was washed with 1 g / l of a detergent / wetting agent and dispersion for 15 minutes at 45 ° C, then rinsed with water, squeezed and dried for 45 minutes. at 120 ° C.

The details of the recipes are shown in Table 3. ΡΕ1957705 15

Table 3

Products / Revenue: 3 B 4 Sandozin NRW liq conc (commercial wetting agent *) g / 1 0.3 0.3 0.3 Arkofix NZF New liq (DMeDHEU commercial re-agent) g / 1 440 200 Concentrated sulfuric acid c / 11 Catalyst NKD liq (commercial magnesium chloride catalyst *) g / 1 Sandolube SVN liq (commercial non-ionic polyethylene propylene softener *) g / 1 50 50 Ceraperm MW liq nonionic silicone microemulsion *) g / 1 30 30 bath pH 1.1 4.2 3.5 * available from Clariant

Results: 0 = untreated tissue

Table 4

Example 0 2 ex comp 2 ex comp 3 Permanent Ironing (lx washing at 60 ° C, drum drying) 1 3 3.2 Tear resistance -Elmendorf (cn frame 995 1148 802 795 16 ΡΕ1957705 (continued)

Example 0 2 ex comp 2 ex comp 3 Tear strength -Elmendorf (weft) cN 683 694 540 545 Degree of whiteness (CIE) 0 75, 1 77, 8 73.5 74.9 Degree of attachment o 0 48 67

The results clearly show that the present process provides improved textile properties, especially by solving the yellowing problem and the tear resistance being quite better. It may also be noted that the improvement in tear strength and whiteness can not be achieved from an additional washing step after a padding-drying-cure process, but can only be achieved with the present process.

Lisbon, February 14, 2012

Claims (11)

A process for the finishing of textiles comprising the following steps: a) impregnating a tissue containing cellulose under acidic conditions with a bath containing a catalyst or a mixture of catalysts and the cis or trans isomer, or mixtures thereof , of a non-formaldehyde crosslinking agent of formula (I) X in which X is O or S, 12. λ. R 1 and R 2 are identical or different and are a linear or branched C 1 -C 20 alkyl or a linear or branched C 2 -C 20 alkyl substituted by one or more functional groups selected from hydroxy, amino, carboxyl, amide, ester, ether , and halogen, R1, R2 are identical or different and may form part of the same cyclic structure, and are H 2 ΡΕ 1957705 or a linear or branched C 1 -C 20 alkyl, or -H 2 f jn R 5 where n is 1 to 20 , and R 5 is H or a linear or branched C 1 -C 4 alkyl, b) drying at a temperature of 130 ° C or lower to a residual moisture of 3 to 30%, and c) hardening at a temperature of 50 ° C or lower. A process according to claim 1, in which X is O, R 1, R 2, are the same or different and are straight or branched C 1 -C 8 alkyl or straight or branched C 2 -C 8 alkyl substituted by one or more more functional groups selected from hydroxyl, amino, carboxyl, amide, ester, ether, and halogen, R 3, R 4 are the same or different, and are H or a linear or branched C 1 -C 8 alkyl, or ΡΕ1957705 3 CH3 -CHO • 1 SR5 Jn -H where n is 1 to 6, R5 is H. A process according to claim 2, in which X is O, R1 and CS] are methyl, R3 and R4 are H or -CH2 -CH2 -OH. A process according to claim 3, in which the non-formaldehyde cross-linking agent of formula (I) is 1,3-dimethyl-4,5-dihydroxy-2-imidazolidinone. A process according to any one of the preceding claims, wherein a) impregnation of said cellulose-containing fabric is carried out in a bath containing between 30 and 500 g / l of the non-formaldehyde crosslinking agent of formula (I) and having a pH of less than 3, b) drying is carried out at a temperature below 100øC to a residual moisture of 5 to 15%, c) curing is carried out at a temperature below 40øC for 5 to 30 hours. 4 ΡΕ1957705 A process according to claim 5, wherein a) impregnation of said cellulose-containing fabric is carried out in a bath containing between 10 and 300 g / l of the non-formaldehyde crosslinking agent of formula (I) and having a pH less than 2, b) drying is carried out at a temperature of less than 100 ° C to a residual moisture of 5 to 15%, c) hardening is carried out at a temperature below 40 ° C for 5 to 30 hours. A process according to claim 6, wherein a) impregnation of said cellulose-containing fabric is carried out in a bath containing between 10 and 300 g / l of the non-formaldehyde crosslinking agent of formula (I) and having a pH from 0.8 to 1.5, b) the drying is carried out at a temperature of 60 to 90 ° C to a residual moisture of 6 to 10%, c) the hardening is carried out at a temperature below 40 ° C for 15 minutes. to 25 hours and the tissue is maintained in rotation. 5 ΡΕ1957705 The method of any one of the preceding claims, wherein the fabric is treated with a further topcoat. Process according to any one of the preceding claims, in which the catalyst or mixture of catalysts is selected from hydrochloric acid, sulfuric acid, phosphoric acid or ammonium chloride. A process according to any one of the preceding claims, in which wetting agents, lubricants or softening agents are used for the impregnation bath. Textile obtained by a process according to any one of the preceding claims. Lisbon, February 14, 2012