CA2046966A1 - Soil-repellent treatment of textile material made of nylon or wool - Google Patents

Abstract

Abstract:

Process for soil-repellent finishing of textile material made of nylon or wool Process for the soil-repellent treatment of textile material made of wool or nylon, which comprises treating the textile material with a condensation product of a bicyclic phenol of the formula 1

Description

HOECHST AKTIENGESELLSCHAFT HOE 90/P 212 Dr. GT/rh Description Soil-repellent treatment of textile material made of nylon or wool Modern carpet finishes contain in the main fluorocarbon resins which confer water- and oil-repellent properties on the material. Such formulations additionally contain a ~oil-repellent component, a stain blocker. Various condensation products of formaldehyde and sulfonated aromatic hydroxy compounds are known for this purpose (EP 242 496, EP 328 822, EP 332 343, US 4 839 212, US 4 822 373). All of these products have in ~ommon that one sulfo group is attached directly to the aromatic ring.

The present invention provides a process for the 80il-repellent treatment of textile material made of nylon or wool, which comprises treating the textile material with a condensation product of a bicyclic phenol of the formula 1 (HO)n ~ ~ ~OH)n~
~ ~ (1) (SO3Me)m (SO3Me)m.

where X is a direct bond or a bridge member of the formula -SOz-, -SO-, -S-, -CH2-, -C(CH3) 2- or -CO-, prefer-ably -SO2-, n and n' are aach 1 or 2, m and m' are each ~, 1 or 2 and 2~ Me i~ hydrogen or an alkali metal, alkaline earth metal or ammonium ion, with formaldehyde and amidosulfuric acid or alkali metal, alkaline earth metal or ammonium salt~
thereof.

In contradistinction to the prior art stain blockers, the - 2 - 20~6~6 condensation products to be used according to the present invention have not only sulfonic acid groups but al80 groups of the formula -CH2NHSO3Me. These condensation products and the preparation thereof are known from DE 25 49 533. This document describes the suitability of these condensation products for use as auxiliaries for improving the wet fastness properties of polyamide dyeings. It does not mention any ~tain blocking effect.

Bicyclic phenols of the formula 1 are dihydroxydiphenyl sulfone, dihydroxydiphenyl sulfoxide, dihydroxydiphenyl sulfide, dihydroxydiphenylmethane, dihydroxydiphenyl-dimethylmethane, dihydroxybenzophenone and dihydroxybi-phenyl, where the hydroxyl groups may be in the 4,4'-, 2,2'- or 4,2~-position, 2,4,2~,4~-tetrahydroxy-diphenyl sulfone, -diphenyl sulfoxide, -diphenyl sulfide, -diphenylmethane,-diphenyldimethylmethane,-benzophenone and -biphenyl, and al~o the derivatives derived therefrom by substitution with ~ulfonic acid group~. Of particular advantage are those bicyclic phenol~ of the formula 1 where X is a bridge member of the formula -S02-. For preparing the condensation products preference is further given to those bicyclic phenols of the formula 1 which contain at least one sulfo group.

Of very high suitability for preparing the condensation products to be u~ed according to the pre~ent invention sre al~o crude reaction products of phenol der~vatives, in particular phenol itself, with sulfuric acid, oleum or sulfur trioxide, which can be sbtained for example as described in Ullmann, volume 13, page 452. These products can be used in~tead of the bicyclic phenol of formula 1 without isolation.

The formaldehyde used for preparing the condensates of the present invention can be used in the form of its aqueous ~olution, preferably a from 30 ~o 39% strength by weight solution. However, instead of formaldehyde it is also possible to use equivalent amounts of those ~ 3 ~ 20469~6 substances which eliminate formaldehyde under the reaction conditions, such as paraformaldehyde, urotropine or trioxymethylene.

To prepare the condensation products to be used according to the present invention, the quantities used of bicyclic phenol and formaldehyde are ~uch that the molar ratio of bicyclic phenol to formaldehyde is between l.OsO.7 and l.Os2.5. The preferred sulfamates are sodium, potassium, calcium and ammonium sulfamate. These sulfamate~, or amidosulfuric acid, are used in such an amount that the molar ratio of bicyclic phenol to these modifiers i8 between 1.0:0.1 and 1.0:1.5.

The resins thus modified additionally contain on the rings of the bicyclic phenol of the formula 1 the group-ing -CH2-NH-SO3Me, formed by reaction of methylol groups in the resin with the modifiers.

The condensation is carried out by heating mixtures of the bicyclic phenol of the formula 1 with formaldehyde or a formaldehyde-donating substance, a modifier, water and, 20 if the setting of a specific pH i~ desired, an acid or a ~ase to temperatures of from about 60 to 140C, prefer-ably from 90 to llO~C, with stirring. The pH of the reaction mixture during the conden~ation time ~hould preferably be between 7 and 11. In another version of 25 this process, it is also possible in addition to pre-condense a mixture of bicyclic phenol and formaldehyde and then in a second step to react this precondensate again with formaldehyde and sulfamate or amidosulfuric acid. The condensation times required depend on the desired degree of conden~ation. The degree of conden~a-tion has a great bearing on the effectiveness of the condensation products. Substantially water-soluble condensation products are obtained after a short condens-ation time. The preferred degree of conden~ation is such that the condensation products have a K value of from 7 to 17 in 5% strength aqueous solution.

~ 4 ~ ~0~6 9 ~ 6 The aqueous 601utions thus obtained can be used directly as stain blockers. However, these aqueous solutions can also be converted first, by drying, into powder form and then these powders can be redissolved in water. The condensation products described can be applied to dyed or undyed, amino-containing substrates such as wool or nylon or blends thereof with other fibers. They can be applied to these substrates alone or together with other water-, oil- and/or soil-repellent products which contain per-fluoroalkyl groups, provided this is permitted by theionic character. The condensation products can be applied by the exhaust method, by padding or by spraying.
They can also be included in the dyebath.

The quantities required to obtain a protective effect on the substrate are between 0.2% and 5%, customarily from 1% to 2.5%, of active substance on weight of fiber.

The condensation products are usually used at a pH
between 2 and 5. If pH 2 is used, the amount of product used can be reduced. The affinity (for the textile material) can also be increased by addinq magnesium sulfate. The products go on readily even at low temper-atures, for example at room temperature. However, a more effective protective effect i8 obtained on increa~ing the bath temperature to 60-80C. For instance, an excellent protective effect i~ obtained by exhaust application tof 0.8% on weight of fiber) at pH 2 and 70C.

Padding must be followed by steaming, before the goodP
are sub~ected to a perfluoro overspray and then dried and/or condensed. An effective protective effect i~
obtained at pH 2 with as little a~ 1% on weight of fiber.

The proces~ described here make~ it possible to obtain the same blocking effect as in conventional processes with smaller amounts of ~tain blocker. The high effi-ciency of application coupled with the high protective ~ 5 - 20~96~
effect and the low yellowing tendency is a significant advantage of the invention.

Application of stain blw kers by the exhaust method (Linitest method) In the exhaust method the stain blockers are applied to hanks of nylon carpet yarn, freed of troublesome spin finish residue~, in an automatic Linitest dyeing machine.
Each hank is put into a separate screw-top stainless steel cylinder together with the finishins liquor. Up to twelve cylinders are held in a frame which rotates in a water bath whose temperature, heating-up rate, dyeing time and cooling time can be controlled automatically.

Typically, the stain blocker~ are applied in a liquor ratio of 20:1 in an amount of 1~ or 2.5~ on weight of lS fiber. The stain blockers are applied at a pH of 2.5, set by adding amido~ulfuric acid. To improve the affinity 2%
of magnesium sulfate on weight of fiber may be added.

After the solutions have been made up they are introduced into the cylinders. The nylon hanks to be treated are slightly wetted with demineralized water and then intro-duced into the cylinders ~o that they are fully immersed in the solutions.

The cylinders are introduced into the dyeing machine at 30-C and left for 5 minutes for conditioning. The water bath is then heated at two degrees per minute to the temperature desired for the application of the stain blocker. Usually the goods are treated at 70C + 2-C in order to ensure that the products go on. Once this temperature is reached, the solutions are left to act on the goods for 20 minutes ~efore being cooled down to 30C.

The treated goods are removed from the cylinders and thoroughly rinsed with cold demineralized water. One 20~69~6 after the other the hanks are each rinsed with fresh water at a liquor ratio of 40:1 at room temperature and squeezed off by hand. The rinsed goods are centrifuged or 6queezed off on a pad-mangle to remove excess liquid.
They are then dried at 90C in a through-circulation drying cabinet for 20 minutes.

The dry samples can then be tested in respect of soiling by the test methods described hereinafter.

Soiling test This test is used for a rapid asses~ment of the stain blocker effect in respect of the staining of carpets with lemonade drinks which contain acid dyes, for example C.I. Acid Red 40. The drinks used for testing, whîch ~180 contain ~ugar, citric acid, aromas, vitamins and mineral~, are commercial products in the form of powder which is dissolved in demineralized water in accordance with the manufacturer~s in~tructions. The dye-containing powder dissolved in this way is used to prepare the dyeing liquors required for staining the finished goods.
The dyeing li~uors contain 90 g of the powder per liter at a pH of about 3.

The staining test is carried out in an automatic Llnitest dyeing mach$ne with up to 12 screw-top stainless steel cylinder~,. The cylinders are each charged with a test specimen and the staining liquor.

The test specimens used are made of nylon 6 SNIA carpet yarn 357. This is a trilobal yarn of thickness 12, set and without prior fluorine treatment. To remove spin finish residues the specimens ~5 g + 0.5 g) which are ~n hank form are washed at a liquor ratio of 40:1 at the boil in the presence of an oleylsarcoside (1 gJl of (R~Arkomon A conc.) for 20 minutes.

This is followed by rinsing with deionized water for 2~6966 about 5 minutes to remove foam, centrifuging or cqueezing off of excess liquid and drying at 90C in a through-circulating drying cabinet for about 20 minutes.

To carry out the tests the goods are thoroughly wetted with water and excess water is removed by centrifuging.
Each stainless steel cylinder is charged with one still moist test specimen and the staining liquor 8c that the goods can be treated at a liquor ratio of 20:1 at 20C i 2C for 30 minutes. All the while the cylinders are held by a frame which i8 rotated in a water bath to guarantee constant ayitation of the liquor.

The stained samples are then rinsed under running cold demineralized water until the rinsing water is no longer colored. The rin~ed goods are centrifuged or squeezed off lS to remove excess liquid and then left at 90C in a through-circulation drying cabinet for 20 minutes.

Not less than an hour later the dye-stained specimens are assessed visually against a standard. The assessment criterion is the depth of staining.

UV yellowing test (Xenote~t) The yellowing tendency of stain blocker-finished matsrial is determined by irradiating the material with W light for 16 hour~. Treated specimens of 12 cm x 4 cm or yarns wound tight over a width of 1 cm are irradiated in a Xenotest 150 S at 30C and 60~ relative humidity while rotating. They are then vi~ually assessed against a corotating standard.

The following Examples will illustrate the process:

- 8 - 2~ ~9 ~ 6 Examples 1. Under N2 the following are introduced in the stated sequence:
125.2 g (0.5 mol) of 4,4~-dihydroxydiphenyl 6ulfone 275 g of demineralized water 60.5 g (0.5 mol) of 33% strength NaOH
25 g (0.25 mol) of 30% strength formaldehyde ~olution and heated to 100C for 2 hours. To this reddish brown clear solution are added after cooling down to room temperature 193.7 g (0.65 mol) of 40% strength sodium sulfamate ~olution, the mixture is heated to 100C, 65.1 g (0.65 mol) of 30% ~trength formaldehyde solu-tion are added dropwise over 3 hours, and the mixture is maintained at that temperature for a further 6 hours. This produces 736.4 g of a brown clear product;
pHs 9.0; solids content: 31.3%; K value: 8.9.

2. A 500 ml stirred autoclave under N2 i8 charged in succession with 125.2 g (0.5 mol) of 4,4'-dihydroxydiphenyl ~ulfone 275 g of demineralized water 63.1 g (0.65 mol) of amidosulfuric acid 139.4 g (1.15 mol) of 33% strength NaOH
90.1 g (0.9 mol) of 30% strength formaldehyde solu-t~on and the contents are heated at 130-135C and 3-6 bar for 1.5 hours. This produces a reddish brown clear liquid. pHs 9.0; solids contents 34.6%; R values 11.4.

3. A 500 ml stirred autoclave under N2 i8 charged with 75.1 g (O.3 mol) of 4,4'-dihydroxydiphenyl sulfone 165 g of demineralized water 37.8 g (0.39 mol) of amidosulfuric acid 83.6 g (0.69 mol) of 33% 6trength NaOH
54.1 g (0.54 mol) of 30% strength formaldehyde solution - 9 - 2~469~6 and the contents are heated at 130-135C and 4 bar for 1 hour. This produces 404 g of a reddish brown clear liquid. pH: 9.0; ~olids content: 36.8%; R value: 7.9.

4. Composition as for Example 3 with a reaction time of 10 hour~ at 110C and 3 bar. 152 g of demineralized water are added. pH: 8.8; solid6 content: 23.8%;
D20 = 1.12; R value: 10.4; iodine color number: 40-60.

5. Composition as for Example 3 with a reaction time of 30 hours at 90C and 5 bar. pH: 9.1; solids content:
36.6%; D20 = 1.20; R value: 13.1; iodine color numbers 90 .

6. A 500 ml stirred autoclave under N2 i8 charg0d with 125.2 g (0.5 mol) of 4,4~-dihydroxydiphenyl sulfone 233 g of demineralized water lS 60.5 g (0.5 mol) of 33~ strength NaOH
55 g (0.55 mol) of 30% strength formaldehyde solution and the contents are heated at 110C for 2 hours.
After cooling down to room temperature 193.7 g (0.65 mol) of 40% strength sodium sulfamate solution are added dropwise, and the mixture is heated to reflux. At that temperature 65.1 g (O.65 mol) of 30~ strength formaldehyde solu-tion are ~dded dropwi~e over 3.5 hours and the mixture i8 refluxed for a further 3.5 hour~. ~his produce~
714 g of a reddiRh brown clear liquid. pHs 9.2; solids contents 33.9~; X values 11.5.

7. A SOO ml stirred autoclave i8 charged under nitrogen in succe~sion with 100.1 g (0.5 mol) of 4,4'-dihydroxyd~phenylmethane 270 g of demineralized water 58.3 g (0.6 mol) of amido~ulfuric acid 133.3 g (1.1 mol) of 33% strength NaOH
90.1 g (O.9 mol) of 30~ strength formaldehyde ~olution lO- 20~6~66 and the contents are heated at 90C for 30 hours. Thi~
produces a clear viscous liquid. pH: 8.9; R value:
10.5.

8. In a 1-1 four-necked flask 225.6 g (2.4 mol) of phenol are melted at 50-60C under a blanket of nitrogen.
Then 117.6 g (1.2 mol) of concentrated sulfuric acid are added dropwise with ~tirring over about 30 min-utea, during which the temperature rises to a maximum of 100C. Then 123 g (1.1 mol) of chlorobenzene are added, and the mixture is boiled under a water separa-tor (internal temperature about 135C), w$th the heavy phase (chlorobenzene) running back into the flask.
After 41 g of water have been distilled off, the mixture is cooled down to 90C, the water sephrator i8 exchanged for a separator for solvents which are heavier than water, the water previously distilled off and a further 100 g of demineralized water are added to the reaction mixture, and the chlorobenzene is separated off by distillation. In the cour~e of the chlorobenzene distillation a further 100 g of deminer-alized water are added. Once all the chlorobenzene has been removed, 100 g of water are also di~tilled off.
The mixture i~ cooled down to 70C and 146 g (1.2 mol) of 33% ~trength sodium hydroxide solution are metered in. Then 108 g (1.08 mol) of 30% ~trength formaldehyde ~olut~on and finally 72 g (0.24 mol) of 40~ ~trength sodium sulf~mate solution are added dropwise. Sub-sequent heating under reflux for 10 hours produce~ a reddish brown viscous liquid.

Application example~

Concerning Example 1 The product thus obtained was applied by the exhaust method at 2.5~ (0.8~ of active substance), on weight of fiber, to nylon carpet yarn as described. The pH was ~et with amidosulfuric acid to 3.5 and 2. On testing the blocking effect it was found that pH 3.5 permits a ~mall amount of staining, pH 2 gives no staining, whl~Q ~9 6 6 treated control material is colored deep red. Specimens treated with this product and exposed to W irradiation in a Xenotest for 16 hours show no yellowing.

Concerning Example 3 The exhaust method was used as described to apply the solution thu~ obtained to nylon carpet yarn at 2.5%
(1% of active substance) on weight of fiber at a pH of 3.5, set with acetic acid. The yarn thus treated was then examined in respect of the protective effect using the method described. The treated hank was only slightly colored, while the untreated control material had deep red color. Specimens which have been treated with this solution and exposed to W irradiation in a Xenotest for 16 hours do not show sny yellowing.

Concerning Example 5 As in the preceding application example, the solution thus obtained was applied by the exhaust method to nylon carpet yarn st 2.5% (1% of active substance) on weight of fiber at a pH of 3.5, set with acetic acid, and was then examined for anti-soil properties. The treated hank was not di~tinctly ~tained while the untreated control material is ~tained deep red. Specimens treated with this solution and then ~ub~ected to W irradiation in a Xenotest for 16 hours do not show any yellowing.

Claims (3)

1. A process for the soil-repellent treatment of textile material made of wool or nylon, which comprises trea-ting the textile material with a condensation product of a bicyclic phenol of the formula 1 (1) (1) where X is a direct bond or a bridge member of the formula -SO2-, -SO-, -S-, -CH2-, -C(CH3)2- or -CO-, preferably -SO2-, n and n' are each 1 or 2, m and m' are each 0, 1 or 2 and Me is hydrogen or an alkali metal, alkaline earth metal or ammonium ion, with formaldehyde and amido-sulfuric acid or alkali metal, alkaline earth metal or ammonium salts thereof.

2. The process of claim 1, wherein the textile material is treated with a condensation product of a bicyclic phenol of the formula 1 where X is a bridge member of the formula -SO2- with formaldehyde and amidosulfuric acid or an alkali metal, alkaline earth metal or ammonium salt thereof.

3. The process of claim 1, wherein from 0.2 to 5% by weight of the condensation product is applied to the textile material.