CA2154670C

CA2154670C - Bis(hydroxyphenil) sulfone resoles as polyamide stain-resists

Info

Publication number: CA2154670C
Application number: CA 2154670
Authority: CA
Inventors: Robert Craig Buck; Engelbert Pechhold; Donald Douglas May
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1993-02-02
Filing date: 1994-02-01
Publication date: 2007-07-31
Anticipated expiration: 2014-02-01
Also published as: US5460891A; JPH08506388A; DE69407169T2; DE69407169D1; AU6089594A; JP3296561B2; AU676272B2; US5447755A; EP0682726B1; CA2154670A1; EP0682726A1; WO1994018378A1

Abstract

Polyamide fibrous substrates which resist staining by acid dyes, and processes for preparing the same which comprise applying a base-catalyzed condensation product formed by the reaction of a bis(hydroxyphenyl)sulfone with formaldehyde to give a product known as a resole. The resulting non-sulfonated, non-carboxylated resole stain-resist agents can be applied at higher pH values than prior art stain-resists which were sulfonated or carboxylated.

Description

TITLE
Bis(Hydroxyphenyl)Sulfone Resoles As PoIvamide Stain-Resists FIELD OF THE INVENTION
The present invention relates to rendering polyamide textile substrates resistant to staining by acid dyes by treatment with bis(hydroxy-phenyl)sulfone/formaldehyde resole condensation products.
BACKGROUND OF THE INVENTION
Polyamide substrates, such as nylon carpeting, upholstery fabric and the like, are subject to staining by a variety of agents, e.g., foods and beverages. Acid dyes are especially troublesome staining agents, e.g. FD&C
Red Dye No. 40, commonly found in soft drink preparations. Various types of treatments have been proposed in the prior art for inhibiting staining of polyamide substrates by acid dyes, including application of stain-resist agents comprising sulfonated phenol-formaldehyde condensates, alone, or in combination with hydrolyzed maleic anhydride copolymers or polymers of methacrylic acid, acrylic acid, or itaconic acid, or combinations of sucli stain-resists. In accordance with those prior art treatments, the presence of acid groups, sulfonic acid groups in the sulfonated phenol/formaldehyde condensates and carboxylic acid groups in the foregoing polymers, are necessary in order to impart water-solubility to said condensates and polymers. In addition, it is also reported in the prior art that as the ratio of units containing one -SO3X radical to units containing no -SO3X radicals increases, the product becomes a better stain blocker. Moreover, it has been reported in the prior art that in order to be effective, stain-resists must be applied below pH of 4.5, preferably below 3Ø However, operating at any such low pH has the potential for causing corrosion of equipment as well as safety and environmental problems.
A formaldehyde/naphthol condensate having no carboxylic or sulfonic acid groups and having restraining effects to anionic dyes has been described in the prior art. Testing of the resulting compound, 2,2'-dihydroxy-1,1'-dinaphthylmethane (compound I), by the procedures described in the present specification showed it to be unacceptable as a stain-resist agent for polyamide fibers. On the other hand, base-catalyzed condensation products of a bis(hvdroxy-phenyl)sulfone and formaldehyde have been described in WO 94/18378 ~15070 PCTIUS94/00610 ~

the prior art as melt additives useful in improving the flame retardancy and thermal stability of polyamide fibers.
BRIEF SUMMARY OF THE INVENTION
The present invention -elates to polyamide fibrous substrates which resist staining by acid dyes and to processes for preparing the same.
Such acid dye stain-resistance is imparted to polyamide substrates by applying a base-catalyzed condensation product formed by the reaction of a bis(hydroxyphenyl)sulfone (BHPS) with formaldehyde to give a product known as a resole which contains neither sulfonate nor carboxylate groups.
The non-sulfonated, non-carboxylated stain-resist agents of this invention are less sensitive to the pH at which they are applied to the polyamide substrate than previously known stain-resists which were sulfonated or carboxylated or both. The stain-resists of this invention can be applied at higher pH values than the aforesaid prior art stain-resists, and for that reason those of the present invention are less corrosive and more environmentally suitable.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to the use of water-soluble or water-dispersible base-catalyzed resole condensation products of formaldehyde and BHPS as stain-resists for polyamide fibers and the resulting substrates. The BHPS used in this invention may consist of 4,4'-sulfonyldiphenol or its isomers, such as 2,4'-sulfonyldiphenol, 2,2'-sulfonyldiphenol, etc. or mixtures of the same. The base useful in the condensation and referred to herein may be any inorganic compound with a pKa of 8.5 or greater which when dissolved in water renders it basic and which does not add to formaldehyde; for example, ammonia should not be used. Examples of the base used for the purposes of this invention include but are not limited to alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal borates, alkaline earth metal hydroxides, alkaline earth metal carbonates, alkaline earth metal borates or miatures thereof. The preferred base is sodium or potassium hydroxide, most preferably sodium hydroxide.
The resoles used in this invention are made by the condensation of BHPS with formaldehyde in basic aqueous medium under an inert atmosphere, for safety, at elevated temperature and under autogenous pressure. The molar ratio of formaldehyde to BHPS is in the range between 0.6:1.0 and 4.0:1.0, preferably in the range between 0.6:1.0 and 1.1:1.0, and most preferably in the range between 0.7 and 0.9. The molar ratio of base to ~WO 94/18378 2154670 PCT/US94/00610 BHPS is in the range between 0.1:1.0 and 3.5:1.0, preferably in the range between 0.2:1.0 and 1.0:1Ø
When the formaldehyde to BHPS molar ratio is in the range b2tweer. 0.6:1.0 and 1.1: 1.0, all the base can be added at the start of the reaction and the preferred molar ratio of base to BHPS is in the range = between 0.2:1.0 and 0.8:1Ø Too high or too low a molar ratio of base to BHPS yields a resole product which is incapable of imparting satisfactory acid dye stain-resistance to polyamide substrates. Reaction conditions may vary; i.e. in order to complete the condensation reaction, temperatures should be in the range between 100 and 200 C, and the reaction should be run over a time period of one-quarter hour to twenty four hours.
At formaldehyde to BHPS molar ratios in the range between 1.1:1.0 and 4.0:1.0, it is preferred that the base be added in two stages so as to prevent gellation. It is also preferred that in the range between 0.2 and 0.8 mole of base per mole of BHPS be added at the start of the reaction and that the reaction be run at 80-100 C, preferably 100 C, for 4-12 hours, most preferably at 100 C for 6 hours. After completion of the 4-12 hour reaction time period, additional base is added. The amount of additional base is in the range between 0.4 and 3.3 moles of base per mole of BHPS, preferably 1.0 mole of base per mole of BHPS. The reaction is then heated to a temperature in the range between 100 and 200 C, preferably in the range between 125 and 150 C, over a time period of one-quarter hour to 24 hours, preferably one-quarter to six hours. Reaction times at temperatures greater than 100 C are monitored to prevent product gellation. If the molar ratio of formaldehyde to BHPS is too high without sufficient base present, gellation will occur and if the molar ratio of formaldehyde to BHPS is too low, a significant amount of unreacted BHPS will remain in the product and the reaction can yield a resole product which is incapable of imparting satisfactory acid dye stain-resistance to polyamide substrates. At the end of the condensation reaction, whether one or two stages, the product is cooled to room temperature, and, if necessary, dissolved in sufficient aqueous base to give a translucent brownish solution. Bases suitable for dissolving the resole resins of this invention are the same as those used in the condensation reaction.
Polyamide fiber can be rendered stain-resistant to acid dyes when contacted with aqueous solutions or dispersions of the resole condensates at various pH values with or without electrolytes, and optionally WO 94/18378 PCT/US94/00610=

surfactants, followed by steaming or heating. The resole condensates of this invention can be effectively applied by a wide variety of methods knoNvn to those skilled in the art, such as:
knife over roll overflow applicator (e.g., Kusters Rull), padding, spraying (e.g., Otting Spray Applicator), foaming in conjunction with foaming agents (e.g., KustersFoam Applicator, Kusters Fluicon), batch exhaust in beck dyeing equipment, or continuous exhaust during a continuous dyeing operation (e.g., Kusters Flex-Nip, or Kusters Fluidyer).
The resole condensates of this invention can be applied by the aforesaid methods to dyed or undyed polyamide textile substrates, or to polyamide fiber via a finish during fiber spinning, twisting, or heat setting. In addition, the resole stain-resists of this invention can be applied to such substrates in the absence or presence of fluorinated oil-, water-, and/or soil repellent materials. In the alternative, such a fluorinated material can be applied to the textile substrate before or after application of the resole stain-resists of this invention thereto. The quantities of the resole stain-resists of this invention which are applied to the polyamide fiber or textile substrate, are amounts effective in imparting stain-resistance. For practical reasons, the resoles of this invention are applied to polyamide fiber or fabric at concentrations which are as low as will be suitable for commercial applications. Such concentrations can be readily determined by those skilled in the art by using test methods which are well-known in the art, such as those set forth hereinbelow. For example, the stain-resist can be applied at a concentration in the range between 0.1 and 5.0 % of the resole based on the weight of fiber or fabric (owf), preferably between 0.3 and 2.0 % owf. The bath concentration is adjusted to the desired weight % with water.
In contrast to many prior art stain-resists which require application at a pH below 4 (preferably 3 or lower) in order to impart to polyamide substrates commercially adequate resistance to staining by acid dyes, the resole condensates of the present invention can be applied by any of the techniques described above at a pH between 2 and 9. A surfactant is required for application below pH 6, with more surfactant being necessary at lower pH than at a pH approaching 6. The amount of surfactant is that necessary to provide a homogeneous stable aqueous dispersion of the stain-'~o WO 94/18378 2~.546 PCT/US94/00610 resist or blend of stain-resist. Thus the required amount can be determined by one skilled in the art by observing the aqueous system in which it is used.
For example, one can use an alkylated disulfonated diphenyl oxide (such as that sold by Dow Chemical Co. undei the trademark Dowfax, by Pilot 5 Chemical Co. under the trademark Calfax and by American Cyanamid Co.
under the trademark Aerosol DPOS), alpha-olefin sulfonates (such as that sold by Pilot Chemical Co. under the trademark Calsoft) or sodium lauryl sulfates (such as those sold by Witco Chemical Co. under the trademark Duponol WAQE), usually in quantities in the range between 0.1% and 10%
owf, preferably between 1% and 5% owf. Acid dye stain-resistance is enhanced by the use of electrolytes, usually at concentrations in the range between 2.5 and 500% based on the weight of resole condensate, preferably between 50 and 250%. The electrolyte can be any water-soluble compound which contains a monovalent or polyvalent cation or anion. Monovalent cations such as ammonium, lithium, sodium, potassium are preferred below pH 5.5. Polyvalent cations include barium, calcium, magnesium, strontium, aluminum, zinc, etc. Monovalent or polyvalent anions can be used in this invention, such as fluoride, chloride, bromide, iodide, hypochloride, chlorate, bromate, iodate, carbonate, bicarbonate, sulfate, sulfite, bisulfite, thiosulfite, thiosulfate, nitrate, nitrite, phosphate, hypophosphate, monohydrogen phosphate, dihydrogen phosphate, pyrophosphate, tripolyphosphate, polyphosphate, borate, silicate, metasilicate, cyanate, thiocyanate, formate, acetate, propionate, oxalate, tartrate, citrate, glycolate, thioglycolate, tetraborate, dithionate, etc. Exhaust or fixation the resole condensate can be accomplished at bath or solution temperatures ranging from 20 to 95 C over a few seconds to one hour, preferably 50 to 80 C.
The following examples are given in further illustration of the invention but not by way of limitation. The kinematic viscosity of the resole stain-resists was determined at 10 weight % and pH 9 at 25 C according to ASTM 446 using a Cannon-Fenske glass capillary.

Into a 100 m1316 stainless steel shaker tube was charged 16.7 g (67 mmols), of 98% 4,4'-sulfonyldiphenol, 4.05 g (50 mmols) of 37% aqueous formaldehyde, and 1.78 g (13 mmols) of 30 weight % sodium hydroxide in 40 ml of deionized water. The air was replaced by nitrogen before closing the tube. The reactants were then heated to 150 C with shaking and held for 24 hours at this temperature under autogenous pressure. The tube was then WO 94/18378 ~ I a- 4 6 ~ ~ PCT/US94/00610=

cooled to room temperature and discharged after release of pressure. The grayish solid dispersed product was dissolved with 10 weight % sodium hydroxide to a tannish solution containing 13 weight % of BHPS resole condensate The kinematic viscosity of a 10 weight % solution adjusted to a pH value of 9.0 measured at 25 C was 1.38 centistokes.
EXAMPLES 2- 8 & CONTROLS A-C
The resole condensate resins of Examples 2 through 8 and Controls A-C were prepared in a manner similar to Example 1 as described in Table 1.

Mols per Mol BHPS Temp. Viscosity Example Formaldehyde NaOH Hrs. C Centistokes 1 0.75 0.2 24 150 1.38 2 0.75 0.6 24 150 1.42 3 0.75 0.8 24 150 4 0.9 0.4 24 150 1.59 5 1.0 0.4 24 150 2.01 6 1.1 0.4 24 150 59.85 7 0.75 0.4 12 160 1.47 8 0.75 0.4 6 170 1.42 Control A 0.75 0.0 24 150 Control B 0.5 0.4 24 150 1.05 Control C 1.2 0.4 24 150 gelled Into a 400 ml stainless steel shaker tube was charged 83.4 g (0.33 mol) of a BHPS consisting of 90 weight % 4,4'-sulfonyldiphenol and approximately 10 weight % 2,4'-sulfonyldiphenol, 20.25 g (0.25 mol) of 37 weight % aqueous formaldehyde, 18.0 g (0.13 mol) of 30 weight % sodium hydroxide in 200 ml deionized water. After replacing the air with nitrogen the tube was closed and heated with shaking for 24 hours at 150 C. The tube was then cooled to room temperature and discharged after release of pressure to give a grayish solid after filtration. This product was dissolved with 10 weight % sodium hydroxide to a tannish solution containing 19.8 weight % of BHPS resole condensate. The kinematic viscosity of a 10 weight % solution adjusted to a pH value of 9.0 measured at 25 C was 1.66 centistokes.

J =

Into a reaction flask equipped with a condenser, mechanical agitator and thermometer was charged 33.3 g (133 mmols) of 98 weight ic 4,4'-sulfonvldiphenol, 7.57 g (93 mmols) of 37 weight % aqueous formaldehyde, 7.2 g (54 mmols) of 30 weight % sodium hydroxide and 80 g of deionized water. The reactants were refluxed under agitation and nitrogen for 24 hours. The resole condensate product was then cooled to room temperature, and enough 10 weight % sodium hydroxide was added to give a clear, tannish colored solution. The kinematic viscosity of a 10 weight % solution adjusted to a pH value of 9.0 and measured at 25 C was 1.45 centistokes.
EXAMPLES 11-14 & CONTROLS D & E
The resole condensate resins of Examples 11 through 14 and Controls D and E were prepared in a manner similar to Example 10 as described in Table 2.

Mols per Mol BHPS Temp. Viscosity Example Formaldehyde NaOH Hrs. C Centistokes 9 0.76 0.4 24 150 1.66 10 0.7 0.4 24 100 1.45 11 0.75 0.4 24 100 1_51 12 0.9 0.4 24 100 1.60 13 1.0 0.4 24 100 2:26 14 1.1 0.4 24 100 5.74 Control D 0.5 0.4 24 100 0.96 Control E 1.2 0.4 24 100 gelled Into a one-gallon stirred autoclave was charged 202.5 g (2.5 mols), of 37 weight % aqueous formaldehyde, 834.0 g (3.34 mols) of BHPS
consisting of 95 weight % 4,4'-sulfonyldiphenol and 5 weight % 2,4- .
sulfonyldiphenol, 180 g (1.35 mols) of 30 weight % sodium hydroxide and 2000 g of water. The autoclave was sealed, swept with nitrogen and heated for 24 hours at 150 C. The reaction mixture was allowed to cool to about 70 C before the addition of 300 g of 30 weight % sodium hydroxide.
After stirri.ng for 90 minutes, the reaction product was discharged as a translucent, homogeneous, amber colored liquid containing approximately 24.7 weight % of BHPS condensates.

AMENDED SHEET

~WO 94/18378 2154670 The kinematic viscosity of a 10 weight % solution adjusted to a pH value of 9.0 measured at 25 C was 1.52 centistokes.

Into a reaction flask fitteu with condenser, magnetic stirrer and 5 thermocouple was charged 30 g (120 mmol) of 99.5 weight % 4,4'-sulfonyldiphenol, 15 g (185 mmol) of 37 weight % aqueous formaldehyde, 4 g (50 mmol) of 50 weight % sodium hydroxide 2 g (10 mmol) sodium tetraborate hydrate and 155 g of deionized water. The contents were refluxed under agitation for 4 hours. Upon completion of reflux, the clear solution was heated to 125 C or 4 hours in a stainless steel autoclave to give a yellow-brown viscous liquid.

Into a reaction flask fitted with condenser, magnetic stirrer and thermocouple was charged 20 g (80 mmol) of 99.5 weight % 4,4'-sulfonyldiphenol, 10.5 g (130 mmol) of 37 weight % aqueous formaldehyde, 2.5 g (30 mmol) of 50 weight % sodium hydroxide and 65 g of deionized water. The contents were refluxed under agitation for 6 hours and an additional 5 g (60 mmol) of 50 weight percent sodium hydroxide was added.
The resulting mixture was heated for 16 additional hours at 100 C. After this time, the amber colored liquid solution was used as a stain resist agent.

Into a reaction flask fitted with condenser, magnetic stirrer and thermocouple was charged 20 g (80 mmol) of 99.5 eight % 4,4'-sulfonyldiphenol, 12 g (148 mmol) of 37 weight % aqueous formaldehyde, 2.5 g (30 mmol) of 50 weight % sodium hydroxide and 65 g of deionized water.
The contents were refluxed under agitation for 6 hours and an additional 10 g (120 mmol) of 50 weight percent sodium hydroxide was added. The resulting mixture was heated for 16 additional hours at 100 C. After this time the amber colored liquid solution was used as a stain resist agent.
3 o EXAMPLE 19 Into a reaction flask fitted with condenser, magnetic stirrer and thermocouple was charged 20 g (80 mmol) of 99.5 weight % 4,4'-sulfonyldiphenol, 6 g (74 mmol) of 37 weight % aqueous formaldehyde, 2.7 g (32 mmol) of sodium bicarbonate and 70 g of deionized water. The contents were refluxed under agitation for 24 hours. After this time, the amber colored liquid solution was used as a stain resist agent.

."E f OA 1 cJ ~ ~ -~õ~t~;..i Vfl = WO 94/18378 ~ ~ ~ ~ ~ ~ ~ PCT/US94/00610 Into a reaction flask fitted with condenser, magnetic stirrer and thermocouple was charged 20 g (80 mmol) of 99.5 weight % 4,4'-sulfor_yldiplIenol, 6 g (74 mmol) of 37 weight % aqueous formaldehyde, 11 g (40 mmol) of 50 percent aqueous sodium carbonate and 60 g of deionized water. The contents were refluxed under agitation for 24 hours. After this time, the amber colored liquid solution was used as a stain resist agent.
EVALUATION METHOD I
Nylon fiber was treated with 1.2 % owf resole condensate stain-resist at a goods-to-liquor ratio of 1:32 at the desired pH value for 45 minutes at 60, 70, or 80 C in the presence or absence of 0.5-1.0 % on the weight of the bath (owb) electrolytes such as sodium chloride or sodium sulfate. In some instances 0.1 to 5% owf of a commercial alkylated disulfonated diphenyl oxide surfactant ('Dowfax" 2A-4, Dow Chemical Co.) was added to the treatment bath. The fiber was then washed with water, air-dried and exposed at room temperature to a dye solution consisting of 0.2 g of FD&C Red Dye No. 40 and 3.2 g of citric acid in one liter of deionized water at a goods-to-liquor ratio of 1:40. After approximately 65 hours, the dye adsorbed onto the fiber was determined at a wavelength of 498-502 nm by comparing the absorbance with that of a control. Thus a % dye absorbed number of 90 means 90 % of the dye is adsorbed, indicating little stain-resistance to the dye. The lower the number, the better is the resistance to stain. The results of the evaluations are set forth in Tables 3, 4, 5, 6 and 7.

WO 94/18378 PCT/US94/00610=
~y 10 '" 2 ~.5TABLE3 % DYE ABSORBED

EXAMPLE pH 6.0-6.21 DH 7.8-8.0 2 69 2 =

4 _2 4 16 15.8 39.4 17 2.5 5.6 18 0.88 2.6 19 0.72 2.4 20 0.68 2.8 Control A 93 88 Control B 87 94 Control D 85 89 Control F3 75 75 1Treatment bath cloudy.
2Not run.
32,2'-dihydroxy-1,1'-dinaphthylmethane.

~WO 94/18378 2 154 GPCT/US94/00610 '~

'T'ABLE 4 Effect of ,pH Surfactant and Electrolyte on Stain Resistance (Nylon 6/6 treated with 1.2% OWF of Example 15 at 80 C, 45 min.) j?H DOWFAX 2A44 Sodium Sulfate Jo OWB % Dve Absorbed 2.0 No 0 12 = 2.0 Yes 0 4 2.5 No 0 21 2.5 Yes 0 11 2.5 Yes 0.2 3 2.5 No 0.2 13 3.5 No 0 44 3.5 Yes 0 26 3.5 Yes 0.2 3 3.5 No 0.2 9 4.5 No 0 59 4.5 Yes 0 30 4.5 Yes 0.2 2 4.5 No 0.2 27 5.5 No 0 20 5.5 Yes 0 10 5.5 Yes 0.6 2 5.5 No 0.6 34 6.5 No 0 7 6.5 Yes 0 5 6.5 Yes 0.6 1 6.5 No 1.0 2 7.5 No 0 15 7.5 Yes 1.0 1 7.5 No 1.0 1 .

4Dodecyl diphenylether sulfonate surfactant.

Effect of Electrolvtes on Stain Resistance Nylon 6/6 treated at 1.2% OWF of Example 15 at 80 C, 45 min % Dye Absorbed DOWFAX No 0.2% 0.2% 0.2% 0.2% 0.2% 0.01% 0.01%
-pH 2A4 Electrol3ie NHq Cl LiCl NaC1 KCI Na2S04 CaCl MgSQ_4 2.5 Yes 11 1 0 1 1 3.5 Yes 26 1 0 1 1 3 9 8 4.5 Yes 30 1 0 1 1 1 13 11 1 o 5.5 Yes 10 NM NM 1 NM 2 NM 05 6.5 Yes 5 NM NM NM NM 1 NM 05 6.5 No 7 NM NM 1 1 1 NM NM
7.5 Yes 15 NM NM NM NM 1 NM 15 7.5 No NM NM NM NM NM 1 NM NM
NM = not measured.

50.07%OWB.

~WO 94/18378 2~ ~ ~ 670 PCT/US94/00610 Effect of Treatment Temperature on Stain Resistance Nylon 6/6 treated with 1.2% OWF of Example 9 resole condensate and 1.0% OWB Sodium Sulfate Electrolyte % Dye RH Temp. Dowfax 2A4 Absorbed 6.5 60 Yes 3 6.5 60 No 3 7.5 60 Yes 2 7.5 60 No 3 6.5 70 Yes 4 6.5 70 No 10 7.5 70 Yes 2 7.5 70 No 0 EVALUATION METHOD II
The BHPS condensate prepared according to Example 15 was exhaust applied using a Launder-O-Meter onto 40 oz./sq. yd. carpet from Du Pont Antron nylon 1150 bulk-continuous filament two-ply 3.75x3.75 twist, Superba heat set fiber using a 20:1 liquor-to-goods ratio. A Launder-O-2 o Meter is an automated dyeing machine. The carpet sample is contained in each of several (up to twenty), 500 ml, stainless steel, screw-cap canisters.
The canisters are held in a rack that rotates in a water bath whose temperature is automatically controlled for rate of heating, time at temperature, and cooling. Treatment bath temperature as well as electrolyte concentration were varied. After heat-treating for 20 minutes, the carpet samples were rinsed with water and the excess liquid removed by centrifugation. The samples were then oven-dried for 30 minutes at 90 C and stain tested according to the procedure listed below. Results are given in Table 7.
STAIN TEST
The carpet specimen (approximately 3x5 inch) is placed on a flat non-absorbent surface. Twenty ml of a red dye solution consisting of 0.2 g FD&C Red No. 40 and 3.2 g citric acid in one liter of deionized water is poured into a 5 cm diameter cylinder which is placed tightly over the specimen. The cylinder is removed after all the red dye solution has been absorbed. The stained carpet specimen is left undisturbed for 24 hours, after which it is rinsed thoroughly under cold tap water and squeezed dry. The WO 94/18378 2 la 4 670 PCT/US94/00610 specimens are visually inspected and the amount of color remaining in the stained area rated according to the following stain rating scale:
= no staining 4 = slight staining 5 3 = noticeable staining 2 = considerable staining 1 = heavy staining Thus a stain rating of 5 is excellent, showing outstanding stain-resistance, whereas 1 is the worst rating, comparable to an untreated control sample.
SHAMPOO-WASH DURABILITY TEST
A treated carpet specimen (approximately 3x5 inch) is submerged for 5 minutes at room temperature in a detergent solution consisting of sodium lauryl sulfate (dodecyl sodium sulfate) such as 'Duponol WAQE" (1.5 g per liter) and adjusted with dilute sodium carbonate to a pH
value of 10. The specimen is then removed, rinsed thoroughly under tap water, de-watered by squeezing, and air-dried. The dry carpet specimen is then tested according to the stain test described above.

Stain-Resistance of Launder-o-Meter Treated Nylon 6/6 Carpet Temp. % owb Stain Shampoo Example % A.I.6 Qwf pH C Electrolyte7 Test Test 15 0.4 7.0 66 0.4 3.5 3.0 15 0.4 7.0 66 1.5 4.5 4.0 15 0.6 7.0 66 0.4 4.5 4.0 15 0.4 7.0 77 0.4 4.5 4.0 15 0.4 7.0 85 0.4 5.0 4.5 EVALUATION METHOD III
The BHPS condensate prepared according to Example 15 was applied on a continuous dye range using a Kusters Flex-Nip onto 40 oz/sq.
yd. carpet from Du Pont Antron nylon 1150 bulk-continuous twist, Superba heat set fiber by aqueous bath at 350% wet-pick-up (WPU) followed by heating in a vertical saturated cloud steamer for approximately two minutes.
6Active ingredient, condensate solids.
71.0% owb sodium sulfate.

~WO 94/18378 PCT/US94/00610 The carpet was then washed, vacuum extracted, and dried for approximately fifteen minutes at 250 F in a horizontal electric tenter frame.
The treatment baths were prepared and applied at ambient temperatur: (approximately 20 C) with varying pH and concentration of 5 electrolyte.
Stain resistance was evaluated by exposing 0.5 grams of fiber from the treated carpet to a room temperature solution consisting of 0.2 grams FD&C Red No. 40 and 3.2 grams citric acid in one liter of de-ionized water at a goods to liquor ratio of 1:40. After approximately 24 hours, the 10 dye absorbed by the fiber was determined at a wavelength of 498-502 nm by comparing the absorbance with that of a control. Thus a dye absorption number of 90 means 90% of the dye was absorbed indicating little stain resistance to the dye. The lower the number the better is the resistance to staining. The results of the evaluation are set forth in Tables 8 and 9.

Stain Resistance of Flex-Nip Treated Nylon 6/6 Polyamide Carpets Resole Condensate with Electrolytes grams/liter of application bath % Dye (+ 1%) Example % A.I. OWF 12H Electrolvte Electrolyte Absorbed 15 0.8 7.7 10.0 Na2SO4 0.6 15 0.8 7.6 1.5 Magnaflo8 10.0 Na2S04 1.2 15 0.8 7.4 1.5 Magnaflo 2.0 Na2SO4 1.3 .

8A commercially available, widely used, Mg2+ salt solution sold by Sybron Chemicals Inc.

WO 94/18378 16 PCT/US94/00610io Stain Resistance of Flex-Nip Treated Nylon 6/6 Polyamide Carpets Resole Condensate with Electrolytes and Surfactant9 grams/liter of =
application bath % Dye ( 1%) Example % A.I. OWF pH Electrolyte Electrolyte Absorbed 0.8 6.7 2.0 Na2SO4 0.0 15 0.8 6.2 2.0 Na2SO4 0.0 910% on-weight of condensate Dowfax 2A4 surfactant.

Claims

1. Use of a resole condensate, which is free from sulfonate and carboxylate groups, for imparting to polyamide substrates resistance to staining by acid dyes wherein said resole has been prepared by reacting bis(hydroxy-phenyl)sulfone with formaldehyde in the presence of a base comprising an inorganic compound having a pKa of 8.5 or higher, at a formaldehyde:bis(hydroxyphenyl)sulfone molar ratio in the range between 0.6:1.0 and 4.0:1.0 and a base:bis(hydroxyphenyl)sulfone molar ratio in the range between 0.1:1.0 and 3.5:1Ø

2. The use as claimed in Claim 1 wherein said base is an alkali metal hydroxide, alkali metal carbonate, alkali metal bicarbonate, alkali metal borate, alkaline earth metal hydroxide, alkaline earth metal carbonate, alkaline earth metal borate or mixtures thereof.

3. The use as claimed in Claim 2 wherein said formaldehyde:bis(hydroxyphenyl)sulfone molar ratio is in the range between 0.6:1.0 and 1.1:1Ø

4. The use as claimed in Claim 3 wherein said formaldehyde:bis(hydroxyphenyl)sulfone molar ratio is in the range between 0.7:1.0 and 0.9:1Ø

5. The use as claimed in Claim 2 wherein said base:bis(hydroxyphenyl)sulfone molar ratio is in the range between 0.2:1.0 and 1.0:1Ø

6. The use as claimed in any one of Claims 1 to 5 wherein said bis(hydroxyphenyl)sulfone consists essentially of 4,4'-sulfonyldiphenol.

7. The use as claimed in Claim 2 wherein said resole is prepared by reacting between 0.6 and 1.1 moles of formaldehyde per mole of 4,4'-sulfonyl-diphenol in the presence of 0.2 to 1.0 mole of an alkali metal hydroxide per mole of 4,4'-sulfonyldiphenol.

8. The use as claimed in Claim 7 wherein the molar ratio of formaldehyde to bis(hydroxyphenyl)sulfone is in the range between 0.7:1.0 and 0.9:1Ø

9. The use as claimed in Claim 7 or Claim 8 wherein said alkali metal hydroxide is sodium hydroxide.

10. A process for providing a polyamide substrate with resistance to staining by acid dyes which comprises applying to said substrate, at a pH in the range between 2 and 9, an effective amount of an aqueous composition comprising a nonsulfonated resole condensate prepared by reacting bis(hydroxyphenyl)sulfone with formaldehyde in the presence of a base comprising an inorganic compound having a pKa of 8.5 or higher, at a formaldehyde:bis(hydroxyphenyl)sulfone molar ratio in the range between 0.6:1.0 and 4.0:1.0 and a base:bis(hydroxy-phenyl)sulfone molar ratio in the range between 0.1:1.0 and 3.5:1Ø

11. The process of Claim 10 wherein said base is an alkali metal hydroxide, alkali metal carbonate, alkali metal bicarbonate, alkali metal borate, alkaline earth metal hydroxide, alkaline earth metal carbonate, alkaline earth metal borate or mixtures thereof.

12. The process of Claim 11 wherein said formaldehyde:bis(hydroxyphenyl)sulfone molar ratio is in the range between 0.6:1.0 and 1.1:1Ø

13. The process of Claim 11 wherein said formaldehyde:bis(hydroxyphenyl)sulfone molar ratio is in the range between 0.7:1.0 and 0.9:1Ø

14 The process of Claim 11 wherein said base:bis(hydroxyphenyl)sulfone molar ratio is in the range between 0.2:1.0 and 1.0:1Ø

15. The process of either Claim 10, 11, 12, 13, or 14, wherein said aqueous composition contains an electrolyte comprising a water-soluble compound which contains a monovalent or polyvalent cation or anion.

16. The process of Claim 15 wherein said bis(hydroxyphenyl)sulfone consists essentially of 4,4'-sulfonyldiphenol.

17. The process of Claim 11 wherein said resole is prepared by reacting between 0.6 and 1.1 moles of formaldehyde per mole of 4,4'-sulfonyl-diphenol in the presence of 0.2 to 1.0 mole of an alkali metal hydroxide per mole of 4,4'-sulfonyl-diphenol.

18. The process of Claim 17 wherein the molar ratio of formaldehyde to 4,4'-sulfonyldiphenol is in the range between 0.7:1.0 and 0.9:1Ø

19. The process of Claim 17 or 18 wherein said alkali metal hydroxide is sodium hydroxide.