AU618533B2 - Method to enhance stain resistance of carpet fibers - Google Patents

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AU-AI-17019/88 PCT WORLD INTELL A OPIA O I NIZPN INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 (11) International Publication Number: WO 89/ 02949 D06M 15/41 Al (43) International Publication Date: 6 April 1989 (06.04.89) (21) International Application Number: PCT/US88/01112 (74) Agent: WINTER, Richard, Allied-Signal Inc., Law Department McNally), P.O. Box 2245-R, Morristown, (22) International Filing Date: 6 April 1988 (06.04.88) NJ 07960 (US).

(31) Priority Application Number: 101,65:, (81) Designated States: AT (European patent). AU, BB, BE (European patent), BG, BJ (OAPI patent), BR, CF (OAPI patent), (32) Priority Date: 28 Se.tember 1987 (28.09.87) CG (OAPI patent), CH (European patent), CM (OAP'. patent), DE (European patent), DK, FI, FR (Europearn pa- (33) Priority Country; US tent), GA (OAPI patent), GB (European patent), HU, IT S(European patent), JP, KR. LK, LU (European patent), MC, MG, ML (OAPI patent), MR (OAPI patent), MW, NL (Eu- (71) Applicant: ALLIED-SIGNAL INC. [US/US]; Law Department ropean natent), NO, RO, SD, SE (European patent), SN McNally), P.O. Box 2245-R, Morristowi, NJ 07960 (OAPI p, ent), SU, TD (OAPI patent), TG (OAPI patent).

(US).

(72) Inventors: HANGEY, Dale, Alan 629 Glenmeadow Road, Published Midlothian, VA 23113 HARRIS, Paul, Wesley 2321 With international search report.

Hey Road, Richmond, VA 23224 CORCORAN, Daniel, Joseph, Jr, 912 Westureek Drive, Richmond, VA 23226 FRIEDBERGER, Michael, Philip 1726 Berkeley A O.J. P 1 J U 1389 Avenue, Petersburg, VA 23805 COLE, Charles, Jayroe 11560 Teterling Road, Chester, VA 23831 ARCHIE, William, Alexander 1911 Walker A\enue, Petersburg, VA AUSTRALIAN 23803 SPITZ, Roger, Neil 601 West 113th Strt-a, Apartment 8F, New York, NY 10025 18 APR 199 PATENT OFFICE (54) Title: METHOD TO ENHANCE STAIN RESISTANCE OF CARPET FIBERS (57) Abstract This invention relates to improved methods to enhance stain resistance of dye nylon carpet fiber by a continuous afte"treatment and to two-step processes, either batch-batch, batch-continuous or continuo'us-contiiuous. After preheating with water and extracting to a wet pick-up of between 30 to 190 by weight, sulfonated aromatic condensates which can be combined with filorocarbon compounds for soil resistance, thiocyanates, and/or salts having divalent cations, such as magnesium sulfate, ae applied. Also various dispersing agents, buffering acids and sequestering agents are disclosed.

-1- IMPROVED METHODS AND COMPOSITIONS TO ENHANCE STAIN RESISTANCE OF CARPET FIBERS S bCKGRCUND OF THE INVENTION This invention is related to improved methods and compositions to enhance stain resistance of carpet fibers, Sulfonated aromatic condensates alone in a new process or in combination with other compounds are used to improve stain resistance. Related technology is disclosed in Australian Patent Application No. 77027/87 on sulfonated benzotriazoles and Australian Patent Application No. 78750/87 on sulfonated aromatic formaldehyde condensates, such as diphenyl ether condensates.

The following terms are defined for use in this 15 specification.

0 0 By sulfonated aromatic condensate is meant any condensate of an aromatic compound whether sulfonated prior to or after condensation, particularly sulfonated aromatic formaldehyde condensate effective to enhance stain resistance of fiber or carpet fabric.

By thiocyanate is meant any salt, organic or inorganic, containing a cation and the thiocyanate anion.

By fluorocarbon is meant those fluorocarbon compounds effective to improve the antisoiling properties o. 25 of fiber or carpet fabric, 0 0 By ICP is meant index of crystalline perfection, a measured indication of the internal crystal structure of the polymer is an oriented fiber. High ICP indicates an Sopen crystalline internal structure, easily dyeable polymer fiber.

By nylon is meant the polyamide family of polymers, nylon 6, nylon 6,6, nylon 4, nylon 12 and the other polymers containing the rC-N] structure along with

OH

the [CH2] x chain.

By carpet fabric is meant carpet fiber or yarn which has been typically tufted, woven, or otherwise R' v91 014,dbdat.06,17019.res,1 *T (7 WO 89/02949 PCT/US88/01112 -2constructed into fabric suitable for final use in home furnishings, particularly as floor covering.

By fiber is meant continuous filament of a running or extremely long length or cut or otherwise short fiber known as staple. Carpet yarn may be made of multiple continuous filaments or spun staple fiber, both typically pretextured for increased bulk.

By salt having a divalent cation is meant any such salt effective to enhance stain resistance of fiber, particularly high ICP nylon fiber, when combined with an effective amount of a s.a.c.

By dispersing agent is meant any chemical compound or combination of chemical compounds effective to make stable, relA .ively nonprecipitating, noncoagulating mixtures of ot"r- chemical compounds.

By sequestering agent is meant any chelating agent which is effective in sequestration, which is the suppression of certain properties of a metal without removing it from the system or phase. To be practical, the sequestering agent must not cause any undesirable change that would render the system unsuitable for its intended purpose. Chelation produces sequestration mainly j by reducing the concentration of free metal ion to a very low value by converting most of the metal to a soluble chelate that does not possess the properties to be suppressed.

SA chelating agent is a compound containing donor atoms that can combine by coordinate bonding with a single metal atom to form a cyclic btructure called a chelation J 30 complex or, simply, a chelate. Because the donor atoms are connected intramolecularly by chains of other atoms, a chelate ring is formed for each donor atom after the first which coordinates with the metal. The above is from Volume 5, beginning page 339, of the Kirk-Othmer Encyclopedia of Chemical Technology (John Wiley Sons), 1979, hereby incorporated by reference to p. 367.

It is known to use sulfonated aromatic formaldehyde condensates in the yarn finish (during

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WO 89/02949 PCT/US88/01112 -3or after fiber quenching) to improve stain resistance of carpet fiber, see U.S. 4,590,212, in the dye bath for the same purpose, see U.S. 4,501,591 or incorporated into the fiber for the same purpose, see U.S. 4,579,762. All three above U.S. patents are hereby incorporated by reference, in toto. Use of fluorochemical to improve both stain and soil resistance in combination with s.a.f.c.'s is also taught in U.S. 4,680,212, column 5. Other useful fluorochemicals for antisoiling are taught in commonly assigned U.S. 4,192,754; 4,209,610; 4,414,277; 4,604,316; 4,605,587 all also hereby incorporated by reference, in toto.

It is known to use thiocyanates, such as ammonium thiocyanate, at different process cr .2itions as "assists" during dyeing for various purposes. See U.S.

3,652,199; 3,576,588; 3,387,913; 2,899,262; and 2,615,718 all hereby incorporated by reference, in toto.

Use of salts containing a divalent cation, such as magnesium sulfate, with s.a.f.c.'s to improve wet fastness is known in U.S. 3,790,344, hereby incorporated by reference, in toto. Also see page 48 of a textbook by Rosen, M. Surfactants Interficial Phenomena (Wiley, 1978).

It is also known generally to use acid, including citric acid to buffer a dye bath and to use dispersing agents and/or sequestering agents to stabilize a aqueous formulations of chemicals.

Nylon carpets may be permanently discolored or stained by certain artificial colorants, such as food dyes, or oxidizing agents, such as acne preparations containing benzoyl peroxide. applied to the fiber to provide an ionic barrier to food colorants, make the fiber more stain resistant, but are not effective against oxidizing agents. Furthermore, many of the s.a.c.'s used commercially for the preparation of "stain resistant" carpets are themselves, susceptible to oxYidation upon exposure to light and ozone. This results in a yellowing of the s.a.c. and subsequent destruction.

This has a major impact on the carpet properties. The I WO 89/02949 PCT/US88/01112 -4yellow color of the s.a.c. results in a perceptible shift in the color of the carpet. Destruction of the s.a.c.

results in a loss of the stain resistance properties of the carpet.

Use of fluorocarbon compound treated nylon fiber in carpet fabric inhibits wetting of the fiber surfaces which also inhibits any staining agent from being adsorbed onto or absorbed into the fiber. This surface wetting inhibition can be insufficient when the staining agent is dropped on the carpet with enough force to break the surface energy of the fluorocarbon surface barrier or not cleaned from the carpet and left in contact with fibers for extended time.' Carpet treated with compositions containing s.a.c.'s must not interfere with the antisoiling properties of the fluorocarbon.

Application of s.a.c. to the carpet fabric must be effective, economical, and compatible to both untreated and fluorocarbon treated fiber, and to both continuous dyaing- and. Beck or batch dyeing. The same is true of any s.a.c. application formulation. The s.a.c. formulation must achieve effective penetration into the carpet fabric.

Exhaustion of the individual active chemical components of any s.a.c. formulation must also be effective if not complete.

Certain nylon polymer fibers have very open internal crystal structure, namely high ICP polymer fiber, which require large amounts of s.a.c. to impart an effective degree of stain resistance. High ICP polymers are usually the result of high temperature saturated steam heat setting processes.

Some prior compositions and methods are only marginally acceptable regarding durability of the stain resistance when the carpet is steam cleaned with a detergent at a high pH.

SUMMARY OF THE INVENTION S Thi invention errelated embodiments wherein the Sev s.a.c. application app tarc used In the sever- M2rvv y i .~r 4 The first embodiment of this invention is a method to continuously treat dyed nylon carpet fabric to impart improved resistance to staining comprising preheating said dyed carpet fabric with water at a temperature between 60 and 100 0 C (140 and 212 0 F) to a wet pick-up of from 75% to 200% by weight, and a carpet temperature of between 54.4 and 99 0 C (130 and extracting said water from said carpet fabric to a wet pick-up of between 30% to 190% by weight, then applying an aqueous solution of an effective amount of a sulfonated aromatic condensate to improve stain resistance and an effective amount of a thic.yanate wherein the thiocyanate cation is selected from ammonium, sodium, potassium and zinc to reduce yellowing of the 15 sulfonated aromatic condensate treated carpet, to said carpet fabric at a pH of between 1.5 to 5.5, at a concentration of between 0.25 and 40 grams of solids of said condensate per liter of aqueous solution, at a wet pick-up of between 200 and 650% by weight, at an aqueous 20 solution liquor temperature of between 60 and 100 0 C (140 and 212°F), to achieve a carpet fabric temperature ibetween 54.4 and 99°C (130 and 210'F), then holding said carpet in said aqueous solution for between 0.5 to 90 seconds at a temperature above 54.4°C (130°F).

Vj /A L 91 1O14,ddaL086,17019,res,5

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r 'h "i r u gi Yij -6and 210F), then holding the carpet in the aquus solution for between about 0.5 to 90 secondse t a tem-prature above 54.4 C (130nF) The carpet fabric can subsequently be washed in water. The preferred suifonated aromatic condensate has been condensed with formaldehyde.

The method of extracting can be by applying vacuum to the wet carpet fabric or by squeezing the wet carpet fabric with a pair of rollers. The preferred concentration of the condensate is between about 0.25 and 10 grams per 10 liter of aqueous solution. The preferred wet pick-up of the aqueous solution is between about 300 and 600% by weight. When the aqueous solution is applied by pressurized contact with the carpet fabric, the wet pick-up preferred maximum is 450%. When the aqueous 15 solution is applied by spray, the preferred wet pick-up mimimum is 400%. It is preferred that the carpet fabric be held in the aqueous solution for between about 2 and seconds. The preferred wet pick-up after extracting is between about 50 and 150% by weight. The sulfonated aromatic formaldehyde condensate can be formed by condensation of formaldehyde with one or more phenols. At least one of the phenols can be phenol sulfonic acid or the alkali metal salt thereof. It is preferred that one of the phenols be dihydroxy aromatic diphenylsulfone. It 25 is most preferred that the condensate be formaldehyde condensed with the alkali metal salt of para-phenol sulfoni acid and with 4,4'-diphenylsulfone. The beginning dyed carpet fabric of this process may also comprise an effective amount of a fluorocarbon compound intended to 30 improve resistance to soiling of the carpet. The preferred amount of fluorocarbon present is an amount of from about 0.05 to 0.4% by weight of the fabric. The fluorocarbon can contain perfluoroalkyl radical or can be a mixture of fluorinated pyromellitate oligomers. A more preferred fluorocarbon is a mixture of pyromellitate oligomers formed by two reactions, first, the reaction of pyromellitic dianhydride with the fluorinated alcohol, and second, the reaction product of the first reaction further SUBSTITUTE MHrr-r -7reacted with epichlorohydrin. Another preferred fluorocarbon is a reaction product of a perfluoroalkyl alcohol or amide with a suitable anhydride or isocyanate.

Another more preferred fluorocarbon is a reaction product of N-ethyl perfluoroocyl-sulfoamideo ethanol with toluene diisocyanate. Preferably, the thiocyanate cation is ammonium. The aqueous solution of this method may also contain an effective amount of a dispersing agent. The dispersing agent can be a condensed naphthalenic salt, alkyl sulfosuccinate or mixtures thereof. The preferred dispersing agent is a mixture of a sodium salt of condensed naphthalenic sulfonic acid and di-isobutyl sulfonsuccinate. The aqueous solution of this method may also contain an effective amount of a salt having a 15 divalent cation. The preferred salt is calcium, Smagnesium, zinc, or ferrous chloride, sulfate or phosphate wherein the most preferred is magnesium sulfate. The preferred aqueous solution would contain the combination of a sulfonated aromatic condensate, a 20 salt containing a divalent cation, a thiocyanate, and a dispersing agent, the most preferred combination would be wherein the condensate is formaldehyde condensed with the alkali metal salt of para-phenol sulfonic acid and with 4,4'-diphenol-sulfone, the thiocyanate is ammonium thiocyanate, the divalent cationic salt is magnesium sulfate and the preferred dispersing agents are diisobutyl siulfonsuccinate and the sodium salt of condensed naphthalen. sulfonic acid in a mixture. The preferred carpet fabric would comprise a fiber treated with a fluorocarbon. The fluorocarbon is a mixture of pyromellitate oligomers formed by two reactions, first the reaction of pyromellitic dianhydride with a fluorinated alcohol, second, the reaction product of the first reaction further reacted with epichlorohydrin. The amounts of the fluorocarbon present on the carpet fabric used in the method is an amount 911014,dbdatO86,17019res,7

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i r WO 89/02949 PCT/US88/01112 -8butween about 0.05 and 0.4% by weight of the fabric, the magnesium sulfate can be present in the aqueous solution of the method in an amount between about 0.05 and 0.8% on the weight of the fabric, the ammonium thiocyanate can be present in an amount in about 0.03 to 1% on the weight of the fabric, the sulfonated aromatic condensate can be present in an amount of between about 0.15 and 7.5% on the weight of the fabric, the dialkyl sulfosuccinate can be present in an amount of between 0 and 6 parts by weight to the parts by weight of the sulfonated aromatic condensate and the sodium of the condensed naphthalenic acid can be present in an amount between about 0 and 3 parts by weight to parts by weight of the sulfonated aromatic condensate.

The preferred amounts of the compounds are about 0.05 and 0.4% by weight of the fabric of the fluorocarbon, between about 0.08 and 0.4% on the weight of the fabric of the magnesium sulfate, between 0.15 and 0.7% on the weight oC the fabric of the ammonium thiocyanate and between about 0.15 and 1.5% on the weight of'the fabric of the 20 sulfonated aromatic coddensate with the dialkyl sulfosuccinate being present in an amount between 0 and parts by weight to the parts by weight of the sulfonated aromatic condensate and the sodium salt of the condensed naphthalenic acid being present in an amount between 0 and 2 parts by weight to'parts by weight of the sulfonated aromatic condensate. In order to improve yellowing of the carpet fabric, any of the above aqueous solutions can be buffered with an effective amount of citric acid or any other acid with a sequestering agent.

The preferred aqueous solution is buffered with an amount of citric acid between 0.3 and 5.5 grams per liter of aqueous solution.

A two-step process embodiment of this invention uses the aftertreatment process described above but, preceding the initial preheating step of that aftertreatment an effective amount of the sulfonated aromatic condensate is added during dyeing of the carpet fabric so that the total of effective amounts of sulfonated arotqatic 1 j -I ~i 1 WO 89/02949 PCT/US88/01112 -9condensate in both steps is less than the total effective amount useful in either the first dye step, solely, or in the subsequent application step, solely, or so that a more effective degree of stain resistance of the carpet fabric is achieved at the same total of effective amounts of sulfonated aromatic condensate in the two steps as compared to the same amount in either step solely. An effective amount of the salt having a divalent cation can be added during the dyeing so that the s.a.c. exhausts onto the fiber at the possibly higher pH and so that the stain resistance of the nylon fiber in the carpet fabric, especially an easily dyed nylon fiber having a high index of crystalline perfection and having a very open internal crystal polymer structure, is enhanced and durability steam cleaning of the stain resistance is enhanced, or the effective amount of sulfonated aromatic candensate is lower to achieve the same level of stain resistance. The divalent salt again can be calcium, zinc, magnesium or ferrous sulfate, chloride or phosphate. The preferred salt is'magnesium sulfate. The preferred amounts of sulfonated aromatic condensate added during dyeing and after dyeing are between about 0.05% on the weight of the fiber to 0.5% on the weight of the fiber during dyeing, an additional 0.05% on the weight of the fiber to 7.5% on the weight of the fiber after dyeing. Also, the-preferred amounts of magnesium sulfate are 0.03 to 1% on the weight of the fiber added to the dyebath and 0.05 to 1% on the weight of the fiber added after dyeing. The carpet fabric used in the method can comprise a fluorocarbon present before dyeing. The fluorocarbon again can contain Sperfluoroalkyl radical or a mixture of fluorinated pyromellitic oligomers. The preferred fluorocarbon is a mixture of pyromellitic oligomers formed by two reactions, first, the reaction of pyromellitic dianhydride with a fluorinated alcohol, and second, the reaction product of the first reaction further reacted with epichlorohydrin.

The preceding dyeing step can either be a continuous dyeing operation or it can be batch or beck dyeing. The

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beck dyeing can be done in the presence of an effective amount of a salt having a divalent cation so that the stain resistance of the carpet fabric is enhanced. The preferred amount of magnesium sulfate in the dyebath is an 5 amount between 0.2% on the weight of the fiber to 5.6 on the weight of the fiber.

Another method to improve stain resistance of nylon or wool fiber comprises treating the fiber with a combination of an effective amount of each of a sulfonated aromatic condensate and a thiocyanate, whereby improved resistance to oxidation to ozone or 'by other strong oxidizing agents such as benzoyl peroxide is imparted to the s.a.c. and the dye on the fiber. The preferred fiber is carpet fiber, the preferred aromatic condensate is sulfonatad aromatic formaldehyde condensate formed by condensation with one or more phenols. At least one of the phenols can be a phenol sulfonic acid or the alkali metal salt thereof. Or at least one of the phenols can be a sulfone. The sulfone can be a dihydroxy aromatic diphenolsulfone. The preferred condensate is formaldehyde condensed with a alkali metal salt of para-phenol sulfonic acid and with 4,4'-diphenolsulfone. This method of improving stain resistance of nylon or wool fiber using a thiocyanate with the sulfonated aromatic condensate can use a thiocyanate selected from the group consisting of 0or zl- IC ammonium, sodium, potassium, eE -an, frrou-- -ei--'mehy-nd nd phny thiocyanate, The most preferred is awnonium thiocyanate. The dispersing agent can be added to the mixture applied to the fiber in this method also. The dispersing agent can be selected from the group consisting of condensed naphthalenic salt, an alkyl sulfosuccinate or a mixture thereof. The preferred dispersing agent is a mixture of the sodium salt of condensed naphthalene sulfonic acid and di-isobutyl sulfosuccinate. The preferred amounts used in this method are between about 0.05 and 10% on weight of the fiber of the sulfonated aromatic condensate, between about 0.1 and on weight of the fiber of the thiocyanate and the

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V 89/02949 PCT/US88/01112 -11sodium salt of the condensed naphthalenic sulfonic acid is added in an amount between 0 and 3 parts by weight by parts by weight of the sulfonated aromatic condensate and the di-isobutyl sulfosuccinate is added in amount between 0 and 6 parts by weight to the parts by weight of sulfonated aromatic condensate.

Yet another method of improving stain resistance of nylon fiber, particularly fiber hav, igh index of crystalline perfection, for carpet ccM, treating the fiber with a combination of an effective amount each of a sulfonated aromatic condensate, thiocyanate and salt having a divalent cation. The sulfonated aromatic condensate can be a condensate with formaldehyde, can further be formed by the condensation of formaldehyde with one or more phenols and at least one of the phenols can be phenol sulfonic acid and the alkali metal salt thereof or sulfone. The preferred condensate is formaldehyde condensed with a alkali metal salt of para-phenol sulfonic acid and with 4,4'-diphenolsulfone. The preferred thiocyanate is ammonium thiocyanate but the thiocyanate or 411C e can be ammonium, sodium, potassium, -ep-r-sp4re, rr rw-- -fer-r-ic, methyl--per The preferred salt is magnesium sulfate but the salt can be calcium, magnesium or ferrous chloride, sulfate or phosphate. The fiber treated can comprise an effective amount of the fluorocarbon compound intended to enhance soil resistance of the fiber. The preferred fluorocarbon is a mixture of pyromellitate oligomers formed by two reactions, first the reaction of pyromellitic dianhydride with a fluorinated alcohol and second a reaction piocduct of the first reaction further (d reacted with epichlorohydrin. A dispersing agent cat bh added to the combination used to treat the fiber in thi, method. Dispersing agents can be condensed naphthalenic salt or an alkyl sui~osuccinate or a mixture thereof. The preferred amounts are between 0.15 and 7.5% on weight of the fiber of the sulfonated aromatic condensate between 0.15 and 1% on weight of the fabric of the thiocyanate, between 0.05 and 0.8% on weight of the fabric of the o v r 12divalent cation salt, and between 0.05 and 0.4% on the weight of the fabric of the fluorocarbon present on the fiber before dyeing. As above the condensate and thiocyanate can be buffered with an effective amount of citric acid or any acid with a sequesteriig agent so light induced yellowing of the stain resistant fiber is reduced.

A method of improving light induced yellowing of stain resistant nylon in fiber treated with an effective amount of sulfonatfcd aromatic condensate from an aqueous solution comprises using an effective amount of citric acid or any acid with a sequestering agent to buffer the aqueous solution containing the sulfonated aromatic condensate for treating the fiber at a pH between about 1 >e S• 15 and Another two-step treatment is a method to dye and i treat in two steps (both batch or beck) nylon carpet fabric to impart improved resistance to staining e se comprising dying, in a first step, the undyed carpet fabric in a dye bath liquor in the presence of a portion of an eff tivo amount of a sulfonated aromatic condensate to imprce stain resistance of said carpet in an aqueous solvcion at an elevated temperature, then 25 removing the dye bath liquor frorn the dyed carpet ffabric, then i rinsing the dyed carpet fabric, then applying, in a second step, another portion of an 4 effective amount of the tlfonated aromatic condensate to improve stain resistance of said carpet and an effective amount of thiocyanate wherein the thiocyanate cation is selected from ammonium, sodium, potassium and zinc to reduce yellowing treated carpet of a sulfonated aromatic condensate in an aqueous solution, to said dyed carpet fabric, at a pH of between 1.5 to 5.5 and at a liquor temperature of between 110 to 60 to 91°C (195°F), sc that the cotal of said portions of effective amount of m A P w J t91114,dbdatO86,170l9,res,c 2 I 1_ -13 sulfonated aromatic condensate in both steps is less than the total effective amount useful in either the first dye step, solely, or in the subsequent application step, solely, or so that a more effective degree of stain resistance of the carpet fabric is achieved at the same total of effective amounts of sulfonated aromatic condensate in said two steps as compared to the same amount in either step, solely. The dyeing conditions in the first step are a liquor to fabric ratio of about 10:1 to 100:1 at a temperature of 70 to 100 0 C (158 to 212 0

F)

for 15 to 90 mirutes. Preferred conditions for the second step are a liquor to fabric ratio of about 10:1 to 100:1 for a period cf about 5 to 60 minutes. The carpet fabric can be also rinsed subsequent to the second step.

15 The sulfonated aromatic condensate can be condensed with S. formaldehyde, The sulfonated aromatic formaldehyde condensate can be formed by condensation of formaldehyde with one or more phenols. The phenols can be phenol sulfonic acid or the alkali metal salt thereof. Or the phenol can be dihydroxy aromatic diphenol sulfone. The preferred condensate is formaldehyde condensea with a3kali metal salt of para-phenol sulfonic acid and with 4,4'-diphenolsulfone. Here again the dyed carpet fabric can comprise an effective amount of fluorocarbon intended 25 to improve the resistance of soiling of the carpet. The preferred amount of the fluorocarbon is present in an amount of from about 0.05 to 0.4% by weight on weight of the fabric. The fluorocarbon can contain perfluoroalkyl radical or a mixture of fluorinated pyromellitate oligomers. The fluorocarbon can be the reaction product of a perfluoroalkyl alcohol or amide with a suitable anhydride or isocyanate. The fluorocarbon can be the reaction product of N-ethyl perfluorroctylsulfoamideo ethanol with toluene diisocyanate. The preferred fluorocarbon is a mixture of pyromellitate oligomers formed by two reactices, first, the reaction of pyromellitic dianhydride with a fluorinated alcohol, and 911014,dbdatLO8,17019,res,13 13a second, the first reaction product is Zurther reacted with, epichiorodrin. The preferred thiocyanate is ammonium thiocyanate. The aqueous solution of either or both application steps can also contain an effective amount of dispersing agent such a condensed naphthalenic salt, an alkyl. sulfosuccinate or a mixture thereof. The preferred dispersing agent is a mixture of the sodium salt of condensed naphthalene sulfonic acid and diisobutyl sulfosuccinate. The aqueous solutions of both 8teps of 1, so6 b**C 0

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14V r 91 1014,dbdaLO86,17019.rcs,14 WO 89/02949 PCT/US88/01112 -14this invention can also contain an effective amount of salt having divalent cation such calcium, magnesium or ferrous chloride, sulfate or phosphate, preferably magnesium sulfate. The preferred amounts of this method would be having the fluorocarbon present in an amount of 0.05 and 0.4% by weight of the fabric, magnesium sulfate present in an amount of between 0.25 and 4% on the weight of the fabric, ammonium thiocyanate present in an amount between 0.03 and 1% on the weight of the fabric, the sulfonated aromatic formaldehyde condensate present in an amount between 0.15 and 7.5% on the weight of the fabric and the dialkyl sulfosuccinate present in an amount betwen 0 and 6 parts by parts by weight of the sulfonated aromatic condensate and the sodium salt of a condensed naphthalenic acid is present in an amount between 3 and 3 parts by weight by parts by weight of sulfonated aromatic co.densate. The more preferred amounts are where the fluorocarbon is present in an amount of between about 0.05 and 0.4% on the weight of the fabric, the magnesium sulfate is present in an amount between 0.25 and 1.5% on the weight of the fabric, ammonium thiocyanate is pvesent in an amount between 0.05 and 0.75% on the weight of the fabric, sulfonated aromatic formaadehyde condensate is present in an amount between 0.15 and 2.0% on the weight of the fabric and the dialkyl sulRonsuccinate is present in an amount between 0 and 2.5 parts by weight to the parts by weight of the sulfonated aromatic condensate and the sodium salt of a condensed naphthalenic acid is present in an amount between 0 and 2 parts by weight to l 30 the parts by weight of the sulfonated aromatic condensate.

Here again aqueous solution can be buffered with an effective amount of citric acid or any other acid with a sequestering agent to improve the yellowing of the carpet fabric.

naly -ast- ibe>rf&-- -oeis invention a method of improvingxh iacf a water oluble thiar onto polyamide fiber comprising at-- ng-thQ fiber with an effectiveoamo' nt of the WO 89/02949 PCT/US88/01112 -26B- TABLE 1I (CONTINUED) SOLUT'ION AND CARPET ANALYSIS DATA Concurrent and Aftertreatment Portion 1 y WO 89/02949 PCT/US88/01112 fiber has improved resistance to fading of dye, due to strong oxidizing agents such as benzoyl peroxide or ozon, the dye being present in or on the fiber, is disclose.

The thiocyanate can be ammonium, sodium, potassium, copper, zinc, ferrous, ferric, methyl or phenyl thiocyanate. The preferred pH of the method between 1 and 4. The preferred amount of thiocyanate s between about 0.1 and 6% on the weight of the fi r of the thiocyanate, present in or on the fibe after dyeing. The method improves exhaustion so that tween about 0.1 and about 12% on the weight of the fi er of the thiocyanate is present during the contacting d at least 50% of the thiocyanate present during e contacting is exhausted onto or into the fiber. e preferred thiocyanate is ammonium thiocyanate. e thiocy7nate can b contacted with the fiber in th dyebath or after dyeing of the fiber. The fiber eing treated can comprise an effective amount of a flu rocarbon to inhibit soiling of the fiber and a sulfon ed aromatic condensate can be present either on the fib r or with the thiocyanate. The various fluoroc bons are as described above. An effective amount of c ric acid or any acid with a sequestering agent can als be used to buffer for the condensate and thiocyanate o the desired pH for this same anti-yellowing effect. It is preferred to have between about 0.1 and 12% thiocyanate on the weight of the fiber and between about 0.05 and 0.4% f eluroa-bei-the weight of the fiber.

PREFERRED EMBODIMENTS Continuous Aftertreatment Process This process is intended to continuously treat nylon carpet fabric with sulfonated aromatic condensate formulations, for instance on a continuous dye range after steaming but before washing; or piece (or beck) dyed carpets may be continuously treated in a similar fashion by treating in-line on the wet goodu dryer range prior to the dryer. Equipment could be a spray header(s), or the equivalent, for the heated water across the moving carpet U1 -r4 'i2r 9 1; WO 89/02949 PCT/US88/01112 -16fabric with vacuum extractors below or a set of squeeze rolls to remove the water, followed by spray headers for the treatment liquor with a catch pan underneath. An alternative to spray application is use of a pressurized applicator, such as a Kusters Fluidyer, whicI presses the carpet into contact with a narrow slot in a conduit containing treatment liquor under pressure.

The prior art describes the application of similar sulfonated aromatic formaldehyde condensates by a beck (piece) aftertreatment and a continuous manner along with dyestuffs and subsequent steaming. The continuous process of this invention has economical advantages over the beck aftertreatment process by approximately 4 cents per pound of fiber produced as finished carpet (at equal levels of the stain resist agent on the fiber). The continuous aftertreatment process of this invention has the following advantages over the known prior art processes: Post dyeing process. Process conditions 'are optimized for the "exhaustion" of the sulfonated aromatic formaldehyde condensate onto the fiber. These conditions are not necessarily compatible with the dyeing process.

Since the treatment process occurs after dyeing, there is no interference with the dyeing process. Prior art concurrent (with dyes) processes generally result in poorer dyeing quali-y, a loss in dye yield and an effect of the dyed shade of the carpet.

4 More versatile. The process of this invention is applicable to both continuously dyed solid or multicolor patterns with the same process conditions. Furthermore, the process is also applicable to continuously aftertreating piece (or beck) dyed goods at the wet goods dryer.

The process involves the general principle of first, preheating the carpet with heated water followed by hydroextraction and the application of an aqueous solution of the sulfonated aromatic formaldehyde condensate, for which there are specific ranges of pH, concentration, wet 7. 0 9.

-17pick-up and temperatures. This is followed by a dwell period at which the carpet is either held at temperature or is allowed to radiant cool prior to washing the carpet. Prior to the treatment, the carpet has already been dyed by either beck or continuous methods.

For beck-dyed carpets the treatment process is at the wet goods dryer and for continuously-dyed carpets the treatment process is in-line after steaming and prior to the final washing step.

The process, in more detail, involves preheating the dyed carpet with hot water followed by hydroextraction by either squeeze or vacuum methods to a wet pick-up of to 190%. The conditions of the preheating process are established to achieve a carpet temperature of 54.4 to 99°C (130 to 210"F) prior to the treatment stage. The conditions of the preheating process are generally using 200% w.p.u. to total saturation with water at 60 to 100°C (140 to 212 0 As an addition in the continuous dyeing process, this also gives the carpet a washing prior to application of the treatment solution which aids the carpet's receptiveness to the stain resist agent. The treatment.solution is an aqueous solution of the sulfonated aromatic condensate at a 0.25 to 40 grams per liter concentration and a pH of 1.5 to 5.5. The treatment solution is applied at 200 to 600% w.p.u. add-on and a )i temperature of 60 to 100°C (140 to 212 0 The'resulting temperature of the carpet must be in the 54.4 to 99 0

C

(130 to 210"F) range for the treatment to be effective.

It is preferred to keep the difference in carpet fabric temperature between pretreating and application to a minimum. Following the application of the treatment liquor, it is necessary to either maintain the carpet at the application temperature for at least 0.5 to 30 seconds or allow it to radiantly cool to no less than 54.4 0

C

The equipment used for the application of the treatment liquor may be either spray or contact (e.g.

Kusters Fluidyer) in nature, The contact method is s r ISUBSTITUTE

SHEET

V 3~fl CV r WO 89/02949 PCT/US88/01112 -18preferred since it is easier to achieve 100% penetration of the treatment. Spray processes are adequate provided that the solution penetrates to the back of the carpet, and will generally require additional mechanical considerations, such a squeeze or rollers to achieve complete penetration. Other application equipment may also be used as long as the process requirements of preheating, heated treatment and dwell time at temperature are satisfied. The preheating and/or extracting steps of this invention may be carried out on the previously existing equipment.

The practical significance of this invention is that it provides an economical and effective means to apply sulfonated aromatic formaldehyde condensates to impart stain resistance to dyed carpets. The process is applicable to over 90% of all carpets treated with sulfonated aromatic formaldehyde condensates.

The continuous aftertreatment embodiment can also be the second step of another two-step process embodiment of this invention wherein an effective amount of the sulfonated aromatic condensate is added to a continuous dyebath or in batch or beck process for dyeing carpet fabric. The two-step process uses less overall amount sulfonated aromatic condensate for the same effect level of stain resistance. Alternatively, the same total amount of sulfoniated aromatic condensate can be used in the two-step process to achieve a higher level of stain resistance.

Certain nylon substrates (fiber) have very open internal structure (orientation of the polymer chains) which require very high amounts of the sulfonated aromatic condensate composition to impart a marketable degree of stain resistance. Certain sulfonated aromatic condensate composiiions cannot achieve a sufficient level of protection oil these substrates, so they must be excluded.

Also, the continuous aftertreatment method results in only moderate durability of the stain resistance properties to steam cleaning when a high pH detergent is used.

WO 89/02949 PCT/US88/01112 -19- The two-step application process has all of the advantages of the continuous aftertreatment process such as economics, etc. over one-step batch processes. It also has unique advantages over the aftertreatment process alone and all other known continuous application processes for sulfonated aromatic condensates, such as using all of the sulfonated aromatic condensate in dyebach (currently being practiced on a commercial scale).

The level of stain resistance imparted by a given total amount of the sulfonated aromatic condensate is substantially improved. The required add-on for a marketable level of stain resistance reduced by approximately 30% over aftertreatment and greater for other continuous processes, providing economical advantages. The process (with optimized sulfonated aromatic condensate composition for aftertreatment) yields marketable levels of stain resistance on critical substrates described above using reasonable levels of the sulfonated aromatic condensate composition. The durability of the stain resistance, properties to steam cleaning (with and without a high pH detergent) is improved over the aftertreatment only process, yielding improved properties.

The two-step process involves the general principle of applying a portion of'the total sulfonated aromatic condensate composition to be applied in the standard dyebath with an appropriate amount of magnesium sulfate (magnesium sulfate, 0 to 0.35% on the weight of the fabric for each 1% on the weight of the fabric of the sulfonated aromatic condensate). The balance of the total sulfonated aromatic condensate composition (with 0 to 0.35% of magnesium sulfate) is then applied as an aftertreatment. The amount of Epsom Salt required in both portions depends on the sulfonated aromatic condensate and the substrate being treated.

The dyebath composition is based on that typically used for continuous dyeing. The appropriate amount of the sulfonated aromatic condensate composition r~ WO 89/02949 PCT/US88/01112 (based on-the optimum ratio and the total required for the particular:- substrate) is added to the dyebath.

More specific examples of the processes are given in the following Examples.

Preferred Treatment Compositions In addition to a sulfonated aromatic condensate other chemical -ompounds such as a thiocyanate are added to the. formulation used to treat the carpet fabric to overcome oxidative yellowing of the sulfonated aromatic condensate, and to provide the resulting carpet with better.resistance of the dyes to strong oxidizing agents, such- as ozone or the benzoyl peroxide found in commercial anti--acne preparations. Also a salt containing a divalent cation is useful to improve exhaustion of the sulfonated aromatic condensate on high ICP polymer fibers. A dispersing agent(s) is usually necessary in the formulation to prevent precipitation or coagulation due to incompatibility of the components of the formulation for treatment and/or the components with a fluorocarbon treated carpet fabric. Acids are used to buffer the formulations. It has been discovered that citric acid or any acid with a sequestering agent creates an additional improvement in yellowing characteristics of sulfonated aromatic condensate treated fiber or fabric.

Ammonium thiocyanate and sulfonated aromatic condensates- exhaust onto nylon fibers under comparable applicat.ion procedures. T1e two products may be co-applied, providing that the uptake of one material does not.interfere with the other. Therefore, the selection of the sulfonated aromatic condensate is important. Some sulfonated aromatic condensates exhaust preferentially over. ammonium thiocyanate. But to the contrary there was a synergistic effect of Intratex N (which is reported to be formaldehyde condensed with an alkali metal salt of para-phenol sulfonic acid and with 4,4'-diphenolsulfone) and ammonium thiocyanate on benzoyl peroxide spotting resistance.

An additional benefit of ammonium thiocyanate in U I N 89/02949 PCT/US88/01112 -21the composition is as an antioxidant to prevent light induced yellowing of Intratex N. This combination was found to give a sufficient improvement (acceptable lightfastness) for beck applications, but was insufficient for continuous applications (although improved).

The combination of sequestering agents, such as EDTA and sodi; 'ametaphosphate, with Intratex N was found to resul. some improvement in light induced yellowing, but did not yield completely acceptable results for the continuous application. Combination of Intratex N with citric acid (sequestering and antioxidant properties) also gave similar results. The combination of ammonium thiocyanate and citric acid was discovered to achieve the be'st results in the reduction of light induced yellowing for continuous application, showing virtually no yellowing. (Combinations of ammonium thiocyanate and other sequestering agents were not as effective.) A novel dispersant system, using Tamol SN and Monawet MB-45 was developed to prepare a stable composition cotaining Intratex N, ammonium thiocyanate and citric acid in concentrated form for continuous applications. A new dispersant system was developed to prepare a stable concentrate containing Intratex N and ammonium thiocyanate for beck aplications.

Example Compositions: Composition Solids, composition Solids, Component 1, 2, Intratex N* 189 3.8 Intratex N-l* 25 5- Ammonium Thiocyanate 6.00 6 Citric Acid 14.30 7.15 solution) Sulfuric Acid 1.1 1.

Tamol SN (sodium 4.00 3.9 7.32 7.1 salt of condensed naphthalene sulfonic acid) WO 89/02949 PCT/US88/01112 -22- Example Compositions: (Continued) Composition Solids, Composition Solids, Component 1, 2, Monawet MB-45 20.00 9 (di-isobutyl sulfosuccinate) Epsom Salt 6.00 6 (Magnesium Sulfate) 24.7 2.9 Demineralized Water 33.03 0 72.65 Same concentration of same N-1 has pH 7, N has pH 10.5.

H;

Any thiocyanate such as those listed in the Summary of the Invention is expected to be effective, l- hough the coppe e s-.nd..erric-thi-.yanat--may. have to be eel rg-gcmpe- As dispersing agents any agent that is effective can be used, such as for any process formulation, the condensed naphthalenic salts, the alkyl sulfosuccinates, a mixture of them, and for batch process systems salts of polymeric carboxylic acid, and polyethylene glycol ethers.

As sequestering agents, the polyphosphates, such as sodium tripolyphosphate (STPP), aminocarboxylic acids, such as ethylenediamine tetraacetic acid hydroxycarboxylic acids, such as tartaric and citric acid, and the aminoalcohols, such as triethanolamine (TEA) are expected to be effective. See Kirk-Othmer Encyclopedia of Chemical Technology, supra.

Example 1 On a commercial dyeing range Composition 1 was applied both in a two-step (continuous.-continuous) and in a continuous aftertreatment only process to a normal and to a high ICP fiber carpet fabric. The normal fiber was in an 1186 denier Superba heat set textured yarn. 'he high ICP fiber was a 1700 denier textured yarn which was heat set by a proprietary Pharr process with a high heat history giving an ICP of 3.92 compared to normal ICP of about 3.8. Boith fibers were previously treated with a 'a? t WO 89/02949 PCT/US88/01112 -23spin finish containing a soil-release fluorocarbon as described in U.S. 4,604,316 and/or U.S. 4,192,754. The fabric was dyed gray. The prewash and treatment application was by spray just after the dryer but before the final wash on the continuous dye range. Following are the dyes a&9 chemicals used in the continuous dyebath.

Control: 0.135 Nylanthrenel Orange RAR (liquid) 0.092 g/1 Tectilon 2 Red 2B 0.052 g/1 Telon 3 Blue B-AR (powder) (the above dyes are the same for all dyebaths.) g/1 Alrowet 2 D-70 g/1 Chemcogen 4 DCG g/1 Defoamer AC (Fuller) pH 5.5 with Acetic Acid 400% w.p.u. via Kuster Fluidyer Steam in vertical steamer 5 to 6 minutes Dyebath": (Order of addition to bath as listed.) 3.0 g/l Alrowet g/1 Chemcogen DCG g/1 Def~amer AC (Fuller) 10.0 g/1 Composition 1 1.25 g/1 Epsom Salt (Magnesium Sulfate) 0.5 g/l Sequestrene 2 30A Dyes abov4 Approximately 1 g/1 Ammonia to pH Dyebath": (Order of addition to bath as listed.) 3.0 g/l Alrowet g/l Chemcogen DCG g/1 Defoamer AC (Fuller) 20.0 9/1 Composition 1 g/1 Epsom Salt (Magnesium Sulfate) 0.5 g/l Sequestrene 30A Dyes above Approximately 3 g/1 Ammonia to pH r- I.1 1 I II.. -24- Alrowet D-70 is dioctyl sulfosuccinate 70% active Chemcogen DCG is sulfonated alkyl diphenylether 30-38% active.

Defoamer AC is a proprietary defoamer from Fuller Sales.

Sequestrene 30A is ethylene diamIrne tetraacetic acid, 1 of Crompton Knowles 2 Ol Ciba Geigy 3 of Mobay 4 "of Lyndal Chem.

grams per liter The following tables provide Other operating conditions and results, using the aoove dyebatbs and the shown aftertreatments. Trials 3 and 4 were omitted because they had a slightly different, nonpreferred, formulationr.

TABLE I Aftertreatment Application Data ~f;id Trial 1 9 2 6 8 7 11 12 13 Nominal Comp. 1 Add-on from Dyobath, owf 0 0 4.0 4,0 0 0 4.0 0 4 .0 8.0 8.0 Nominal Comp .1 Add-on from A/T, owf 0 1110 7.0 11.0 0 10 9 7.0 14.9 10.9 7.0 '11.0 Total Nominal QOmp- 1 Add-on, owf 0 11.0 11.0 15.0 0 10.9 11.0 14.9 14.9 15.0 19.0 Preheat Liquor Temperaturej 0 c (OF) 61.1 (142) 60.0 (140) 60.6 (141) 60.0 (140) 61.1 (142) 60 .0 (140) 60.6 (141) 60.0 (140) 60.0 (140) 60.0 (140) 60.0 (140) 4 ~alse 9 ~i~li

K*P.

rli r :Y SUBSTITUTE SUEET j rT ,k L~t p I I TABLE I (CONTINUED) Aftertreatment Application Data Trial I. D.* 1 9 10 2 6 7 11 12 13 Carpet Tempe ature Before A/T, e (oF) 53.3 52.8-53.9 53.9-54.4 53.3-53.9 53.3 52.8-53.9 53.3-55.0 53.3-53.9 53.9-55.0 53.9-54.4 54.4 (12P) (127-129) (129-130) (128-129) (128) (127-129) (128-131) (128-129) (129-131) (132i-10) (130)

A/T

Liquor, 7.6 2.9 3.0 2.9 7.6 2.9 3.0 2.8 2.9 3 3 2.9 69.4-70.6 68.3-68. 9 70.0-70.6 68.3-69.4 68.9-70.0 70.0-71.1 70.0-70.6 71,1-72.2 69.4-70.0 71.1-7, .7 69.4-70.6 Post-A/T rarpet Temperature, C (OF) (157-159) (155-156) (158-1s9) (155-157) (156-158) (158-160) (158-159) (160-162) (157-158) (160-161) (15-159) NUmbers 1, 5, 9 and 10 trials are normal carpet fabric; remaining numbers are high 19P carpet fabric. Trials 1 and 2 are a controls.

Both fabrics are 40 oz/sq yd out piles.

A/T Liquor Temperature ranged from 82.2-83.3* 0 C (180-182F).

TA8ILE Ii SOLUTION AND CARPET ANALYSIS DATA Concurrent Portion (in Dyebath) Trial 1 2 6 7 8 9 11 12 13 Targer Nominal C(p.1 Pd-on# owf 0 0 0 0 0 4.0 4.0 4.0 4.0 8.0 8.0 Nominal Comp, I Conc. in Dyebath, g/l 9/1 0 0 0 0 10.0 10.0 10.0 10.0 20.0 20 0 Anal.

Comp.1 Conc. in Dyebath, 0 0 0 0 0 9'2 9.2 9.2 9.3 16.8 16.8 Calc.

Comp.1 Add-on from Analysis, owf 0 0 0 0 0 3,7 3.7 3.7 3.7 6.7 6.7 i;, ,i SU6STiTUTE.

SHEET

I

I

WO 89/02949 PCTIUS88/0l 112 -26- TABLE II (CONTINUED) SOLUTION AND CARPET ANALYSIS DATA Aftertreatment Portion~_______ Actual A/T Target Spray Total A/T Nomi 'nal Conc. Header Liquor Trial Add-on, Del'iv., Pres., Deliv., I.D. owf GPM* psig GPM* 1 0 0 6.7 77 2 0 0 6.6 76 11.2 1.1.9 6.5 6 11.2 1.1is' 6.6 76 7 15.2 1.62 6.6 76 8 7.2 0.76 6.6 76 9 7.2 0.76 6.6 76 3,1.2 1.19 6.7 77 11 11.2 1.19 6.7 76 12 7.2 0.76 6 76 13 11.2 1.19 6.5 Line speed for both fabrics was 30 ft/min.

Throughput =99.8 lb carpet/mmn.

Actual dyeing wet picX-up Was 400% *n all cases.

Aftert-reatnent wet pick-up was alwibys between 626 and 64396.

Aftertreatment pH was always between 2.8 and 3.0 except control was 7.6.

*gallJ.ons per minute WYO 89/102949 PCT/US88/O 11121 Trial I. .D.

1 2 6 7 8 9 11 12 13 26A- TABLE II (CONTINUED) SOLUTION AND CARPET ANALYSIS DATA Aftertreatment Port:Lon Caic. Caic.

Nominal Anal. Cornp.1 A/T A/T Add-on Liquor Liquor from Conc., Conc., Set-up, g/l g/l %owf 1.214. 3 10.9 23.3 22.4 14.9 11.0 11.6 7.0 11.0 11.6 7.0 17.0 18.4 11.0 17.2 18.4 10.9 11.0 11.2 7.0 17.4 13.6 11.0 Calc.

Cornp. 1 Add-on f rom Analysis, owf 0 0 9.3 9.4 14.3 7.4 7.4 11 I 9 11. 7 7.1 8.6 WO 89/02949 PCT/US88/01112 -26B- TABLE II (CONTINUED) SOLUTION AND CARPET ANALYSIS DATA Concurrent and Aftertreatment Portion Calc. Calc. Anal. Anal.

Comp.1 Comp.1 Comp.l s.a.c.

Target Add-on Add-on Add-on Add-on Comp.1 from from from from Trial Add-on, Set-up, ANALYSIS, Carpets, Carpets, I.D. owf owf owf owf owf 1 0 0 0 0 0 2 0 0 0 0 0 11.2 11.0 9.3 10.6 2.6 6 11.2 10.9 9.4 10.9 2.7 7 15.2 14.9 14.3 16.3 8 11.2 11.0 11.1 10.7 2.6 9 11.2 11.0 11.1 11.1 2.7 15.2 15.0 15.6 14.0 11 15.2 14.9 15.4 15.4 3.8 12 15.2 15.0 13.8 15.8 3.9 13 19,2 19.0 15.3 19.6 4.9 Line speed for both fabrics was 30 ft/min.

Throughput 99.8 lb carpet/min.

Actual dyeing wet pick-up was 400% in all cases.

Aftertreatment wet pick-up was always between 626 and 643%.

Aftertreatment pH was always between 2.8 and 3.0 except control was 7.6.

*lc-i -1-cc

LA___

",WO 89/02949 PCT/1JS88/01 112 -27- Trial I. D.

1 9 2 6 8 7 11 12 13 Trial I. D.

TABLE III STAINING DATA Nominal Nominal Comp. 1 Comp. 1 Total Add-on from Add-on from Nominal Comp.1 Dyebath, A/Tf Add-on, owf owf owf 0 0 0 0 11.0 11.0 4.0 7.0 11.0 4.0 11.0 15.0 0 0 0 0 10.9 10.9 4.0 7.0 11.0 0 14.9 14.9 4.0 10.9 14.9 8.0 7.0 15.0 8.0 11.0 19.0 Stain Rating 1 (0=best Time Before Blotting with Water, Hours 1 4 7 Originals 1 8.5 0.25 9 0 0 2 9.0 6 2.5 8 0.1 7 0.25 3.1 0 12 0 13 0 steam cleaning 8.5 0.25 0 0 9.0 2.5 0.5 1.5 0.1 0 0 8.5 0.25 0 0 9.0 2.5 0.1 1.5 0.1 0 0 24 4 24- Af ter s.-c 8.5 8.5 0.25 4.5 0 3.5 0 3.0 9.0 8.0 2.5 4.5 0.25 2.5 1.5 5.0 0.25 3.0 0.1 1.0 0 1.0 2 passes of detergent solution using conventional steam cleaning equipment. Detergent so1lution: 3. oz./gal. ALL-IN-ONE (Certified Chemical Equipment# Cleveland, Off).

1 See Example 6, Part 2, "Performance"$ "Drop Test".

r WO 89/02949 PCT/US88/01 112 -28- TABLE IV AND COLORFASTNESS DATA Trial I. D.

9 10 2 6 a 7 211 12 13

REPELLENCY

Comnp. 1 Add-on from Dyebath, owf 0 0 4.0 4.0 0 0 4.0 0 4.0 8.0 8.0 Comp. 2I Add-on f rom

A/T,

owf 0 2.1.0 7.0 2. 0 0 10. 9 7.0 14.9 10.9 7.0 11. 0 Total Nominal Comnp. 1.

Add-on, %owf 0 11.0 1.1.0 15.0 0 10.9 1.1.0 14.9 14.9 *15 .0 19.0 Repe 2.1en cy Oil Water 5.0 5.0 4.0 4.5 5.0 5.0 5.0 5.0 4.0 4.0 4.0 Grey Scale-Rating Trial I. D.

1 5 9 2 6 a 7 1 12 13 Lightfastness Ozonefastnessl 1 CY** 3 cy 5 cy 20 AFU* 4.5 4.5 4.5 4.*5 4.*0 4.0Q 4.5 4.0 4.0 4.0 3.a5 40 AFU 4.0 4.0 4.0 4.0 3.5 4.0 4.0 4.0 3.*75 3 .25 3.0 3,0 3.5 3.5 3.5 3.90 3.0 3.5 3.0 3.5 3.0 3.0 2.0 3.0 3.0 3.0 2.0 2.5 3.0 3.0 3.0 3.0 3.0 1.5 2.5 2.5 2.5 1.5 2.5 5 2.5 3.0 2.5 2.5 N0 2 4 Fastness -1 cy** *AATCC 16E fading unit **cycles 1AATCC 129 2 AATCC 164 I 9 9 99 I 9 9 -29- 3 Oil Repellency AATCC TM-118, Oil Repellency: Hydrocarbon Resistance Test.

Water Repellency DuPont Isopropanol/water series 1. 2/98 IPA/Water 2. 5/95 IPA/Water (47) 3. 10/90 IPA/Water 4. 20/80 IPA/Water (33) 30/70 IPA/Water (28) Numbers in parentheses represents surface tension of the test fluids.

TABLE V BENZOYL PEROXIDE SPOTTING DATA* Trial

I.D.

1 9 2 6 8 7 11 12 13 Comp. 1 Add-on from Dyebath, owf 0 0 4.0 4.0 0 0 4.0 0 4.0 8.0 8.0 Comp. 1 Add-on from

A/T,

owf 0 11.0 7.0 11.0 0 10.9 7.0 14.9 10.9 7.0 11.0 Total Nominal Agent Add-on, owf 0 11.0 11.0 15.0 0 10.9 11.0 14.9 14.9 15.0 19.0 Spot Visibility 0=Invisible; Benzoyl Peroxide Conc., Soln. in Acetone .01 6.5 0 0 0 5.0 0 0 0 0 0 0 .05 .10 1.0 7.0 1.0 1.0 2.0 6.5 1.0 1.0 0.5 1.0 0.5 0.5 8.0 2.0 2.0 2.0 6.5 1.5 2.0 1.0 2.0 1.5 1.5 9.0 4.5 5.5 5.5 9.0 5.0 6.0 4.5 5.0 4.5 5.0 Sample spotted and exposed in for three days with -ml of benzoyl peroxide solution chamber at 32.2°C (90'F) and 80% R.H.

(color change ceases).

fvty5 r (.1 A;f 0/ !6jj13VT1 'T i WO 89/02949 PCT/US88/01112

I

TABLE VI SOILING DATA Trial

I.D.

1 4 9 2 3 6 8 7 11 12 13 Comp.l Add-on from Dyebath, owf 0 0 0 4.0 4.0 0 0 0 4.0 0 4.0 8.0 8.0 Comp .1 Add-on from

A/T,

owf 0 10.9 11.0 7.0 11.0 0 10.9 10.9 7.0 14.9 10.9 7.0 11.0 Total Nominal Comp.1 Add-on, owf 0 10.9 11.0 11.0 15.0 0 10.9 10.9 11.0 14.9 14.9 15.0 19.0 Soil Rating (0=best, Treads Accl.* Method 5K 5.0 5.5 5.5 4.5 4.5 5.5 5.5 5.5 4.0 5,5 4.0 4.5 4.5

JTCC**

5K 10K 5.5 6.0 6.0 6.0 6.0 4.0 4.5 5.5 5.0 5.5 4.5 5.5 5.5 7.0 7.0 7.5 7.5 7.5 5.5 6.0 6.5 7.0 7.0 7.0 7.0 7.0 Total Soil Rating 17.5 18.5 19.0 18.0 18.0 15.0 16.0 17.5 16.0 18.0 15.5 17.0 17.0

A

Accelerated soiling conducted at Petersburg Rehabilitation Center using "natural soil" with mineral oil added.

John Tyler Community College Maintenance Hall.

6 1 i WO 89/02949 PCT/US88/01112 -31- Example 1 Conclusions The two-step process with composition gives considerably better stain resistance than the aftertreatment (only) process, at equal total add-on levels. This shows potential for achieving acceptable performance at lower total add-on levels.

The two-step process also gives acceptable stain resistance on the "high ICP" substrate at levels comparable to that currently being used for s,a.c. normal substrates by aftertreatment only.

Stain resistnace improves and lightfastness is adversely effected (yellowing) as the Composition 1 concentration in the concurrent portion increases, with total add-on level constant. Acceptable yellowing and stain resistance was achieved at 4% on the weight of the fiber of Composition 1 in the concurrent portion, "Optimum" two-step systems had improved ozone and benzoyl peroxide spotting resistance properties. Some reduction does occur as the concentration applied by the aftertreatment portion is reduced in favor of the concurrent portion.

Example 1 Summary of Results Staining Performance Table III: In general, the standard Superba heat set (H/S) substrate performed beter than the high ICP substrate at equivalent application conditions, while analyzed add-on's were equal. This is normally observed because of undesired deep penetration of s.a.c. into fiber of high ICP.

When applied by aftertreatrent only, Composition 1 on the high ICP fabric did not yield acceptable staining performance. When the level of Composition 1 was increased from 11 to 15% owf on the high ICP fabric, stain resistance was further improved to a "Marginal" performance level (stain rating of 1.5 at 4- and 24-hour blot times).

The two-step process gave considerably better stain resistance than the aftertreatment only process on both substrates, at equal total application levels. No WO 89/02949 PCT/US88/01112 -32staining at 24 hours was obtained on the Superba H/S fabric, using: on the weight of the fiber in the Dyebath and 7% on the weight of the fiber in the A/T. These same levels on the high ICP substrate gave staining performance equal to the Superba fabric aftertreated (only) with 11% on the weight of the fiber of Composition 1 (stain rating of 0.5 at 24 hours).

Example 1 Summary of Results Colorfastness Table IV: ISD No light induced yellowing was observed at AFU on. any of. the trials -conducted, but begn to be noticed at 40 AFU.

Light induced yellowing (at 40 AFU) became more noticeable as the amount in the concurrent portion was increased (and aftertreatment was reduced). Trials with 8 on the weight of the fiber Composition 1 in the concurrent portion (high ICP substrate) were marginal to unaLcceptable for lightfastness.

The improvement in resistance to ozone fading, obtained with Composition 1 by aftertreatment was aso observed with Composition 1 and also using the two-step process with Composition 1 (at lower level).

Benzoyl Peroxide Spotting Table V: The two-step process gave only a slight reduction in the benzoyl peroxide spotting performance than the aftertreatment process, at equal add-on levels.

Repellency Table IV: There was no significant effect in any of the trials on oil and water repellency. As the amount of Composition 1 (and magnesium sulfate) in the concurrent portion was increased, the oil repellency tended to decrease srighttly Soiling Table VI: only a slight negative effect in soiling was observed on all trial samples compared to the control.

Composition 1 showed slightly more soiling when applied by aftertreatment, as the concentration applied was increased.

.a I I .1 -33- With total add-on constant, the two-step process had less impact on soiling than aftertreatment alone.

Two-Step Process Guidelines (Best Mode) For The Continuous Application of Composition 1 Concurrent (with dyestuffs) Portion: For Suessen H/S Substrates: 2.0% owf For Superba H/S Substrates: 3.0% owf For "High ICP" Substrates: 4.0-5.0% owf Dyebath Make-up Procedure: 1st Wetting and leveling agents (defoamer, if required) 2nd Composition and Epsom Salt** (MgSO 4 -7H 2 0) owf Epjom Salt for each 4.0% owf Composition 1) 3rd 0.25-0.50 g/l Sequestering agent (EDTA) 4th Dyestuffs Adjust to desired pH with either acetic acid, ammonia or caustic soda* Notes: Composition 1 has low pH. -se in the dyebath will result in pH's of 3.0-3.5, requiring an alkalai to adjust pH, Only phosphates which form water-soluble complexes with magnesium ion may be used in the presence of magnesium sulfate.

Aftertreatment Portion: Composition 1 Concentration: For Suessen H/S Substrates: 3,0% owf For Superba H/S Substrates: 5.0% owf For "High ICP" Substrates: 7.0 Application Parameters: Preheat/wash spray at 71.I1C (160°F) and extract (vacuum) to 75-125% w.p.u. to give carpet temperature of 0 C (140 0

F).

Apply treatment solution at 81.20C (180 0 F) and 400-500% w.p.u. to give a post-A/T carpet temperature of 71.1 0 C (160*F).

sL SUBSTITUTE

SH

et~hn~F -34- Example 2 This is a further example of the continuous aftertreatment process of the invention, using Composition 2 in the treatment of the carpet fabric. The fabrics treated were a fabric tufted from an 1186 denier continuous filament textured medium dye fiber in a Superba heatset yarn to a 28-ounce cut pile fabric and a textured 3.15/2 cotton count yarn from a 19 denier per filament staple deep dye fiber heat in a Suessen and tufted into 48-ounce fabric. Both were pretreated with the fluorocarbon of Example 1 and were to be dyed light gray. The nominal application conditions were (140*F) preheat water temperature, 81.2 0 C (180 0

F)

application liquor temperature, 500 to 600% w.p.u.

application liquor, the dyes and dyebath additives were as in Example 1, except no sequestrene was used. No Composition 2 or other s.a.c. was added to the dyebath.

The following Tables show the application conditions and results.

TABLE VII APPLICATION DATA Target Actual Target Nominal A/T Target Nominal Nominal Epsom Spray A/T A/T Comp.2 s.a.c. Salts Header Liquor Liuqor Trial Applied, Level, Level, Pres., Deliv., Conc., I.D. of owf psig GPM g/ 1 0 0 0 6.2 73.3 0 2 15.0 2.8 0 6.2 73.3 25.0 3 0 0 0 6.5 75.2 0 4 9.0 1.7 0 6.5 75.2 17.2 Actual w.p.u. was between 523 and 532%, pH was 8.3 for control; 3.0 for Trial 2; 3.3 for Trial 4.

Preheat liquor tGmperature was 60*C (140°F). Carpet temperature was 52.8-54.4*0 (127-130°F). Application liquor temperature was 81.7-83.5*C (179-182*F) and carpet temperature Was 68.9-71.7°C (156-161°F).

M^s SUBSTITUTE SHEET b- a 1

LI

4 0 4 *l 44 *4 44 TABLE VII (CONTIN1UED) APPLICATION DATA Trial I .D.

1 Caic.

Conc.

Comp. 2 Liquor g/l 0 Anal.- Conc.

Comp. 2 Liquor g/1l 0 Caic. s.a.c.

Caic. Caic. Add-on Anal.

Comp.2 s.a.c. from s.a.c.

Add-on Add-on Anal. Add-on from from A/T from Set-up Set-up Liquor Carpets owf owf owf owf 0 0 0 0 Caic.

Epsom Salt Add-on owf 0 2 30.4 3 0 4 20.9 21.2 17.7 3.4 2.3 0 0 0 14.4 1019 2.1 0 1.5 2.62 0 0 0 1.89 0 Actual w.p.u. was between 523 and 532%, pH was 8.3 for control; 3.0 for Trial 2; 3.3 for Trial 4.

Preheat liquor temperature was 60*C (140*F). Carpet temperature was 52.8-54-4 0 C (127-130 0 Application liquor temperature was 81.2-83.3 0 C (179-182 0 F) and carpet temperature w~is 68.9-71.7 0 C (156-161 0

F),

TABLE VIII STAINING PERFORMANCE, DURABILITY TO STEAM CLEANING AND CHANGE-OF-SHADE DATA Sample I. D.

1 2 3 4 Nominal Comp. .2 Applied, 0 Stainl Rating (0=best, l0=worst) Time Before Blotting with Water, Hr 0.05 8.5 15 0.25 0 4.5 9 0 Stain Rating (0-=best, Time Before Blotting with Water, Hr 8 24 8.5 8,5 0.5 8.5 0.25 7.0 0 1 8.5 0.75 7.0 0 4 0.1 Sample I D.

1 2 S'C' 4 5.0 3.0 Shade Change* M-N (Y) 1.75 0.1 2.0 7.0 041 M (Y) *Nwnos acceptablej Mwmearginall Y:4yellow.

Letter in parentheses indicates direction of color change from the control.

*steam cleaned.

SUBSTITUTE SHEET

A'

WO 89/02949 WO 8902949PCT/US88101 112 -36- 'ABLE IX COLORFASTNESS DATA S ampl.e 1. D.

1 2 3 4 Nominal Cornp.2 Applied, 0 15.0 0 9.0 Grey Scale Rating Lightfastness, AFU 20 4.0 2.5 4.5 3.5 S>4cale Ratj Sample

I.D.

1.

2 3 4 0zonefastnes s 3.

3,5 3.5 2. 3.0 3.0 3 2.0 2.5 2.5 3.0 75_ 1.0 2.0 2.0 2.5

NO

2 Fastness 1 cy *High nitrogen dioxide (AATCQ TM-164).

TABLE X SENZOYL PEROXIDE SPOTTING DATA* Spot Visibility (0=Invisib.e; originals Sample 1. D.

3 4 Nominal Comp. 2 Applied, 0 0 9 iBenzoyl Peroxide Conc., solution in Acetone o0.01 2.0 2.0 o0,05 7.5 6.5 7.5 ,5 o0110 8.0 7.0 8.0 8.0 1,0 8.5 9.0 5 .0 *Sample spotted with I ml of bonzoy3. peroxide solution and exposed in (ohamber at 909F (32,29C) and1 80% R.H.

for three days (color change ceases).

U -37- TADLE X (CONTINTUED) BENZOYL PEROXIDE SPOTTING DATA* Spot Visibility (O=Invisible; l0=Bright) Steam Cleaned Benzoyl Peroxide Conc., San.ple Solution in Acetone I.D. 0.01 0.05 0.10 1.0 1.1.0 5.0 7.0 9.0 2 0.25 5.0 7.0 8.5 3 0.5 5.0 7.0 8.5 4 0.3 4.5 6.5 8.0 *Sample spotted with 1 ml of benzoyl peroxide solution and exposed in thamber at 32.2 0 C (90 0 F) and 00% R.H.

for three days (color change eases).

Sample 1. D._ 1 2 3 4 TABLE XI REPELLENCY DATA (FINISHED CARPETS) Nominal Comp.2 Repellency Applied, Oil Water 0 4.0 15.0 4.0 0 3.0 .O 3.0 This Example 2 deimonstrates the effectiveness of the suIO2onated arzomatic condensate With only a dispersing agent and further demonstra~tes the effectiveness of the continuous aftertreatment process of this in.ventioi.

MV

SUB~STITUTE SHEET -38- Example 3 Part 1 This example demonstrates the effective use of the process of this invention on fabric which has not been previously treated with any fluorocarbon compound for antisoiling properties. The Composition 2 used in the continuous aftertreatment process (no two step) of this invention as set forth in Example 1. Dyebath formulation was as in Example 2. Conditions were as in Example 1, more specifically, preheat water temperature was 90.6°C (195 0 F) at 100% w.p.u. to achieve carpet temperature of 57.2 to 60 0 C (135-140 0 Aftertreatment liquor temperature was 82.2 to 85 0 C (180-185*F) to achieve carpet temperature of 71.1 to 76,7 0 C (16C-170F). Aftertreatment dwell time was 0 seconds before washing at 40:1 liquor to fabric Catio, hydroextraction and drying. Both compositions were applied at both 1.5 and 3.0% on the weight of the fabric. Samples of fabric pretreated with fluorocarbons, which are also part of the invention, were run alongside the fabric untreated with fluorocarbon. The results show that higher amounts of sulfonated aromatic condensate must be applied to the fabric untreated with fluorocarbon to achieve the nearly same level of stain resistance. The following tables give application conditions and results.

TABLE Y1 I EVALUATION OF STAIN BLOCKING FOR CONTINUOUS AFTERTREATMENT Stain Rating Totall 20 AFU Rank 2 No.inal Fabric Fabric Fabric Fabric Sample Add-on, With Without With Without I.D. Fluoro. Fluoro. Fluoro. Fluoro.

1 0 54.0 45.0 2 3 2 3.0 1.5 1.4 4 7 3 3.0 0.3 0.3 4 9 4 3.0 1.2 1.5 4 9 Samples 2 and 4 applied at pH 3. Samples 1 and 3 were applied at pH 2.

1 Total of ratings at lI 4, 7 and 24-hour tests, High numbers indicate most stain.

2 Lower numbers are better.

qrS1TITUTE

SHEET

t WO 89/02949 PCT/US88/01112 -39- TABLE XII (CONTINUED) EVALUATION OF STAIN BLOCKING FOR CONTINUOUS AFTERTREATMENT

NO

2 Rank 2 Fabric Fabric Soiling Rating** Fabric Fabric Sample With Without With Witho ID. Fluoro. Fluoro. Fluoro. Fluor 1 1 1 4 8 2 2 2 9.5 9 3 2 3 10 4 2 2 5.5 Soiling evaluated under Accelerated Method, 0=best, 2 Lower numbers are better.

ut o.

TABLE XIII ANALYSIS DATA Sample

I.D.

1 2 3 4 SNominal Add-on, 3.0 3.0 3.0 S.a.c. Analyzed, owf* Fabric With Fabric Without Fluoro. Fluoro.

3.09 3.47 2.94 2.96 3.36 2.86 Samples 2 and 4 were applied at pH 3. Samples 1 and 3 were applied at pH 2.

Extracted from carpets with 0.1N NaOH for four hours and analyzed by HPLC against original material.

Example 3 Part 2 The conditions of Example 3 Part 1 were repeated except Composition 1 was used with the results shown in the following tables. All fabric was without fluorocarbon treatments.

-7 WO 89/02949 PCT/US88/01 112 TABLE XIV STAINING AND CHANGE-OF-SHADE DATA Trial I. D.

1 2 3 4 Nominal Comp.l1 Add-on, owf 5.0 6.0 7.0 8.0 Stain Rating Time Before Blotting With Water, Hr 1 7.0 0.25 0.1 0.1 0.1 4 7.0 1.0 0.75 0.25 0.25 7 7.0 1.0 0. 75 0 .25 0.25 24 0.75 0.5 0. 25 0.25 Shade Change M (Y) M (Y) Mi (Y) M (Y) Trial 1. D.

1 2 3 4 5 Nominal Conp. .1 Add-on, owf 5.0 6.0 7.0 8.0 TABLE XV COLORFASTNESS DATA Grey Scale Rating Lightfastness, Ozonefastness, AFU cy 20 40 1 3 4.0 3.5 3.5 2.0 4.5 4.0 4.0 3.0 4.5 4.0 4.0 3.5 4.5 4.0 4.0 3.5 4.5 4.0 4.5 4.0 N02 Fastness, cy..

1 i WO 8902949 PCT/US88/01112 -41- TABLE XVI ANALYSIS DATA Nominal Comp.l Nominal Conc.

Comp.l A/T Trial Add-on, Liquor I.D. owf g/1* 1 2 5.0 12.5 3 6.0 15.0 4 7.0 17.5 8.0 20.0 Applied at 400% w.p.u.

Non-detected Anal.

A/T

Liquor Conc.

of sac g/l 11.8 15.0 19.6 23.5 s.a.c.

Add-on Based on Anal.

A/T

Liquor owf 4.7 6.0 7.8 9.4 Anal.

sac Add-on from Carpets owf

N/D**

5.1 7.3 7.5 8.3 Anal.

sac in Rinse Bath g/l

*N/D

N/D

N/D

N/D

N/D

Example 4 The process and conditions of dyeing formulations of Example 2 using Composition 2 were repeated with and without citric acid to adjust pH in the continuous aftertreatment application process of this' invention the fabric was in 32 ounce per square yard cut pile construction of a 1185 denier bulked continuous filament, Superba H/S, beck-dyed grey. The fiber had been treated with fluorocarbon for antisoiling properties.

Also all dispersing agents (Tamol) were omitted from Composition 2 for another set of samples. Epsom salt (49% MgSO 4 was added to another set of samples. Citric acid was used as a rinse and in the application liquor, Use of citric acid in the treatment liquor or to adjust pH resulted in improved yellowing of the sulfonated aromatic condensate treated fiber. The combination of Epsom salt and citric acid further reduced the tendency to yellow whether due to exposure to ozone or to NO 2 The following tables provide application conditions and results.

3 I N L '7 1 WO 89/02949 PCT/US88/01112 -42- TABLE XVII EVALUATION OF CITRIC ACID USE FOR CONCENTRATE pH ADJUSTMENT ON LIGHT INDUCED YELLOWING APPLICATION AND ANALYSIS DATA Sample

I.D.

6 1 2 3 4 7 8 9 10 11 12 13 14 s.a.c.Used Not Treated Composition 2 Composition 2 Composition 2 Composition 2 Composition 2 Composition 2 Composition 2 Composition 2 Composition 2 Intratex N Intratex N Intratex N Intratex N Nominal s.a.c.

Applied, 0 3. U 3.0 3.0 3.0 3.0 3.0 3.0 3.0 Other Agents/Conc.

0.09 g/1 Citric 0.09 g/1 Citric 0.75 g/1 Citric 0.75 g/1 Citric Citric Acid (pH Citric Acid (pH 0.72% owf Epsom Citric Acid (pH 0.72% owf Epsom Citric Acid (pH Acid Acid Acid Acid adj) adj) Salt adj) Salt adj) 1.25 g/1 citric acid required for pH adjustment.

-43- TABLE XVII (CONTINUED) EVALUATION OF CITRIC ACID USE FOR CONCENTRATE pH ADJUSTMENT ON LIGHT INDUCED YELLOWING APPLICATION AND ANALYSIS DATA Sample

ID.

Appl.

pH s.a.c.

Analyzed Rinse 6 1 2 3 4 5 7 8 9 11 12 13 14 7.5 3.1 3.1 3.1 3.1 3.1 3.1 3.1 2.9 2.9 3.0 3.0 3.0 3.0 Normal Cold Water Normal Cold Water 0.09 g/l Citric (pH 4.1) 0.25 g/l Citric (pH 3.5) 0.75 g/l Citric (pH 3.1) 5.9 g/l Citric (pH 2.5) Normal Cold Water No Rinse Normal Cold Water No Rinse Normal Cold Water No Rinse Normal Cold Water No Rinse 0 1.87 2.18 2.29 2.32 2.44 1.90 2.10 2.04 2.30 2.67 2.39 2.89 2.89 Notes: Carpet temperature before A/T ranged from 55.6-58.9°C (132 to 138°F).

A/T liquor temperature wap 83.9-85 0 C (183 to 185*F).

Actual temperature after A/T ranged from 72.8-77.2C (163 to 171 0

F).

d xo.A~~~ P~J!c eJ SUBSTITUE

SHEET

J

WO 89/02949 WO 89/02949PCT/US88/011 12 -44- TABLE XVIII EVALUATION OF CITRIC ACID USE FOR CONCE;NTRATE pH ADJUSTMENT ON LIGHT INDUCED YELLOWING STAINING PERFORMANCE AND CHANGE-OF-SHADE

DATA

Stain Rating _(O=best,1O=worst) Time Before Blotting With Water,Hr Sample I. D.

6 1 2 3 4 5 7 a 9 11 12 13 14 0.05 9.5 0 0 0 0 0 0 0 0 0 0.1 0 0 0 0.54 9.5 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.1 0.5 0.25 0.25 0.25 1 4 -8 24F Shade Change* 9.5 9.5 9.5 0.5 1.0 1.0 1.0 H-N 0.25 0.5 0.5 0.75 PM-N 0.25 0.5 0.75 1.0 M-N 0.25 0.5 0.75 0.75 M-N 0.5 0.5 1.0 1.5 bl-N 0.25 0.25 0.25 0.25 M-N(Y) 0.25 0.5 1.0 1.0 M-N(B) 0.25 0.25 0.5 0.75 M-N(B) 0.1 0.5 0.5 0.5 M-N 0.5 0,5 0.5 1.0 M-N 1.0 2.0 2.5 2.5 M-N 0.25 0.25 0.25 0.25 (B) 0.5 0.5 0.5 u.5s- s M=margiial, N~none, Y=ye11ow, Bblue j fyi WO 89/02949 PCT/US88/01 112 TABLE XIX EVALUATION OF CITRIC ACID USE FOR CONCENTRATE pH ADJUSTMENT ON LIGHT IN4DUCED YELLOWING COLORFASTNESS DATA Grey Scale Rating Sample 1.D.

6 1.

2 3 4 7 8 9 10 11 12 13 14 Lightfastness,

AFU

20 40 4.0 3.5 2.5 3.0 2.5 3.0 2.5 3.0 3.0 3.0 3.0 3.0 2.5 3.0 2.5 3.0 3.0 3.0 2.5 3.0 3.0 3.5 3.0 3.5 4.0 3.5 4.0 3.5 Ozone fastnE 1 2 3.0 3.0 3.0 3.0 3.5 3.5 3.0 3.0 3.5 3.5 3.5 3. 5 3.5 3.5 2.5 2.5 2.5 2.5 3.0 3.0 3.0 2.5 3.0 3.0 3.0 3.0 3.0 3.5 1 3 N0 2 ~ss, cy Fastness, 3 5 i cy .5 1.0 2.0 .0 2.5 .0 2.5 .0 2.5 .0 3.0 .5 3.0 3 3 3 3 High R.H nitrogen dioxide (AATCC TM-164).

r -46- TABLE XX EVALUATION OF CITRIC ACID USE FOR CONCENTRATE pH ADJUSTMENT ON LIGHT INDUCED YELLOWING BENZOYL PEROXIDE SPOTTING DATA* Spot Visibility (0=Invisible; Sample Benzoyl Peroxide Cone., Soln. in Acetone I.D. 0.01 0.05 0.10 1.0 6 3.0 7.0 8.0 9.0 1 0.75 5.5 6.5 7.5 13 0 0.25 0.5 1.5 14 0 0.25 0.5 1.5 Sample spotted with 1 ml of benzoyl peroxide solution and exposed in chamber at 32.2 0 C (90 0 F) and 80% R.H. for three days.

Example The process on the fabric of Example 4 was repeated, also using Composition 2 with and without the Tamol dispersant, and also adding NH 4 SCN to show its benefits.

Following are the standard continuous process aftertreatment conditions used: Prewet/heat carpet at 90.6°C (195 0 F) and 100% w.p.u. to achieve a carpet temperature piror to treatment of 57.2 to 600C (135 to 140 0

F).

Apply A/T liquor at 400% wop.u. and 79.4 to 82.2*C (175 to 180 0 F) to achieve a post-A/T carpet temperature of 71.1 to 76.7C (160 to 170 0

F).

Aftertreatment, 30-second dwell time before drying.

Summary of Results 1. Application The addition of NH 4 SCN to the Composition 2 bath was found to affect pH only at the lowest concentration. This is an indication of the buffering capacity of Composition 2 solutions.

,xAG SUBSTITUTE

SHEET

fA.

WO 89/02949 PCT/US88/01112 -47- During the make-up and running of the treatment solutions, it was observed that considerably more foaming occurs with Intratex-N alone than does Composition 2.

2. Stain Resistance Composition 2 tended to exhibit better staining performance than Intratex N alone at comparable levels.

The differences between the two diminish as the overall concentration increases.

The addition of NH 4 SCN did not adversely affect the staining performance and, in fact, samples with NH 4

SCN

tended to perform better than corresponding samples without NH 4 SCN. This difference diminishes as the Intratex N concentration increases and overall performance improves.

3. Light and NO 2 Induced Yellowing (Table XXIII) Intratex N and Tamol SN (by themselves) were found to behave differently when exposed to light.

A Intratex N yellows/browns severely at short light exposures (20 afu). This yellowing or browning then fades as the lightfastness exposure is continu'ed. Tamol, on the other hand, greens when exposed to 20 afu and upon continued exposure the green fades to yellow. The overall rating of the shade change does not necessarily improve i from the 20 to 40 afu exposures. The severity of shade change is about equal for Intratex N and Tamol SN.

The break of Composition 2 at short lightfastness exposures (20 afu) appears as a hybrid of Intratex N and Tamol SN alone (at the respective levels in Composition 2).

At both 20 and 40 afu, the break of Composition 2 samples were no worse-to-slightly better than the corresponding Intratex N and Tamol SN only samples.

The addition of NH 4 SCN gives a slight improvement in light induced yellowing. The reduction is greatest at the lower Intratex N levels and decreases as the- Intratex N level increases. Similar behavior is observed between Composition 2 and Intratex N alone, but Tamol SN is less affected, i WO 89/02949 PCT/US88/01112 -48- Yellowing diminishes as the NH 4 SCN level increases. The yellowing is significantly reduced using approximately 0.3% owf NH 4 SCN for every 1.0% owf Intratex

N.

Tamol SN was found to be unaffected by exposure to NO 2 while Composition 2 and Intratex N yellowed severely. The addition of NH 4 SCN improved NO 2 yellowing only slightly, but not enough to raise Grey Scale ratings above 1-2.

4. Ozonefastness (Table XXIII) Intratex N had a significant impact on ozonefastness, both alone and as Composition 2. While overall fastness ratings tended to be better at extended cycles compared to the nontreated control, a significant yellowing occurs.

The yellowing of Intratex N overwhelms any improvement achieved by the addition of NH 4 SCN. Samples incorporating NH4SCN tend to yellow less when exposed to ozone and higher levels yield more improvement. The significant 'improvement in ozonefastness of NH 4 SCN alone was not achieved, but were improved over nontreated samples.

Benzoyl Peroxide Spotting (Table XXIV) The dispersant, Tamol SN, had no effect on the benzoyl peroxide spotting performance. Table XXIV shows the benzoyl peroxide performance identical when 0.3% owf

NH

4 SCN is applied with either Composition 2 or s.a.c. at several levels.

The performance of NH4SCN is not effected at varied s.a.c. levels (as Composition 2 or alone) as shown in Table XXIV.

Benzoyl peroxide spotting improves as the NH4SCN concentration is increased from 0.3 to 0.6% owf.

The improvement becomes more noticeable at the highest benzoyl peroxide concentration and probably beyond.

Conclusions The dispersant, Tamol SN, contributes to the light induced yellowing of Composition 2 but is not the WO 89/02949 PCT/US88/01112 -49sole cause. Elimination of Tamol SN from Composition 2 would not significantly improve or resolve yellowing on Superba H/S substrates. The elimination of Tamol SN could reduce staining performance slightly at lower add-on's and increase the foaming of the treatment liquor upon spray application.

Intratex N is the sole cause of yellowing upon exposure to NO 2 of Composition 2.

Tamol does not interfere with any of the NH 4

SCN

benefits.

Intratex N has a significant impact on ozonefastness (yellows) and overwhelms the ozonefastness improvement benefits of NH 4 SCN. There is, however, a reduction in the yellowing and an improvemeint over Composition 2 alone at a nominal 0.6% owf NH 4

SCN.

NH

4 SCN has no adverse impacts on Composition 2 stain blocking benefits.

There is a reduction in light induced yellowing when NH 4 SCN is applied with Composition 2. The degree of improvement has varied from marginal to significant dtring all internal trials. Higher NH4SCN levels always yield greater improvement.

Benzoyl peroxide spotting performance may be further improved, particularly at higher benzoyl peroxide concentrations, by increasing the NH 4 SCN level to 0.6% owf.

16 TABLE XXI APPLICATION AND ANALYSIS DATA Nominal s.a.c. s.a.c.

Applied Nominal Nominal Nominal Anal, as s.a.c. Tamol SN NH 4 SCN (As Sample Comp.2, Applied* Applied* Applied Rec'd) I.D. pH 1 7.4 0 28 0.3 2.8 0 2 1.0 3.5 1.05 3 1.0 0.3 4.6 108 4 1.0 0.6 4.7 1.05 2.0 3.1 1.91 6 2.0 0.3 3.2 1 93 7 2.0 0.6 3.2 2.16 8 3,0 30 3.19 9 3.0 0.3 3.0 3.58 3.0 0.6 3.0 3.24 11 4.0 2.8 3.23 12 4,0 0.3 2,9 4.20 13 4,0 0.6 2.9 3.90 14 20 3!2 2.10 2.0 0.3 3.2 2.43 16 3.0 2.9 3.83 17 31.0 0.3 2 8 4.20 18 440 2.7 4.97 19 4.0 0.3 2.7 4.73 1.93 29 21 1.93 0.3 2,9 22 2,90 2.8 23 2,90 0.3 2o8 24 3.89 2.8 3-89 0.3 2.9 Materials applied as supplied, not blended or part of a composition.

Notes t carpet temperature before A/T ranged from 55.6 to 62.2 C (132 to 144'F).

A/T liquor temperature was 55o6 to 62.2C (178 to 183 0

F).

Actual temperature after A/T ranged from 70 to 77.80C (158 to 172E).

j K. I SUBSTITUTE SH'E:T

-IA

V

I

WO 89/02949 WO 8902949PCTIUS88/011 12 -51- TABLE XXII STAINING PERFORMANCE DATA Stain Rating (0=best,10=worst) Sample I .D.

1 4 7 8 9 13.

12 13 14 17 19 Time Before Blotting With 0.05 U.5 1 4 Water, Hours 9.5 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 9.5 1,10 1.0 0.5 0.25 0.25 0 0.25 0 0 0 0 0.

0.25 0 0.1 0 9.5 2.0 1.5 0.75 0.5 0.25 0.25 0.2.5 0. 10 0 0.1 0 1.0 0. 2 q 0. 25 0. 1, 0 9.5 3.5 2.0 1.5 1 .01 1.0 0.5 0.75 0.25 0.25 o.5 0.*25 0.*25 0.5 r 5 U.25 0. 25 3.5 3.0 1.0 1.0 1.0 0.5 0.75 0.*25 0.*25 0.25 0.*25 2.0 0.5 0.25 0.25 0.1 24 1 0,75 0.25 0. 0.25 0.05 0.25 0.25 0.1 PCT/US88/O1 112 WO 89/02949 -52- TABLE XXII.

COLORFASTNESS DATA Grey ScaleRating Sample

I.D.

28 2 3 4 6 7 a 9 i1 12 13 14 is 16 17 18 19 21 22 2 3 24 Lightfastness,

AFU

20 40 3.0 4.0 3.0 2.5 3.0 3.0 3.5 3.5 3.5 2.5 2.5 2.5 2.5 3.0 3.0 2.0 2.5 2.0 2.5 2.5 2.5 2.0 2.0 2.0 .2.0 2.5 2.5 2,5 2.5 3.0 2.5 2.0 2.0 2.5 2,5 2-(0 2.0 2.5 2.0 1,9. 5 2.5 21.; 2.5 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Ozonefastness,_cy 1 2 3 5 3.0 2.5 2.0 1.0 3.5 3.0 3 0 3.0 2.5 2.5 2.0 3.0 2.5 2.5 2.5 3.0 2.5 2.5 2.5 2.5 2.5 2.0 2.0 3.0 2.5 2.5 2.0 3.0 2.5 2.5 2.5 2.5 2.5 2.0 2.0 2.5 2.5 2.5 2.0 3.0 3.,0 2.5 2.5 2.5 2.5 2.0 2.0 2.5 2.5 2.0 2.0 3.0 3.0 2.5 2.5 2.5 2.5 2.0 2.0 2,5 2.5 2.0 2.0 2.5 2.5 2.0 2.0 2.5 2.5 2.5 240 2.0 2.0 2.0 2.0 2.5 2.5 2.0 2,5 2.5 3.0 3.0 3.0 2.5 3.0 2.5 3.0 2.5 J.0 2.5 N0 2 Fastness, 1 cy 115 115

I

High R.H nitrogen dioxide (AATCC TI-J64) Ar '1 -53- TABLE XXIV BENZOYL PEROXIDE SPOTTING DATA* Sample I. D.

2 3 4 6 7 8 9 11 12 13 .44 Spot Visibility (0=Invisible;10=Bright) Benzoyl Peroxide Conc., Soin. in Acetone 0.005 0.01 0.05 0.1 1.5 6.5 8.0 0 0 0.75 1.0 0.25 2.0 6.75 8.0 0 0 1.25 4.0 o 0 0.25 0.5 0.5 1.75 5.5 6.5 0 0 0.5 1.0 0 0 0.1 0.75 0.25 2.0 7.25 7.5 0 0 0.5 1.25 0 0 0.25 0.5 0.75 1.0 2.5 7.5 8.0 0 0 0.5 1.0 0 0 0.1 0.5 1.25 0.5 1,5 6.5 7.5 0 0 0.5 1.0 18 1 9 0.25 0 1.0 0 6.5 0.5 7.5 0.75 1.75 *Sample spotted and exposed in three days.

with 1 ml of benzoyl perox.de solution chamber at 32.2*C (90 0 F) Fnd 80% R.H. for t ;131TTU T E S it irZ -54- Example 6 This example demonstrates the two-step, batch-batch (beck-beck) process embodiment of this invention.

Prior art has shown that application of sulfonated aromatic condensates (stain blockers) to nylon improves resistance to staining by most food colors. In the prior art, the preferred mode of application has been a low temperature (48.9 to 82.2"C (120 to 180"F) treatment with the stain blocker after dyeing has been completed. Also, prior art includes application of stain blockers concurrent with dye application. This invention embodies application of a portion of the total stain blocker concurrently with dye application, and application of the remainder in a low temperature aftertreatment step.

(two-step process).

The two-step process results in a level of stain Sperformance superior to that which is achieved by the 1 prior art at, the same total add-on concentration of stain blocker. In addition, use of ammonium thiocyanate in tle aftertreatment step improves dye fastness to ozone, benzoyl peroxide (acne medications) and light.

I It is theorized that the improvement over prior art is achieved by maximization of the concentration of stain blocker in a thin zone near the fiber surface and that this condition results in better stain resistance.

The two-step process promotes this condition by sorption of a portion of the stain blocker during the dyeing 4| operation which is fully penetrated into the cross-section of the nylon fiber. The sorption of the portion of stain blocker subsequently applied in the low temperature aftertreatment step in retarded by the presence of the existing portion already on the fiber, therefore, increasing the effective concentration near the fiber surface. The presence of magnesium sulfate in both steps of the process accelerates rate of sorption of the stain blocker by increasing the bath electrolyte concentration V 2 TITUTE

SHEET

*T

i -I Lw

I

WO 89/02949 PCT/US88/01112 and by complexing with the stain blockers thus reducing molecular mobility in the nylon.

Example 6 Part 1 This example shows that two-step process is superior to either concurrent or aftertreatment.

Carpet Fabric: 1185 denier fluorocarbon treated Superba Heat Set Process: A total of 2.0% owf Intratex N was applied to carpet.

The total was distributed between dyebath and aftertreatment in the following ways: Dyebath, Aftertreatment, 0 100 50 100 0 Varying amounts of Magnesium Sulfate were used owf to 4% owf).

Dyebath conditions were typical of industry practice.

Dyeing procedure as follows: 1. Load fabric and wet out at 20:1 Liquor Ratio 2. Add 1.0% owf Dowfax 2Al-sodium mono-and didodecyl disulfonated diphenyl oxide (45% active) 3. Add the specified amount of Intratex N-1 4. Add the specified amount of Magnesium Sulfate Run 5 minutes 6. Add 0.5% Sequestrene 30A (EDTA) or equiv.

7. Add 1% owf ammonium sulfate 8. Add 0.5% owf ammonium hydroxide 9. Add predissolved dyes Run 10 minutes 11. Raise temperature to boil 12. Boil 30 minutes 13. Drop and rinse cold i: 7 -56- 14. Aftertreat if indicated Aftertreatment procedure as fol.ows: 1. Refill Beck at 20:1 Liquor Ratio 2. Add specified amount of Magnesium Sulfate 3. Add specified amount of Intratex N1 4. Run 10 minutes Lower pH to 2.0 to 2.1 with sulfamic acid 6. Raise temperature to 71.1 0 C (160*F).

7. Hold at temperature 20 minutes 8. Drop bath and rinse cold Performance: Reference samples Nos. 17 through 31 in Table XXV Samples 23, 24 and 25 prepared with the 50%/50% two-step process are superior. Those samples which passed the dip test were further tested by the drop test.

Test Protocols: 1. "Dip Test" Immerse a 5 gram sample of unfinished carpet into a large excess of Cherry Kool-Aid (unsweetened) at room temperature for 30 minutes. Rinse with cold water, dry and assess vhe stain.

2. "Drop Test"- Drop 30 ml. Cherry Kool-Aid 1 (unsweetened) onto the finished carpet from a height of 12 inches. Allow to stand for seven hours. Blot with paper towels using water spray to aid in removal.

Example 6 Part 2 This example shows use of ammonium thiocyanate in two-step process for irmpoved resistance to benzoyl peroxide and light fading.

Carpet Fabric: 1700 denier Superba Heat Set (High ICP fiber)

'I

i i Process: Using the process of Part 1, a total of 2.8% Intratex N was applied using the 50%/50% two-step mode.

A second sample was prepared in the same way but an Intratex N pre-formulated mixture containing ammonium thiocyanate (Composition 3) was used in the aftertreatment step. Composition 3 is 40% Intratex N-l, 12% ammonium thiocyanate, 21.5% Monawet MB45, 26.5% Water.

1 Registered of General Foods Corporation.

41 :rl .1 V1m k4V WO 89/02949 PCT/US88/01112 -57- Performance: Reference samples and in Tables XXVI to XXVIIT. Using the "Drop Test" Protocol from Example 1, sample has good stain resistance (somewhat poorer than but very significant improvements in benzoyl peroxide and light fading.

Example 6 Part 3 This example shows that 50%/50% two-step mode is preferred and the 2% magnesium sulfate is optimum.

Carpet Fabric: .1185 denier fluorocarbon treated autoclave Heat Set (high ICP fiber) Process: Using the process of Part 1, a total of Intratex N-l was applied using the two-ste- 'e.

The total was distributed betwee ath and aftertreatment in the following ways: Dyebath, Aftertreatment, 0 100 5 Varying amounts of magnesium sulfate were used owf to 4% owf) Performance: Reference samples 2 through 23 Table XXIX.

Using the test protocols from Example 1, samples through 23 (50%/50% application mode) have best stain resistance. Sample 20 is best of group (uses 2% and 2% owf magnesium sulfate).

r WO 89/02949 -58- TABLE XXV Dyebath Aftertreat No. s.a.c. ES* a..

1 0 0- 2 0 0 1.6 3 0 0 1.6 4 0 0 1.6 0.8 0 0.8 6 0.8 0 0.8 7 0.8 0 0.8 8 0.8 2.0 0.8 9 0.8 2.0 0.8 0.8 2.0 0.8 11 0.8 4.0 12 0.8 4.0 0.8 13 0.8 4.0 0.8 14 1.6 0 1,6 2.0 16 1.6 4.0 17 0 0 2.0 18 0 0 2.0 19 0 0 2.0 1.0 0 1.0 21 1.0 0 1.0 22 1.0 0 1.0 23 1.0 2.0 1.0 24 1.0 2.0 1.0 1.0 2.0 10 26 1.0 4.0 1.0 27 1.0 4.0 1.0 28 1.0 4.0 1.0 29 2.0 0 2.0 2.0 31 2.0 4.0 32 0 0 2.8 33 0 0.

*Epsom~ ,a&lt P~pass S=:4slight st~ain mrent

ES*

0 2.0 4.0 0 2.0 4.0 0 2.0 4.0 0 0 2.0 4.0 0 2.0 4.0 0 4.0 0 0 PCT/US88/O1 112 "Dip" Test

F

F

F

F

F

F

F

S

P

S

F

F

S

F

F

F

F

F

F

P

s

P

F

F

F

WO 89/02949 1 WO 8902949PCT/US88/O1 112 -59- TABLE XXV (CONTINUED) Dyebath No. s.a.c. ES* Aftertreatrnent s.a.c. ES* 34 36 37 38 39 41 42 43 44 46 0 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 2.8 2.8 2.8 0 0 0 0 2.0 2.0 2.0 4.0 4.0 4.0 0 2.0 2.8 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 1.4 4.0 0 2.0 4.0 0 2.0 4.0 0 2.0 4,0 K/A "Dip" Test

F

F

F

F

S

P

P

P

P

P

F

P

P Pass 'N Stain) F =Fail (Noticeably Stained) S Slight Stain (just Detectable) *Epsomn salt No.

1 2 3 4 6 7 8 311 12 13 *Drop test 7-Flour (ool-Aic 3tainiic 7.5 1.5 0.75 1.0 1.0 0.7.5 0.25 TABLE XXV (Continued) Gray Sc~±1e Xenon Light-Fastness Chade 20 AFU Change 3.0 3.0 3.5 3Q0 2.5 3.0 3.5 3.5 3.5 3.5 3.5 4,0 WO 89/02949 WO 8902949PCT/US88/01 112 TABLE XXV (CONTINUED).

Gray Scale

I

a No.

14 16 17 18 19 22 23 24 26 27 28 29 31 32 33 34 36 37 30 38 39 41 42 43 44 46 0.5 0 0.1 0.5 0 7-Hour Kool1-Aid Staining 1.0 Xenon Light-Fastness 20 AFU 2.5 2.0 3.0 4.0 3.5 4.0 4.0 3.5 4.0 3.5 3.5 3.5 1. 0 3.0 2.5 2.5 2.5 3.5 4.0 4.0 2.5 2.5 2.5 2.0 2,5 2.5 3.0 3.0 3.0 2.0 2.5 3.0 Shade Change 315 3.45 0.5 0.1 0 0 0 0 0.1 0.1 -61- TABLE xxv: No.

A

B

C

D

E

Description Control Aftertreatments 5.0% Intratex N-1+4% ES* 10% Composition 3 10% Composition 3+4% ES 12.5% Composition 3 Two-Step 1 l.0 IntratexN-l+2.0'OES 1,4% IntratexN-l+2.0%ES 1.4% IntratexN-l+4.0%ES 1.4% IntratexN-1+2.0%ES Original Samples Before Blot, Hours 1 7 0.10 0.75 0.75 0.25

F

G

H

I

I.0% 1.4% 1.4% 3.5% Intratex +2.0%ES Intratex +4.0%ES Intratex +4.0%ES Comp. 3 +4.0%ES 4.50 1.00 0.10 1.00 ES-Epsom salt Original Samples Before Blot, Hours N.4 7 24 A 8100 8.00 8.00 B 0.25 0.50 0.50 c 1.00 1.50 1.00 D 1.00 1.00 1.50 E 1.00 1.00 1.50 F 3.50 4.00 3,00 G 2.00 2.00 1,50 H- 0.10 0.25 0,50 1. 1.00 1.50 0.75 Error I~n application s.a.c.

by analysis 13.58* 4.45 4.64 5.83 1.69 2.14 2.57 2.14 Steam Cleaned Before Blot, Hours 1 4 7 24- 2.00 3.50 3.00 3.50 2.50 4.00 3.50 4.00 4.00 3.00 4.00 4.00 1.50 4.50 3.50 4.00 6.00 5.50 6.50 6.50 4.00 4.00 5.00 4-503 5.50 4.50 4.50 5.00 4.00 5 5.00 4.50 Note: All aftertreatments at p11 Drop test 0-beat 10 worst 71.1 *C (160*F) 9 j SUBSTITUTE

SH-EET

il LA 2 WO 89/02949 PCT/US88/011~12 -62- TABLE XXVII S-Dot Visibility* Benzoyl Peroxide Spotting Data No.

A

B

D

E

F

G

H

I

0. 005 3.50 3 .00 0 0 0 3.00 4.50 4.00 0.25 0.01 6.50 6.50 0.*50 0.*25 0.*10 6.50 6.50 6.00 0.*75 10= Bright 0.05 7.50 7 .50 1.00 1 .00 0.75 7.50 7.50 7.00 1.50 0.1 9.00 8.00 2.00 3 .00 1.*50 8.00 8.00 8.00 3.00 9.00Q 8. 00 2 3 .00 1.00 9.00 8. so 8.50 3 .00 0 =invisible; TABLE XXVII.I Gray Scale F,..ng k No.

A

B

C

D

E

F

00 Lightfastmn;ss,

AAFU

20 40 60 4 3 2-3 3 2-3 2 -3 4 3-4 3 4 3-.4 3 4 3-4 :3 4-5 4 4 4 3-4 3 3-4 3 3 4 3 3-4 Ozorie Fastness, cycles 1 2 3-4 2-3, 4-5 4 4-5 4 4 3-4 4-5 4 4-s 4 4 3-4 4 3-4 4 3--4 tio, 2 Fastness, Cycle 1 2 2- 3 2-3 2-3 2 3 Shade.

Change 3 .3-4 3-4 4 2 3 2-3 3 MMMMMRWT 04 WO 89/02949 PCT/US88/O1 112 -63- TABLE XXIX Dyebath %owf No. s.a.c. ES* 1 0 0 2 0 0 3 0 0 4 0.15 2.0 0.15 2.0 6 0.15 4.0 7 0.15 4.0 0 .3 2.0 9 0.3 2.0 0.3 4.0 11 0.3 4.0 12 0.6 2.0 13 0.6 1.

14 0.6 4.0 0.6 4.0 16 0.9 ,2.0 17 0.9 2.0 18 0.9 4.0 19 0.9 4.0 1.5 2.0 21 1.5 2.0 22 1.5 4.0 23 1.5 4.0 *ES Ep-Epsoi salt *Forced ranking (K/A 1 =Best Aftertreat. %owf S.a.c. b 3.0 3.0 2.85 2.85 2,85 2,85 2 .7 2.7 2.7 2.7 2.4 2.4 2.4 2.4 2.1 2.4 2.1 2,1 1.5 1.5 1.5 1.5 K(ool-Aid) 2.0 4.0 2.0 4.0 2.0 4.0 2.-0 4.0 2.0 4.0 2.0 4.0 2.0 4.0 2.0 4.0 2.0 4.0 2.0 4.0 2.0 4.0 -Dip est** 23 22 21 17 13 16 14 18 12 9 19 11 7 a 6 1 4 2 3 9 ii WO 89/02949 PCT/US88/O1 112 -64- TABLE XXIX (CONTINUED) 7-Hour Kool-Aid No. Staining* 1 7.50 2 2.50 3 3.00 4 1.0GO 1.50 7 1.50 8 1.00 9 1.50 1.00 11 1.50 12 1.00 13 1.00 14 1.50 1.50 16 0.75 17 0.50 18 0.75 19 1.00 0.10 21 0150 22 0.10 23 0.75 3C *drop test Xenon Liihtfastness 20 AFU 3-4 4 4 4 3-4 4 4 4-5 3 3-,4 3 3-4 4 3-4 3 3-4 4 3-4 3-4 3-4 3-4 3 Shade Change 4 4-5 5 5 4-5 4-5 4-5 4 4 4-5 4-5 4 4-5 4 4 4-5 4-5 4 4 4 4 4-5 s. a. C.

by analysis 3.78 3.93 3. 33~ 3 .4 3. 3 tl 3 3.60 3.60 3.38 3.29 3.24 3 .00 3.15 3.22 3.15 3 .00 3.03 3.10 2. 72 2.86 2.*82 2.91 rl Example 7 This example describes use of a sequestering agent in the continuous aftertreatment process of this invention. The c'eneral procedure was as in Example 2.

Experimental Summary Substrate 1185 denier fluorocarbon treated Superba H/S in 32 ounce per square yard cut pile fabric construction and beck dyed into Argent Grey shade.

Continuously aftertreated using nominal add-on 15.9% owf Composition 2 owf Intratex N) with no additional pH adjustment (actual pH 2.9).

Calquest ADP (Mfrs. Chem.) added to treatment bath containing Comp. 2 at levels corresponding to 0.5 and 1.0% owf.

Standard Continuous Process Prewet/heat carpet at 90.6 0 C (195*F) and 100% w.p.u. to achieve a carpet temperature prior to treatment of 57.2 to 60°C (135 to 140 0

F).

Apply A/T liquor at 400 w.p.u. and 79.4 to 82.2 0 C (175 to 180 0 F) to achieve a post-A/T carpet temperature of 71.1 to 76.7 0 C (160 to 170*F).

After treatment, 30-second dwell time before washing (at 40:1 liquor ratio), hydroextraction and drying.

Summary of Results The change in the dyed shade was reduced (went more to the blue side) when the sequestering agent was used.

Light induced yellowing was improved between 1/ to 1 gray scale unit at 20 AFU using the sequestering agent. No further improvement was noted going from the low to the high concentration. There also appeared to be more of an in: rovemert (or fading) of the yellowing in going from 20 to 40 AFU's when the sequestering agent was included.

Yellowing upon exposure to ozone was also minimized when the sequestering agent was included. Only a l SBSSTITUTE SHEET 9 1

I

WO 89/02949 PCT/US88/01112 -66slight reduction in the yellowing upon exposure to nitrogen dioxide was observed.

There was no impact on staining, but a slight reduction in the Intratex N analyzed on carpet level was observed when the sequestering agent was used.

Conclusions The use of sequestering agent in the Composition 2 formulation shows reduced yellowing at low lightfastness exposures and upon exposure Lo ozone, j i i f t i ii di TABLE XXX EFFECT OF SEQUESTERING AGENTS ON LIGHT INDUCED YELLOWING (NOMINAL 3.0% OWF INTRATEX N ANALYSIS, STAINING PERFORMANCE,

CHANG

r -OF-SHADE AND COLORFASTNESS DATA Sample

I.D.

1 2 '3 4 Nominal Comp. 2 Conc., owf

N.T.

,3.0 3.0 3.0 Nominal Seq.

Agent Cone., owf* 0.5 1.0 Stain Rating Time Before Blotting With Water, Hours Intratex N Analyzed, 0 4.22 3.41 3.66 0.05 0.5 1 7.0 8.5 8.50 0 0 0 0 0 0 0 0 0 4 0.1 0.1 0.1 Stain Rating (0=best,10=worst) Grey Scale Rating_ 35 Time Before Light- Ozo Blotting With fastness, fast: Sample Water, Hours Shade AFU c I.D. 8 24 Change 20 60 1 1 8.5 8.5 3.5 2.5 3.0 2 0.1 0.1 M(B) 2.5 3.0 3.0 3 0.1 0.1 M-Y(8) 3.5 4.0 3.0 4 0.1 0,1 M-Y(B) 3.5 3.5 3.0 Calquest ADP (Manufacturers Chemical) N.T. Not treated High R.H. Nitrogen Dioxide. AATCC TM-164.

neness y 2 2.5 2.5 3.0 3.0

NO

2 Fastness, cy 1 WO 89/02949 WO 8902949PCT/US88/01 112 -67- Other sequestering agents would also be useful, for example, the polyphosphates, such as Calgon w'hich is sodium hexamet-aphos ph ate, aminocarboxylic acids, such as EDTA or ethylenediaminetetraacetic acid, the amino alcohols, and the hydroxycarboxylic acids, including citric acid.

TABLE XXXI ADDITION OF SEQUESTERING AGENTS TQ INHIBIT LIGHT INDUCED YELLOWING .0 (1185 Fluorocarbon Treated Superba Substr~ate, Nominal 15.9% owf Composition 2 3.0% Intratex N) Analysis and Colorfastness Data Sample I D 1 2 3 4 6 7 8 9 Additives Not Treated No Additive (Cornp. 2 only) 0.50% owf Calguest AUP 0.10% owf Sequestrene 30A 0.25% owf Sequestrene 30A 0.50% owf Sequestrene 30A 0.10% owf SHNIP* 0.25% owf SEIMP* 0.50% owf SHMP* A/T pH 3.0 3.3 3.2 3.7 3.* 3.0 3.3 3.6 Analyzed 0 2.46 2.95 2.75 3.02 2.*54 2.80 2.95 3.09 Grey Scale Ratingj Lightfastness, Ozonefa Sample AFU c I.D. 20 40 1 1 5.0 4.5 3.0 2 3.0 5 3,5 3 3.0 3.5 4.0 4 4.0 4.0 3.5 4.0 3.5 4.0 6 4.0 3.5 3.5 7 4.0 3.5 3.5 a 3.5i 3.5 3.0 9 3.5 3.5 3.5 *Sodium Hexarnetaphosphate.

**Sulfamic Acid required to lower pH added to A/T liquor.

~stness, 2 2.5 3.0 3.0 3.0 3.0 3.0 3.0 2.5 3.0 NO02 Fastness, cy -1 after the additive WO 89/02949 PCT/US88/01112 -68- TABLE XXXII ADDITION OF SEQUESTERING AGENTS TO INHIBIT LIGHT INDUCED YELLOWING STAINING DATA Stain Rating (0=best 10 worst Sample I.D. A/T pH 1 2 3.0 3 3.3 4 3.2 3.7 6 3.3 7 3.0 8 3.3 9 3.6 M=moderate N=no Time Before Blotting With Water, Hours 1 9.5 0.25 0.75 0.25 0.5 0.5 0.25 0.5 0.25 4 9.5 0.25 0.75 0.75 1.0 0.5 0.75 1.0 0.5 8 9.5 0.75 0.75 0.75 1.25 1.0 0.75 1.0 1.0 24 1.25 0.75 0.75 1.25 1.5 0.75 1.0 1.0 Shade Change*

M-N

M-N

M-N

N

M-N

N

N

N

I rl Example 8 Method for Exhausting Ammonium Thiocyanate Onto Dyed Nylon Firie.- t Improve its Resistance to Oxidizing Agents Description of the Embodiment Dyed carpet fiber, especially that made from nylon, whether or not it is treated with a sulfonated aromatic condensate or other treatments, is susceptible to significant color fading due to exposure to ozone, benzoyl peroxide and products containing chlorine. The problem was lessened to some extent when the dye industry changed over to acid dyes from disperse dyes. Acid dyes were less able to migrate and be destroyed by ozone because they were electronically bound to the nylon. However, the use of acid dyes did not eliminate these color fastness problems.

There are many antioxidants and antiozonants available on the market. These products are usually aromatic and contain amine or sulfur functionalities.

These products have several disadvantages: aromatics usually yellow the fiber upon further heat treatment, and the amines and sulfur functionalities cause a reduction in nylon lightfastness. Also, these chemist'ries probably act as sacrificial agents and it has been difficult to apply enough onto the fiber to have long term benefit.

The thiocyanates, such as ammonium thiocyarate, are antiozonants that are well known. The cation of the thiocyanate may be ammonium, sodium, potassium, zinc, copper, ferrous, ferric, methyl or phenyl. They had the additional advantage over the other antioxidants in that they do not reduce lightfastness. However, it has not been economically possible to apply enough of the thiocyanat-. during dyeing to have long term effectiveness as it is also a sacrificial agent. (Ammonium thiocyanate also appears to aglomerate the dye molccules which also improves ozone fastness.) In order to apply ammonium thiocyanate economically, it is necessary to devise a process in which it essentially exhausts onto the fiber. At pH=7 and 100°C (212'F) (normal dyeing conditions), the ammonium thiocyanate will not exhaust onto the fiber as it is water soluble and not very substantive to nylon. However, it has been found that at acidic pH's, especially at about pH to pH 5, the ammonium thiocyanate will exhaust onto the nylon.

Comparison of Various Thiocyanates A comparison was made of the performance of several organic and inorganic thiocyanate compounds which had been aftertreated onto fluorocarbon treated nylon carpet fiber knitted into sleeves at pH=2, 60°C (140*F), SUZiT~tS ,i X n i,? r ,i r

:I

Ek WO 89/02949 PCT/US88/01112 20:1 liquor:goods and 20 minutes. No dyes were added.

The following thiocyanates were evaluated: Added as Received, Thiocyanate Activity, 0.30 NH 4 SCN 100 0.32 NaSCN 100 0.38 KSCN 100 0.48 CuSCN 100 2.57 CH 2

(SCN)

2 3.13 Ph(S)N=CCH 2 SCN Tho amounts added introduced an equivalent quantity of thiocyanate concentration onto the fiber.

The amriionium, sodium and potassium thiocyanates were all equally superior to untreated nylon in resistance to ozone, benzoyl peroxide and chlorine bleach fastness.

The other 15 thiocyanates were slightly more resistant to these color fade tests than the untreated nylon. The xenon lightfastness of all the samples were similar to untreated nylon except CuSCN which was more resistant and the phenyl-based thiocyanate which was much worse.

Effect of pH Using the same conditions as above but varying pH and using only NH 4 SCN, the percent exhaustion of i NH 4 SCN onto fiber was measured at the pH levels shown.

i H Exhaustion, 1 2 3 4 6 8 7 9 Effect of Temperature In another test at the same conditions pH 2 temperature was varied to achieve the following exhaustion levels.

I/L I i I I -il- -71- Temperature, Exhaustion, "F °C 23.9 100 37.8 66 120 48.9 63 140 60.0 180 82.2 200 93.3 98 Thus by raising the temperature, it is expected that more complete exhaustion can be achieved at higher pH levels.

In a separate test at the same conditions but varying time, it was found that time between 5 and minutes had little effect on exhaustion levels. On the other hand, increasing the concentration of NH 4 SCN lowers the level of exhaustion. It was also found that putting increasing amounts of NH 4 SCN on the fiber has only a very small effect on ozonefastness over 2,000 ppm, a little effect over 1,000 ppm, but a large effect between 0 and 1,000 ppm. It was noted that the E in the standard 5-cycle AATCC ozonefastness changed from 6 at 500 ppm to only 2 at 1,000 ppm.

DISCUSSION

The above examples are but a few of the many embodiments and variations of this invention. One skilled in the art would be able to select the proper conditions and amounts of chemical compounds for other embodiments of this ivention to achieve the results desired after learniug the teachings of this invention, including the Examples and the broader teachings of the Summary of the Invention above. The broader teachings are based on economic, technical and practical limitations to practice the invention. However, it may sometimes be useful to operate outside these economic or practical limitations for special reasons.

The following discussion will describe some of the practical, economical and/or technical limitations of the parameters of the embodiments of this invention.

A4 tFSUTITUTE SHEEy 0* 1 1 2 -72- First, regarding the operating conditions of the continuous aftertreatment method, including two-step application methods, of this invention, the following table lists reasons for the limitations given.

Limitation Variation Reason preheat water temp. below less uniform application 0 C (140 0 F) and carpet during the following treattemp. below 54.4 0 C (130 0 F) ment and less effective or economic to heat carpet 0 preheat water temp. above atmospheric process, water 100°C (212 0 F) and carpet cannot be heated above the above 99°C (210 0 F) boiling point less than 75% w.p.u. less uniform, poor preheat step penetration 5 extracting to less than less uniform, poor w.p.u. penetration extracting to above 190% dilutes following appliw.p.u. cation liquor, less effective 0 application pH below 1.5 corrosive application pH above 5.5 less effective, due to compounds of aqueous soln.

penetrating too deep into fiber, at very high pH no exhaustion of compositions application less than less effective 200% w.p.u.

application over 650% w.p.u.

conc. of s.a.c. less than 0.25 g/1 cone. of sa.c. over 40 g/1 application soln. temp.

under 60°C (140 0 F) and carpet temp. under 54.4°C (130°F) application soln. temp.

over 100°C (212 0 F) and carpet temp. over 99°C (210°F) less than 0.05% ow4 MgS04 more than 0.8% owf MgSO 4 carpet fabric cannot hold much more aqueous solution less effective uneconomical less effective atmospheric process, water cannot be heated above the boil less effective adverse color fastness results SUBSTITUTE

SHEET

1 cZ r t I '9 -73less than 0.03% owf NH 4

SCN

more than 1% owf NH 4

SCN

less than 0.15% owf s.a.c.

more than 7.5% owf s.a.c.

more than 6 or 3 parts to parts of s.a.c. of the respective dispersing agents less effective uneconomical less effective uneconomical uneconomical, possible adverse chemical activity The following table lists reasons for limitation parameters for the two-step, batch-batch method of this invention.

Limitation Variation Reason second gitep pH below 1.5 second step pH above 5.5 second step temp. below 43 0 C (10?) second step temp. above 91°C (195°F) first second step liquor: fabric ratio below 10 first second step liquor: fabric ratio above 100 first step temp. below 70°C (158 0

F)

first step temp. above 100°c (212 0

F)

first step treating time less than 15 minutes first step treating time over 90 minutes second step treating time under 5 minutes less than 0.05% owf fluorocarbon on pretreated fabric over 0.4% owf fluorocarbon on pretreated fabric corrosive less effective, due to compounds of aqueous soln.

penetrating too deep into flber, at very high pH no exhaustion of compositions uneconomical, takes too long less effective, due to compounds of aqueous soln.

penetrating too deep into fiber less uniform, poor wetting and penetration uneconomical unecozomical, nonuniform application, takes too long atmospheric process, water cannot be heated above the boil blotches and streaks, nonuniform uneconomical nonuniform application does not provide antisoiling effect uneconomical SUBSTITUTE

SHEET

WO 89/02949 PCT/US88/01112 -74- Limitation VF.iation Reason below 0.25% owf MgSO 4 ineffective over 4% owf MgS0 4 poor lightfastness, uneconomical, poor dyeing, shade changes below 0.03% owf NH 4 SCN ineffective above 1% owf NH 4 SCN uneconomical below 0.15% owf s.a.c. ineffective above 7.5% owf s.a.c. fabric discolors, fabric stiff, poor dye yield, yellowing The benefits of the best mode of this invention using Composition 1 in a two-step, continuous-continuous process as described.above in Example 1 are given below, Most or some of the individual benefits given are also achieved by the other embodiments of this invention.

improved stain resistance, particularly for carpet fabric of high ICP nylon fiber, substantially eliminates light induced yellowing of .sulfonated aromatic condensate treated fiber, reduces NO2 yellowing of sulfonated aromatic condensate treated fiber, improves resistance of dye on sulfonated aromatic condensate treated fiber to fading from zaone and oxidation by benzoyl peroxide, improves penetration of sulfonated aromatic condensate and treatment chemicals into the carpet fabric, including the base or backing, does not significantly impact the soil resistance of the fluorocarbon treatment on the fiber of the carpet fabric, improves durability of the sulfonated aromatic condensate and treatment chemicals to steam cleaning with high pH detergents.

Claims (14)

1. A method to continuously treat dyed nylon carpet fabric to impart improved resistance to staining comprising: preheating said dyed carpet fabric with water at a temperature between 60 and 100 0 C (140 and 212°F) to a wet pick-up of from 75% to 200% by weight, and a carpet temperature of between 54.4 and 99 0 C (130 and 210*F). extracting said water from said carpet fabric to a wet pick-up of between 30% to 190% by weiaht, then applying an aqueous solution of an effective amount of a sulfonated aromatic condensate to improve stain resistance and an effective amount of a thiocyanate wherein the thiocyanate cation is selected from ammonium, sodium, potassium and zinc to reduce yellowing of the sulfonated aromatic condensate treated carpet, to said carpet fabric at a pH of between 1.5 to 5.5, at a Sconcentration of between 0.25 and 40 grams of solids of said condensate per liter of aqueous solution, at a wet pick-up of between 200 and 650% by weight, at an aqueous solution liquor temperature of between 60 and 100*C (140 and 212 0 to achieve a carpet fabric temperature between 54.4 and 99°C (130 and 21007), then 25 holding said carpet in said aqueous solution for between 0.5 to 90 seconds at a temperature above 54.4 0 C (130-F).

2. The method of claim 1 wherein the dyed carpet fabric also comprises an effective amount of a fluor-carbon compound to improve resistance to soiling of the carpet.

3. The method of claim 1 or 2 wherein said aqueous solution also contains an effective amount of dinpersing agent to disperse said thiocyanate and said sulfonated aromatic condensate. i 911014,dbdat086,17019,res,75 ,0 (I 1 I- I ui, -76-

4. The method of any one of the preceding claims wherein said aqueous solution also contains an effective amount of a salt having a divalent cation to improve the stain resistance of said carpet. The method of claim 2 wherein said aqueous solution also contains an effective amount of a divalent cation to improve stain resistance of said carpet.

6. The method of any one of the preceding claims wherein said aqueous solution is buffered with an effective amount of citric acid or any other acid with a sequestering agent to improve yellowing of said carpet 15 fabric.

7. The method of claim 1 wherein preceding said initial, preheating step a portion of said effective amount of said sulfonated aromatic condensate is added during dyeing of said carpet fabric, so that the total of effective amounts of sulfonated aromatic condensate in both steps is less than the total effective amount useful in either the first dye step, solely, or in the subsequent application step, solely, or so that a more 25 effective degree of stain resistance of the carpet fabric is achieved at the same total of effective amounts of sulfonated aromatic condensate in said two steps as compared to the same amount in either step, solely.

8. The method of claim 7 wherein an effective amount of a salt having a divalent cation to improve stain resistance of said carpet is also added during said dyeing so that stain resistance o- the nylon fiber in the carpet fabric, especially an easily dyed nylon fiber having a high index of crystalline perfection and having a very open internal crystal polymer structure, is enhanced and durability to steam cleaning of said stain S/ 911014,dbdat086,17019.res,76 ,M -77- resistance is enhanced, or said effective amount of sulfonated aromatic condensate is lower to achieve the same level of stain resistance.

9. The method of claim 7 or 8 wherein said fabric comprises a fluorocarbon present before dyeing. The method of improving stain resistance of nylon or wool fiber comprising treating said fiber with a combination of an effective amount of each of a sulfonated aroIatic condensat and a thiocyanate to improve resistance to oxidation by ozone or other strong oxidizing agents, such as benzoyl peroxide. 15 11. The method of improving stain resistance of nylon fiber, particularly fiber having a high index of i. crystalline perfection, for carpets comprising treating i Ssaid fiber with a combination of an effective amount of S' each of a sulfonated aromatic condensate, thiocyanate and a salt having a divalent cation to improve stain resistance of said carpet without yellowing. |14 S 12. The method of claim 11 wherein said fiber also comprises an effective amount of a fluorocarbon compound 25 to enhance soil resistance of the fiber.

13. The method of claim 10 wherein an effective i amount of citric acid or any acid with a ,oequestering agent is to buffer the condensate and thiocyanate so that light induced yellowing of the stain resistant fiber is reduced.

14. The method of claim 11 wherein an effective amount of citric acid or any acid with a sequestering agent is used to buffer the condensate and thiocyanate so that light induced yellowing of the stain resistant fiber is reduced. l At A 9ll0914d' -aL086,170l9.res,77 re r -78- A method of dye and treat, in two batch steps, nylon carpet fabric to impart improved resistance to staining comprising dying, in a first step, the undyed carpet fabric in a dye bath liquor in the presence of a portion of an effective amount of a sulfonated aromatic condensate to improve stain resistance of said carpet in an aqueous solution at an elevated temperature, then rEmnoving the dye bath liquor from the dyed carpet fabric, then rinsing the dyed carpet fabric, then applying, in a second step, another portion of an effective amount of a sulfonated aromatic condensate to improve stain resistance of said carpet and an effective 15 amount of thlocyanate wherein the thiocyanate cation is selected from ammonium, sodium, potassium and zinc to reduce yellowing of the sulfonated aromatic condensate treated carpet in an aqueous solution, to said dyed carpet fabric, at a pH of between 1.5 to 5.5 and at a liquor temperature of between 110 to 60 to 91 0 C (195°F). S" so that the total of said portions of effective amrount of sulfonated aromatic condensate in both steps is less than a the total effective amount useful in either the first dye step, solely, or in the subsequent application step, 25 solely, or so that a more effective degree of stain resistance of the carpet fabric is achieved at the same total of effective amounts of sulfonated aromatic condensate in said two steps as compared to the same 0 amount in either step, solely. j 1 16. The method of claim 15 wherein the dyed carpet fabric also comprises an effective amount of a fluorocarbon compound to improve resistance to soiling of the carpet. 911014,dbdat086,17019,res,78 I i~l(l~~llQL4li;( -79-

17. The method of claim 15 or 16 wherein said aqueous solution of either or both application steps also contains an effective amount of dispersing agent.

18. The method of any one of claims 15 to 17 wherein said aqueous solution of both steps also contains an effective amount of a salt having a divalent cation to improve stain resistance of said carpet.

19. A method to continuously treat dyed nylon carpet fabric, substantially as hereinbefore described with reference to the Examples. *t a.. a a a. DATED this 14th day of October, 1991 30 Allied-Signal Inc. By Its Patent Attorneys DAVIES COLLISON d1 .A 911014,dbdat.086,17019.res,79 INTERNATIONAL SEARCH REPORT lnternot~onal Ajplicaliori No P CT/US 88 01.112 1. CLASSIFICATION OF SUBJECT MATTER (it several classific3lion symbcls auly, indicate all) Accordinlg to International Patent Classification (IPC) or to both National Classification and IPC IPC 4:D 06 M 15/41 II. FWILDS SEARCHED Minimum Documentation Searched Classificaiiar. System Classification Symbols 4 IPC D06 M Documentation Searched other than Minimum Documrintation to the Extent that such Documents are Included In the Fields SearchedI

111. DOCUMENTS CONSIDERED TO GE R5LEVANT' I aktegory Citation of Document, "1 with Indication, where aporoorlate, of the relevant Passages 12 Relevant to Claim No. 13 XY US, A, 4680212 (BLYTH-) 14 July 1987, 1,2 see calims; column 5, line 63 column 6, line 24 Y EP, A, 0235989 (DU PONT) 9 Sept,-ember 1 1987, see-claims; page 1, line 24 page 2, line 12 A GB3, A, 842634 (OWENS-CORNING) 27 July 1,6,7,21 1960, see claims; page 3, lines 6?-70 Special categories of cited documental 10 IT" later document published after the International fi'ling date or priority date and not in conflict With the Application but document defining the general state of the art whichi Is not cited to understand the principle of theory Underlying the considered to be of particular relevance Invention earlier document but published on or alter the International "X document of particular relevance, the claimed Inventionl filing date cannot be considered novel or cannot be considered to document which may throw doubts on priority claimls) or Involve en Inventive step which Is Cited to establish ihe publication date of another document of particular relevance; the claimed Invention Citatio~n or other special reason t(as specified) cannot be considered to Involve at, inventive step when the document referring to an orel disclosure, use, exhibition or document Is combined witth one or more other such docuj. other means manic, such 4:ombinstiofl being obvlous to a person skilled 111" document published prior to the Intarnationiml fi'ling date but in the art. later than the Priority dale claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search 24th June 1988 International Searching Authority EU1ROPEAN PATENT OFFICE Form PCTIISA1210 (second sheet) (Janujary 1915) Dale of Mailing of this lntwrtonal Search iqeport ~V N DER PUTTEN ANNE TOTHE NTENATINALSEARH RPOR ON INTERNATIONAL PATENT APPLICATION NO. US 880112 ANNEX S TOTE1NER94NA4EAC RPR This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDI1 ile on 05/07/88 The European Patent Office is in no way liable for these particulars "fiich are merely given for the purpose of information. Patent document Publication Patent family Pulication cited in search reotdate member(s) dt US-A- 4680212 14-07-87 EP-A- 0242496 28-10-87 EP-A- 0235989 09-0G9-137 AU-A- 6869287 20-08-87 JP-A- 62223378 01-10-87 GB-A- 842634 FR-A- 1168270 OS-A- 3039981 SFor more details A it this annex see official Journal of the European Patent Office, No. 12/82