A method and compositions for textile finishing

Abstract: A method and compositions for textile finishing utilizing non-formaldehyde-releasing, reverse-water-soluble polymers as binder resins for textile finishes, Textiles treated by the disclosed method. The present invention is advantageous for health and safety reasons because it utilizes binder resins which do not release formaldehyde into the local environment.

Description: The present invention relates to a method and compositions for textile finishing utilizing non-formaldehyde-releasing, reverse-water-soluble polymers as binder resins for textile finishes and textiles treated by the disclosed method. In order to achieve laundering durability, textile finishes are typically applied with durable-press (D.P.) resins as binder resin. Essentially all commonly available D.P. resins are based on formaldehyde condensates or formaldehyde releasing adducts of nitrogenous compounds; such as: urea, urea/glyoxal, ethylene urea, melamine and related derivatives. Such binder resins have a serious deficiency in that they all can release formaldehyde to the local environment. Therefore, for health and safety reasons, the textile industry is trying very hard to eliminate the use of formaldehyde-releasing resins. It has been discovered that certain polymers which exhibit reverse-water-solubility can be utilized to impart durability to a variety of performance-effect textile finishes. The present invention therefore relates to a method of imparting durability to a textile finish which comprises applying a composition containing a non-formaldehyde-releasing, reverse-water-soluble polymer as binder resin. The RWS (=reverse-water-soluble) polymers utilized in the present method include any reverse-water-soluble polymer that is at least 1% soluble in water at 20°C. The water-solubility of RWS polymers decreases as the temperature rises, resulting in water-insolubility or near water-insolubility at around 38 to 50°C. This change in water-solubility exhibits itself as a cloud point which is defined as the temperature at which an aqueous solution at 1 % active forms an opaque dispersion or precipitate. Generally, RWS polymers of the present method will have a cloud point from about 20°C to about 60°C. Preferably, the cloud point will be from about 30°C to about 50°C. The RWS polymers utilized in the present method contain water-soluble block segments which become less soluble above the cloud point. This is thought to occur because the block segment loses its water of hydration. Polymers utilized in the present method contain at least one block segment selected from the group consisting of poly(oxyalkylene) and/or cellulose ether block segments. Preferably utilized polymers contain at least one poly(oxyethylene)block-segment. segments. In addition to the poly(oxyalkylene) and/or cellulose ether block segments, the polymers utilized in the present method can contain linking groups which connect the poly(oxyalkylene) or cellulose ether segments. These linking groups include, but are not limited to, polyester, polyamide, polycarbonate, polyacrylate and polyurethane and mixtures thereof. The resulting polymers can be linear or branched. Preferred polymers of the method of the present invention are linear or branched poly(oxyethylene) containing polyurethanes wich are at least 1% soluble in water at 20°C and a cloud point from about 20°C to about 60°C. An especially useful class of RWS polymers are the poly(oxyethylene)-poly(oxypropylene) adducts of poly-isocyanates. This class of RWS polymer is represented by formula (I). wherein R is the aliphatic or aromatic residue of a reactant containing 3 or more isocyanate reactive groups, each Z is independently hydrogen, C₁-C₈-alkyl or an additional R group, x is 3 or greater and the sum of m + n is 5 or greater, with the proviso that the ratio of m to n is such that the the polymer is at least 1% soluble at 20°C. In the instance when Z is an additional R group, the poly(oxyethylene)/poly(oxypropylene) block segments are, for example capped with another polyisocyanate where the additional isocyanate groups are reversibly blocked. RWS polymers of formula (I) are preferably those in which x is 3 to 30, m is 0 to 100 and n is 5 to 500. Z is preferably C₁-C₈-alkyl and is most preferably butyl. Compounds of formula (I) are obtained by the reaction of a polyisocyanate containing 3 or more -NCO groups per molecule with a mono-alcoholic-ether of a polyalkylene glycol (such as the product resulting from the addition of ethylene oxide and/or propylene oxide to an alcohol). Examples of reactants containing 3 or more reactive isocyanate groups which form the residue R are polyphenylene polyisocyanate and hexamethylene-diisocyanate trimer. Polyphenylene polyisocyanate is represented by formula II wherein y is 3 or greater. Hexamethylene-diisocyanate trimer is represented by formula (III). Poly(oxyethylene)-poly(oxypropylene) adducts of formula (I) wherein Z is butyl are known as thermosensitizers for aqueous dye dispersions which thermocoagulate dispersed dye particles to inhibit their migration during textile drying operations. Such alkoxylated-polyisocyanates are commercially available and are described in Chem. Abstr., 88 :63182y (1977), and US-A-4,164,535, 4,118,538 and 4,053,440. The composition of the present application further comprises a performance-effect textile finish. The term performance-effect finish is used generically in this application to describe a variety of finishes that modify textile properties. The performance-effect finishes applied by the present method include soil-release agents, soil repellents, water-repellents, softeners, flame-retardants, anti-static agents, light stabilizers, hand modifiers and U.V. absorbers. These finishes can be applied by the inventive method to nearly any type of textile. However, the inventive method is particularly useful for knitted or woven cotton, wool, PES/cotton, polyester, polyamide (nylon), acrylics, rayon and acetate fabrics. The term textile in this application is intended to refer any class of textile material including fibers, yarns, knitted and woven fabrics. Another object of the present invention is an aqueous finishing formulation comprising (a) 10-20 grams/liter of a reverse-water-soluble polymer of the formula wherein R is the aliphatic or aromatic residue of a reactant containing 3 or more isocyanate reactive groups; each Z is independently hydrogen, C₁-C₈-alkyl or an additional R group; X is 3 or greater and the sum of m + n is 6 or greater with the proviso that the ratio of m to n is such that the polymer is at least 1 % soluble at 20°C; and (b) 0.3-0.6 grams/liter of the sodium salt of a naphthalene sulfonic acid condensate. Preferably the formulation of the present invention further comprises (c) 20-40 grams/liter of a fluorochemical stain release agent; and (d) 0-40 grams/liter of a softening agent. Preferably the stain release agent (c) is a perfluoroalkyl-acrylate-polyethylene oxide block A further preferred composition further comprises (e) 40 to 400 grams/liter of an organo-phosphorous type flame-retardant. The invention is illustrated by the following examples. The following test methods utilized in the examples are as follows: Oil Repellency is evaluated by AATCC test method No. 130-1988. 0 is the worst rating (no oil repellency), and 8 is the best rating (high oil repellency). Stain-Release is evaluated by the method published in 3M Scotchgard Stain-Release bulletins - "Stain-Release Method I" for resin treated apparel fabrics; Stain K = Kaydol® mineral oil (Witco); Stain E = vegetable oil from 3M; Stain C = 15% dirty motor oil/85% 30W motor oil; 0 is the worst rating (no oily stain release during laundering), and 8 is the best rating (complete stain release). Wrinkle Recovery is a subjective visual rating test. A rating of 1 is worst. A rating of 5 is best. Used AATCC method No. 143- 1988 ("Appearance of Apparel and Other Textile End Products after Repeated Home Laundering"). The following is a brief description of materials referred to in the following examples. Example 1: A non-formaldehyde-releasing binder for various textile finishes utilizing a poly-(oxyethylene) containing urethane-based polymer of the type described by formula (I) wherein R is based on formula (II), as the reverse-water-soluble polymer consists of an aqueous solution of 0.75% of naphthalene sulfonic acid condensate (for example TAMEL by Rohm and Haas) and 25% of an alkoxylated-polyisocyanate based upon the weight of the solids. The above-described formulation has the following typical properties: Appearance: amber colored, viscous liquid Ionic Nature: Nonionic/anionic Solids: 26% (+/- 10% relative) pH (as is): 7-9 Boiling Point: 100°C (212°F) Solubility in Cold Water: Miscible at all ratios Cloud point (1% actives): 38-42°C Example 2: The following procedure was utilized to bind a stain-release agent to non-resinated knits and wovens. These knits can subsequently be compacted or napped. A finishing formulation composed of 40 - 80 g/l 25% actives of a poly(oxyethylene) containing Reverse-Water-Soluble urethane-based polymer of the type described in formula (I) wherein the residue R is a polyphenylene polyisocyanate of formula II, and 0.75% of a naphthalene sulfonic acid condensate dispersant with a cloud point at of 38 to 42°C. 40 g/l a polyethylene emulsion type textile softener 20 - 40 g/l perfluoroalkyl-acrylate-polyethylene oxide block co-polymer was dispersed in cold water, pad applied to 60-70% wet pick-up, dried at 149°C (300°F) and cured at 160-171°C (320-340°F). Examples 3-11: The following finishing formulations were applied to 50/50 polyester/cotton (PES/CO) red woven fabric to a wet pick-up of approximately 73%. The samples were dried at 149°C (300°F) for 2 minutes and cured for an additional minute at 177°C (350°F). The samples were washed 5 times at 49°C (120°F) with 46 g of detergent (TIDE®), dry tumbled for 45 minutes and tested for oil-repellency. Stain-release was tested on the initial and washed samples after 1 additional wash cycle at 49°C (120°F) with 100 g of detergent. Each of the formulations is an aqueous formulation with the ingredients described in grams/liter formulation. Examples 12 and 13: The following formulations were applied to 100% cotton by padding with a wet pickup of 75%, dried at 138°C (280°F) and cured at 171°C (340°F). The treated material is then neutralized and rinsed. Example 12 utilizes a conventional durable-press resin system. Example 13 utilizes a non-formaldehyde-releasing R.W. S. binder system as described in this application. All concentrations are in grams/liter of formulation. Examples 14 - 17: The following formulations were pad applied at 80-85% wet pickup, dried at 149°C (300°F) for two minutes and cured at 171°C (340°F) for one minute. Examples 14 and 16 represent formulations of this application. Examples 15 and 17 utilize a conventional D.P. resin. Results : Example 18: The following comparative testing was carried out with formulations (A)-(E). Sample (A) represents an untreated control. Sample (B) utilizes a imidazolinone D.P. resin. Samples (C)-(E) utilize formulations of the present invention. All concentrations are in grams/liter. Application Conditions: Pad applied to 50/50 polyester/cotton knit fabric (double-dip/double-nip padding-Galtex laboratory padder model PA1) at 56% wet pick-up. Dried & cured in 1-step at 163°C (325°F) for 2 minutes. TEST RESULTS: The meaning of the compounds (101) to (115) are as follows: (101) = 25% actives of a poly(oxyethylene) containing Reverse-Water-Soluble urethane-based polymer of the type described in formula (I) wherein the residue R is a polyphenylene polyisocyanate of formula II, and 0.75% of a naphthalene sulfonic acid condensate dispersant. The cloud point at 1% actives is 38 to 42°C. (102) = a perfluoroalkyl-acrylate-polyethylene oxide block co-polymer of the type described in U.S. patents 3,574,791 and 3,728,151. (103)= a hydrophylic silicone softener of the type described in US-A-3 402 192. (105) = active methylcellulose. A stock solution is made up at 10% actives. The cloud point at 1% actives is about 60°C heating up and about 35°C cooling down. (106) = a ethylene oxide-propylene oxide-ethylene oxide block copolymer. Stock solution made up at 1% actives. The cloud point at 10% actives is about 30°C. (107) = non-silicone textile softener based on a fatty acid mixture-polyamidecondensation product. (108) = a polyethylene emulsion type textile softener. (109) = an organo-phosphorous type flame-retardant. (110) = melamine-formaldehyde durable-press resin. (111) = amino-silicone based textile softener. (112) = wetting & deaerating agent, polyglycol ether sulfuric acid ester salt (113) = textile softener, mixture of polysiloxane and a fatty acid polyamide condensation product. (114) = modified imidazolidone durable-press resin. (115) is a pre-catalized imidazolinone conventional glyoxal type durable-press resin.

Claims: Claims for the following Contracting States : BE, CH, DE, FR, GB, IT, LI, NL A method of imparting durability to a textile finish which comprises applying a composition containing a non-formaldehyde-releasing, reverse-water-soluble polymer as binder resin. A method according to claim 1, wherein the reverse-water-soluble polymer is at least 1% soluble in water at 20°C and has a cloud point from about 20 to 60°C. A method according to claim 1 or 2, wherein the reverse-water-soluble polymer comprises at least one block segment selected from the group consisting of poly(oxyethylene) and/or cellulose ether block segments. A method according to one of the claims 1 to 3, wherein the reverse-water-soluble polymer comprises at least one poly(oxyethylene) block segment. A method according to one of the claims 1 to 4, wherein the reverse-water-soluble polymer comprises at least one poly(oxyethylene) block segment and at least one linking group selected from the group consisting of polyester, polyamide, polycarbonate and polyurethane. A method according to one of the claims 1 to 5, wherein, the reverse-water-soluble polymer contains linear or branched poly(oxyethylene) containing polyurethanes which are at least 1% soluble in water at 20°C and have a cloud point from about 20 to about 60°C. A method according to one of the claims 1 to 6, wherein the reverse-water-soluble polymer is a compound of the formula wherein R is the aliphatic or aromatic residue of a reactant containing 3 or more isocyanate reactive groups; each Z is independently hydrogen, C₁-C₈-alkyl or an additional R group; x is 3 or greater and the sum of m+n is 5 or greater, with the proviso that the ratio of (m:n) is such that the polymer is at least 1% soluble in water at 20°C. A method according to claim 7, wherein x is 3 to 30, m is 0 to 100, n is 5 to 500, Z is C₁-C₈-alkyl and R is a polyphenylene-polyisocyanate or a hexamethylene-diisocyanate-trimer. A method according to claim 7, wherein Z is butyl. A method according to claim 1, wherein the composition further comprises a performance-effect textile finish. A method according to claim 10, wherein the performance-effect textile finish is selected from the group consisting of soil-release agents, soil repellants, water-repellants, softeners, hand modifiers, flame retardants, anti-static agents, light-stabilizers and ultra-violet absorbing agents. A method according to one of the claims 10 or 11, wherein the textile is selected from the group consisting of cotton, wool, polyester/cotton, polyester, nylon, acrylics, acetates and rayon. An aqueous finishing formulation comprising (a) 10-20 grams/liter of a reverse-water-soluble polymer of the formula wherein R is the aliphatic or aromatic residue of a reactant containing 3 or more isocyanate reactive groups; each Z is independently hydrogen, C₁-C₈-alkyl or an additional R group; x is 3 or greater and the sum of m+n is 5 or greater, with the proviso that the ratio of (m:n) is such that the polymer is at least 1% soluble in water at 20°C, (b) 0.3-0.6 grams/liter of the sodium salt of a naphthalene sulfonic acid condensate, (c) 20-40 grams/liter of a fluorochemical stain-release agent, and (d) 0-40 grams/liter of a softening agent. An aqueous finishing formulation according to claim 13, wherein said fluorochemical stain-release agent si a perfluoroalkyl-acrylate-polyethylene oxide block-co-polymer. An aqueous finishing formulation according to one of the claims 13 and 14, which further comprises (e) 40-400 grams/liter of an organo-phosphorous-type flame-retardant. Textiles finished by the method of one of the claims 1 to 12. Claims for the following Contracting State : ES A method of imparting durability to a textile finish which comprises applying a composition containing a non-formaldehyde-releasing, reverse-water-soluble polymer as binder resin. A method according to claim 1, wherein the reverse-water-soluble polymer is at least 1% soluble in water at 20°C and has a cloud point from about 20 to 60°C. A method according to claim 1 or 2, wherein the reverse-water-soluble polymer comprises at least one block segment selected from the group consisting of poly(oxyethylene) and/or cellulose ether block segments. A method according to one of the claims 1 to 3, wherein the reverse-water-soluble polymer comprises at least one poly(oxyethylene) block segment. A method according to one of the claims 1 to 4, wherein the reverse-water-soluble polymer comprises at least one poly(oxyethylene) block segment and at least one linking group selected from the group consisting of polyester, polyamide, polycarbonate and polyurethane. A method according to one of the claims 1 to 5, wherein, the reverse-water-soluble polymer contains linear or branched poly(oxyethylene) containing polyurethanes which are at least 1% soluble in water at 20°C and have a cloud point from about 20 to about 60°C. A method according to one of the claims 1 to 6, wherein the reverse-water-soluble polymer is a compound of the formula wherein R is the aliphatic or aromatic residue of a reactant containing 3 or more isocyanate reactive groups; each Z is independently hydrogen, C₁-C₈-alkyl or an additional R group; x is 3 or greater and the sum of m+n is 5 or greater, with the proviso that the ratio of (m:n) is such that the polymer is at least 1% soluble in water at 20°C. A method according to claim 7, wherein x is 3 to 30, m is 0 to 100, n is 5 to 500, Z is C₁-C₈-alkyl and R is a polyphenylene-polyisocyanate or a hexamethylene-diisocyanate-trimer. A method according to claim 7, wherein Z is butyl. A method according to claim 1, wherein the composition further comprises a performance-effect textile finish. A method according to claim 10, wherein the performance-effect textile finish is selected from the group consisting of soil-release agents, soil repellants, water-repellants, softeners, hand modifiers, flame retardants, anti-static agents, light-stabilizers and ultra-violet absorbing agents. A method according to one of the claims 10 or 11, wherein the textile is selected from the group consisting of cotton, wool, polyester/cotton, polyester, nylon, acrylics, acetates and rayon.

Inventors: ALLEN DONALD A JR, ISHARANI JAYANTI V, MIDDLETON JOHN W, RAPER JAMES KENNETH, ALLEN, DONALD A., JR., ISHARANI, JAYANTI V., MIDDLETON, JOHN W., RAPER, JAMES KENNETH
Applicants: CIBA GEIGY AG, CIBA-GEIGY AG
Application year: 1991
Main classification: D06M15
IPC codes: D06M101, D06M15, D06M13