WO2009050102A1 - Method for treating wool - Google Patents

Method for treating wool Download PDF

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Publication number
WO2009050102A1
WO2009050102A1 PCT/EP2008/063530 EP2008063530W WO2009050102A1 WO 2009050102 A1 WO2009050102 A1 WO 2009050102A1 EP 2008063530 W EP2008063530 W EP 2008063530W WO 2009050102 A1 WO2009050102 A1 WO 2009050102A1
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WIPO (PCT)
Prior art keywords
weight
wool
composition
water
aqueous composition
Prior art date
Application number
PCT/EP2008/063530
Other languages
French (fr)
Inventor
Marco Luoni
Tiziana Furiosi
Ermanno Mino
Giuseppe Li Bassi
Original Assignee
Lamberti Spa
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Publication date
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Priority to CN2008801121082A priority Critical patent/CN101821445B/en
Publication of WO2009050102A1 publication Critical patent/WO2009050102A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/395—Isocyanates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/44—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing nitrogen and phosphorus
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/568—Reaction products of isocyanates with polyethers

Definitions

  • the present invention relates to a method for treating wool, wool fibres or animal hair (hereinafter "wool") to provide shrink resistance, to reduce fuzzing and pilling and the damages caused by wearing and washing.
  • wool wool, wool fibres or animal hair
  • the above mentioned characteristics are obtained by a process that comprises treating wool with an aqueous solution comprising a cationic polyurethane having filming properties and a non-ionic water dispersible polyisocyanate crosslinker composition.
  • Background Art [0003] In order to achieve shrink resistance, to reduce pilling and improve laundering durability, before or after knitting or weaving resins are typically applied on most woollen textile materials.
  • the present invention provides a method for treating wool which comprises: i) preparing an aqueous composition containing a cationic polyurethane, a non-blocked nonionic water-dispersible polyisocyanate and an ethoxylated phosphated alcohol having one or more phosphoric group in acidic form; ii) impregnating the wool with the obtained aqueous composition; iii) drying the wool.
  • the method of the invention provides shrink resistance and dimension stability, reduces fuzzing and pilling and the damages caused by wearing and washing.
  • the aqueous composition useful for the impregnation of wool typically comprises from 0.5 to 5 % of cationic polyurethane, from 0.3 to 3 % of non-blocked nonionic water-dispersible polyisocyanate and from 0.03 to
  • the aqueous composition may advantageously contain from 0.05 to 0.5 % on the weight of goods of a nonionic surfactant, preferably an ethoxylated fatty alcohol.
  • a nonionic surfactant preferably an ethoxylated fatty alcohol.
  • From 5 to 100 I of aqueous composition per kilogram of wool are normally employed.
  • Step ii) shall take place soon after the preparation of the aqueous composition, preferably within 8 hours from its preparation, because the non-blocked nonionic water-dispersible polyisocyanate slowly reacts with water even at ambient temperature.
  • the wool to be treated can be in the form of top, fibre, yarn or woven or knitted fabric.
  • the method of the invention can also be carried out on loose flocks or on garments made from wool. Best results are obtained by treating the wool in the form of yarn or knitted fabric.
  • the treatment advantageously may be carried out on hanks or cones.
  • the wool may comprise up to 50% by weight of other fibres, such as viscose, polyester or polyamide fibres.
  • the impregnation may be carried out by padding, spraying, slop padding or the like.
  • the impregnation of wool is carried out in the aqueous composition according to the invention at 20-60° C for 10 to 60 minutes, to reach exhaustion of the composition.
  • the pH of the aqueous composition during impregnation shall be regulated at about 4-6; acetic acid is preferably used to regulate the pH to about 5.
  • the wool After impregnation, i.e. saturation of the material, the wool is advantageously centrifuged, and dried , as deemed suitable by the man skilled in the art.
  • Cationic polyurethanes suitable for the preparation of the aqueous composition of the invention are commercially available, for example they are commercialized by Cesalpinia Chemicals with the trade name Rolflex CN 24. They are typically commercialized in the form of 20-40% by weight aqueous dispersion.
  • the suitable cationic polyurethanes are obtained by: a) reacting one or more organic diisocyanates with a mixture of an alkyldiethanolamine and at least one linear polyol to obtain a prepolymer having free isocyanate groups; b) cationising the amine groups; c) extending the obtained cationic polyisocyanate with water or amines.
  • the preparation of the prepolymer and subsequent cationisation may be performed by using for the reactants the molar ratios defined in EP 98752.
  • the useful cationic polyurethane have a typical molecular weight from 2,000 to 100,000 dalton.
  • organic diisocyanates aromatic, aliphatic or cycloaliphatic diisocyanates may be used; preferably the organic diisocyanates are aliphatic or cycloaliphatic and more preferably are 4,4'-dicyclohexyl- methane-diisocyanate, 1 -isocyanate, 3-isocyanate-methyl-3,5, 5- trimethylcyclohexane (or isophorone diisocyanate), hexamethylenediisocyanate and mixture thereof.
  • Polyols which are useful for the preparation of the cationic polyurethane of the invention are typically either polyalkylene ether glycols or polyester polyols, polyalkylene ether glycols being preferred.
  • the most useful polyalkylene ether glycols have a molecular weight of 50 to 5,000 and preferably from about 500 to about 4,000.
  • Examples of the polyalkylene ether glycols are, but not limited to, polypropylene ether glycol, polytetramethylene ether glycol, and mixtures thereof.
  • Particularly preferred for the realisation of the present invention is polytetramethylene ether glycol.
  • Alkyldiethanolamines useful for the preparation of the cationic polyurethane are for example methyl-, ethyl-, isopropyl-, n-butyk t-butyl-, cyclohexyl-, n-hexyl- diethanolamine and mixture thereof.
  • Cationisation is performed by adding an inorganic or an organic acid or by quaternisation with alkylating agents, as described by way of example in US 3,480,592 and US 3,388,087.
  • the extension of the cationic polyisocyanate obtained from step b) is preferably carried out in water.
  • the cationic polyurethanes useful for the method according to the invention are film-forming polymers forming a medium soft film with an elongation to break of 400 to 1 ,000%, as determined according to method ASTM D882-02.
  • a commercially available aqueous dispersion of a suitable cationic polyurethane is diluted in water, optionally in the presence of a non-ionic surfactant, and added into the aqueous bath where impregnation shall take place (for example in a dyeing machine); Subsequently, a composition comprising the non-blocked nonionic water- dispersible polyisocyanate and the ethoxylated phosphatedd alcohols in acid form (Composition II) is added into the bath, preferably soon after dilution in 2 to 20 folds of water.
  • Composition Il according to the invention comprises I) from 30 to 99% by weight of at least one non-blocked nonionic water-dispersible polyisocyanate obtained by reaction of aliphatic or cycloaliphatic polyisocyanates containing from 3 to 10 isocyanate groups per molecule with polyols; II) from 1 to 20% by weight, and preferably from 5 to 15% by weight, of one or more ethoxylated phosphated alcohols in acid form III) from 0 to 50% by weight, and preferably from 5 to 30% by weight, of a non reactive, water miscible solvent.
  • the non-blocked nonionic water-dispersible polyisocyanate are prepared by using as polyols the commercially available 1 ,3- or 1 ,2- non- ionic diols containing only one alkoxy terminated polyethoxylated and/or polypropoxylated chain; said polyols are for example sold by Th. Goldschmidt AG with the trade names Tegomer ® D-3403 and Tegomer ⁇ D-3123.
  • the useful non-blocked nonionic water-dispersible polyisocyanates contain from 1 to 25% by weight, preferably from 3 to 15% by weight, of polyethoxylated and/or polypropoxylated chains deriving from the afore mentioned nonionic 1 ,3- and/or 1 ,2-diols or from other ethoxylated and/or propoxylated alcohols, such as ethoxylated and/or propoxylated derivatives of methanol, n-butanol, cyclohexanol, 3-methyl-3- hydroxymethyloxethane, ethylene glycol, propylene glycol, glycerol and trimethylolpropane, and mixture thereof.
  • Example of aliphatic or cycloaliphatic polyisocyanates containing from 3 to 10 isocyanate groups per molecole useful for the preparation of non- blocked nonionic water-dispersible polyisocyanate are the compounds obtained from trimerization, biurethanization, urethanization or allophanation of polyisocyanates, such as hexamethylenediisocyanate, isophorone diisocyanate, 4-4'-dicyclohexylmethanediisocyanate and mixtures thereof.
  • R is a saturated or unsaturated, linear or branched alkyl group having from 4 to 20, preferably from 12 to 15, carbon atoms, s is a number from 2 to 20, preferably from 4 to 10, and t is 1 or 2.
  • Ethoxylated alcohols phosphated in acid form are commercially available.
  • Composition Il is obtainable by adding one or more commercially available ethoxylated alcohols phosphated in acid form to the non-blocked nonionic water-dispersible polyisocyanate, possibly dissolved in a suitable non reactive solvent, or by preparing the non-blocked nonionic water- dispersible polyisocyanate in the presence of one or more ethoxylated alcohols phosphated in acid form.
  • the method according to the invention optionally comprises a pre- treatment step with a commercial protease formulation which may be performed on wool before step i).
  • the protease pre-treatment is carried out at pH of about 8 in an aqueous bath containing the protease formulation at 40-60° for about 30 minutes.
  • protease pre-treatment improves the absorption of polyurethane and Composition Il on wool.
  • thermometer and cooling device 82.458 g (135 meq) of Tegomer® D-3403, an ethoxylated diol having molecular weight 1220 g/mol, and 100 g of C12-C15 6 moles ethoxylated phoshated alcohol in acid form (%P 7.1 ; acidity No. 200-210) are charged.
  • the mixture is distilled under vacuum to reduce the water content to a value lower than 0.05% (as determined by Karl Fischer titration).
  • Tolonate® HDT LV2 is a hexamethylenediisocyanate isocyanurate, with NCO content 23,0+1 % and 100% solid matter sold by Rhodia).
  • the mixture is brought to 90°C and maintained at 85-90°C for one hour, until the NCO content is 18% (as determined by titration according to
  • a yellow clear liquid composition is obtained having Brookfield® viscosity at 25 o C of 3,200 mPa*s.
  • 1 ,600 g of this composition are mixed with 40 g of dipropylene glycol dimethyl ether, sold by Dow Chemicals as Proglyde® DMM.
  • a composition (Composition II) is obtained having Brookfield® viscosity at
  • Composition Il 25°C of 550 mPa*s.
  • 200 g of Composition Il are diluted with 2,000 g of water at ambient temperature, obtaining Composition B.
  • Treatment of hanks. [0062] Wool hanks (count 2/30) are treated with 4% on the weight on goods of
  • the temperature is raised to 40°C and maintained for 30 minutes.
  • the bath is discharged and the hanks are accurately rinsed.
  • the fresh bath is regulated to pH 5.
  • Basolan® DC and dyed with reactive dyes in a OBEM vertical laboratory dyeing machine Basolan® DC and dyed with reactive dyes in a OBEM vertical laboratory dyeing machine.
  • Knitted fabrics (count 2/30) are treated with 4% on the weight on goods of
  • Basolan® DC and dyed with premetallised dyes in a laboratory "linitest” dyeing machine were then water has been charged and recirculation has started, the pH is regulated to 8 with 30% technical grade ammonium hydroxide. [0086] 4 g/l of Deterlam SI are introduced in the dyeing machine through the expansion vessel.
  • the temperature is raised to 40°C and maintained for 30 minutes.
  • the bath is discharged and the hanks are accurately rinsed.
  • the fresh bath is regulated to pH 5.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Glass Compositions (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

Method for treating wool, wool fibres or animal hair to provide shrink resistance, to reduce fuzzing and pilling and the damages caused by wearing and washing comprising: i) preparing an aqueous composition containing a cationic polyurethane, a non-blocked nonionic water-dispersible polyisocyanate and an ethoxylated phosphated alcohol having one or more phosphoric group in acidic form; ii) impregnating the wool with the obtained aqueous composition; iii) drying the wool.

Description

Description
METHOD FOR TREATING WOOL Technical Field [0001] The present invention relates to a method for treating wool, wool fibres or animal hair (hereinafter "wool") to provide shrink resistance, to reduce fuzzing and pilling and the damages caused by wearing and washing. [0002] In accordance with the present invention, the above mentioned characteristics are obtained by a process that comprises treating wool with an aqueous solution comprising a cationic polyurethane having filming properties and a non-ionic water dispersible polyisocyanate crosslinker composition. Background Art [0003] In order to achieve shrink resistance, to reduce pilling and improve laundering durability, before or after knitting or weaving resins are typically applied on most woollen textile materials. [0004] One of the most commonly used method to increase shrink resistance of wool is to combine chlorination and application of a polymer. [0005] Many resins have been proposed for the purposes just referred to. [0006] It is known for example from JP 2004115950 to use a cationic polyurethane as a shrink-proofing agent for keratin fibres. [0007] WO 0066830 describes the use of aqueous compositions comprising a polyisocyanate prepolymer that is masked with bisulphite for anti-felting finish of wool. [0008] US 4,985,040 relates to the treatment of woollen textile material comprising depositing a polyamide-epichlorohydrin resin and a polyurethane. [0009] Also, various enzymatic treatment have been used for reducing the shrinkage of wool. Disclosure of Invention [0010] The present invention provides a method for treating wool which comprises: i) preparing an aqueous composition containing a cationic polyurethane, a non-blocked nonionic water-dispersible polyisocyanate and an ethoxylated phosphated alcohol having one or more phosphoric group in acidic form; ii) impregnating the wool with the obtained aqueous composition; iii) drying the wool. [0011] The method of the invention provides shrink resistance and dimension stability, reduces fuzzing and pilling and the damages caused by wearing and washing. [0012] The aqueous composition useful for the impregnation of wool typically comprises from 0.5 to 5 % of cationic polyurethane, from 0.3 to 3 % of non-blocked nonionic water-dispersible polyisocyanate and from 0.03 to
0.3% of ethoxylated phosphated alcohol having one or more phosphoric group in acidic form on the weight of goods. [0013] The aqueous composition may advantageously contain from 0.05 to 0.5 % on the weight of goods of a nonionic surfactant, preferably an ethoxylated fatty alcohol. [0014] From 5 to 100 I of aqueous composition per kilogram of wool are normally employed. [0015] Step ii) shall take place soon after the preparation of the aqueous composition, preferably within 8 hours from its preparation, because the non-blocked nonionic water-dispersible polyisocyanate slowly reacts with water even at ambient temperature. [0016] The wool to be treated can be in the form of top, fibre, yarn or woven or knitted fabric. The method of the invention can also be carried out on loose flocks or on garments made from wool. Best results are obtained by treating the wool in the form of yarn or knitted fabric. [0017] When wool in the form of yarn is used as the substrate, the treatment advantageously may be carried out on hanks or cones. [0018] The wool may comprise up to 50% by weight of other fibres, such as viscose, polyester or polyamide fibres. [0019] The impregnation may be carried out by padding, spraying, slop padding or the like. [0020] Preferably, the impregnation of wool is carried out in the aqueous composition according to the invention at 20-60° C for 10 to 60 minutes, to reach exhaustion of the composition. [0021] The pH of the aqueous composition during impregnation shall be regulated at about 4-6; acetic acid is preferably used to regulate the pH to about 5.
[0022] After impregnation, i.e. saturation of the material, the wool is advantageously centrifuged, and dried , as deemed suitable by the man skilled in the art.
[0023] Cationic polyurethanes suitable for the preparation of the aqueous composition of the invention are commercially available, for example they are commercialized by Cesalpinia Chemicals with the trade name Rolflex CN 24. They are typically commercialized in the form of 20-40% by weight aqueous dispersion.
[0024] The suitable cationic polyurethanes are obtained by: a) reacting one or more organic diisocyanates with a mixture of an alkyldiethanolamine and at least one linear polyol to obtain a prepolymer having free isocyanate groups; b) cationising the amine groups; c) extending the obtained cationic polyisocyanate with water or amines.
[0025] The preparation of the prepolymer and subsequent cationisation may be performed by using for the reactants the molar ratios defined in EP 98752.
[0026] The useful cationic polyurethane have a typical molecular weight from 2,000 to 100,000 dalton.
[0027] As organic diisocyanates, aromatic, aliphatic or cycloaliphatic diisocyanates may be used; preferably the organic diisocyanates are aliphatic or cycloaliphatic and more preferably are 4,4'-dicyclohexyl- methane-diisocyanate, 1 -isocyanate, 3-isocyanate-methyl-3,5, 5- trimethylcyclohexane (or isophorone diisocyanate), hexamethylenediisocyanate and mixture thereof.
[0028] Polyols which are useful for the preparation of the cationic polyurethane of the invention are typically either polyalkylene ether glycols or polyester polyols, polyalkylene ether glycols being preferred.
[0029] The most useful polyalkylene ether glycols have a molecular weight of 50 to 5,000 and preferably from about 500 to about 4,000. Examples of the polyalkylene ether glycols are, but not limited to, polypropylene ether glycol, polytetramethylene ether glycol, and mixtures thereof. [0030] Particularly preferred for the realisation of the present invention is polytetramethylene ether glycol.
[0031] Alkyldiethanolamines useful for the preparation of the cationic polyurethane are for example methyl-, ethyl-, isopropyl-, n-butyk t-butyl-, cyclohexyl-, n-hexyl- diethanolamine and mixture thereof.
[0032] Cationisation is performed by adding an inorganic or an organic acid or by quaternisation with alkylating agents, as described by way of example in US 3,480,592 and US 3,388,087.
[0033] The extension of the cationic polyisocyanate obtained from step b) is preferably carried out in water.
[0034] The cationic polyurethanes useful for the method according to the invention are film-forming polymers forming a medium soft film with an elongation to break of 400 to 1 ,000%, as determined according to method ASTM D882-02.
[0035] In the practice of the invention, a commercially available aqueous dispersion of a suitable cationic polyurethane is diluted in water, optionally in the presence of a non-ionic surfactant, and added into the aqueous bath where impregnation shall take place (for example in a dyeing machine); Subsequently, a composition comprising the non-blocked nonionic water- dispersible polyisocyanate and the ethoxylated phosphatedd alcohols in acid form (Composition II) is added into the bath, preferably soon after dilution in 2 to 20 folds of water.
[0036] Composition Il according to the invention comprises I) from 30 to 99% by weight of at least one non-blocked nonionic water-dispersible polyisocyanate obtained by reaction of aliphatic or cycloaliphatic polyisocyanates containing from 3 to 10 isocyanate groups per molecule with polyols; II) from 1 to 20% by weight, and preferably from 5 to 15% by weight, of one or more ethoxylated phosphated alcohols in acid form III) from 0 to 50% by weight, and preferably from 5 to 30% by weight, of a non reactive, water miscible solvent.
[0037] Freshly diluted Composition Il may also be added into the impregnation bath before addition of the cationic polyurethane; in the alternative, its components I) and II) may be separately added into the bath. [0038] Preferably, the non-blocked nonionic water-dispersible polyisocyanate are prepared by using as polyols the commercially available 1 ,3- or 1 ,2- non- ionic diols containing only one alkoxy terminated polyethoxylated and/or polypropoxylated chain; said polyols are for example sold by Th. Goldschmidt AG with the trade names Tegomer ® D-3403 and Tegomer © D-3123.
[0039] The useful non-blocked nonionic water-dispersible polyisocyanates contain from 1 to 25% by weight, preferably from 3 to 15% by weight, of polyethoxylated and/or polypropoxylated chains deriving from the afore mentioned nonionic 1 ,3- and/or 1 ,2-diols or from other ethoxylated and/or propoxylated alcohols, such as ethoxylated and/or propoxylated derivatives of methanol, n-butanol, cyclohexanol, 3-methyl-3- hydroxymethyloxethane, ethylene glycol, propylene glycol, glycerol and trimethylolpropane, and mixture thereof.
[0040] Example of aliphatic or cycloaliphatic polyisocyanates containing from 3 to 10 isocyanate groups per molecole useful for the preparation of non- blocked nonionic water-dispersible polyisocyanate are the compounds obtained from trimerization, biurethanization, urethanization or allophanation of polyisocyanates, such as hexamethylenediisocyanate, isophorone diisocyanate, 4-4'-dicyclohexylmethanediisocyanate and mixtures thereof.
[0041] Useful ethoxylated phosphated alcohols in acid form have the following general formula:
[0042] [RO-(CH2CH2O)s]tP(=O)- (OH)3-t
[0043] wherein R is a saturated or unsaturated, linear or branched alkyl group having from 4 to 20, preferably from 12 to 15, carbon atoms, s is a number from 2 to 20, preferably from 4 to 10, and t is 1 or 2.
[0044] Ethoxylated alcohols phosphated in acid form are commercially available.
[0045] Composition Il is obtainable by adding one or more commercially available ethoxylated alcohols phosphated in acid form to the non-blocked nonionic water-dispersible polyisocyanate, possibly dissolved in a suitable non reactive solvent, or by preparing the non-blocked nonionic water- dispersible polyisocyanate in the presence of one or more ethoxylated alcohols phosphated in acid form.
[0046] The method according to the invention optionally comprises a pre- treatment step with a commercial protease formulation which may be performed on wool before step i).
[0047] The protease pre-treatment is carried out at pH of about 8 in an aqueous bath containing the protease formulation at 40-60° for about 30 minutes.
[0048] It is believed that the protease pre-treatment improves the absorption of polyurethane and Composition Il on wool.
[0049] Best results were obtained by using in the pre-treatment a bath containing Deterlam Sl, a protease formulation commercialised by Lamberti S.p.A..
[0050] EXAMPLE 1
[0051] A. Preparation of the water diluted cationic polyurethane.
[0052] 600 g of Rolflex CN 24, a cationic film-forming polyurethane dispersion sold by Cesalpinia Chemicals having 30% active content was diluted in 442 g of water containing 20 g of ethoxylated isotridecyl alcohol at room temperature under stirring and then with about 3 parts of water. (Composizione A).
[0053] B. Preparation of an aqueous mixture comprising the non-blocked nonionic water-dispersible polyisocyanate and the ethoxylated alcohol phosphated in acid form.
[0054] In a reactor equipped with stirrer, thermometer and cooling device 82.458 g (135 meq) of Tegomer® D-3403, an ethoxylated diol having molecular weight 1220 g/mol, and 100 g of C12-C15 6 moles ethoxylated phoshated alcohol in acid form (%P=7.1 ; acidity No. 200-210) are charged. The mixture is distilled under vacuum to reduce the water content to a value lower than 0.05% (as determined by Karl Fischer titration).
[0055] At 40°C under nitrogen atmosphere and stirring, 817.542 g (4406 meq) of Tolonate® HDT LV2 are charged ( Tolonate® HDT LV2 is a hexamethylenediisocyanate isocyanurate, with NCO content 23,0+1 % and 100% solid matter sold by Rhodia). [0056] The mixture is brought to 90°C and maintained at 85-90°C for one hour, until the NCO content is 18% (as determined by titration according to
ASTM standard D2572). [0057] A yellow clear liquid composition is obtained having Brookfield® viscosity at 25oC of 3,200 mPa*s. [0058] 1 ,600 g of this composition are mixed with 40 g of dipropylene glycol dimethyl ether, sold by Dow Chemicals as Proglyde® DMM. [0059] A composition (Composition II) is obtained having Brookfield® viscosity at
25°C of 550 mPa*s. [0060] 200 g of Composition Il are diluted with 2,000 g of water at ambient temperature, obtaining Composition B. [0061] Treatment of hanks. [0062] Wool hanks (count 2/30) are treated with 4% on the weight on goods of
55-60% sodium dichloroisocyanurate (Basolan® DC, from BASF) and dyed with reactive dyes in a OBEM dyeing machine. [0063] After water has been charged and recirculation has started, the pH is regulated to 8 with 30% technical grade ammonium hydroxide. [0064] 4 g/l of Deterlam SI are introduced in the dyeing machine through the expansion vessel.
[0065] The temperature is raised to 40°C and maintained for 30 minutes. [0066] The bath is discharged and the hanks are accurately rinsed. [0067] The fresh bath is regulated to pH 5. [0068] Through the expansion vessel 8% on the weight of goods of Composition
A are added. The product is charged in the bath and homogenised for 5 minutes.
[0069] 2% on the weight of goods of Composition B is added. [0070] After 5 minutes the temperature is raised to 40°C and maintained for 40 minutes. [0071] The bath is discharged and the goods is centrifuged without any rinse and dried at 80-900C. [0072] The yarn of the hanks is used to knit samples which are tested according to the IWS TM31 5x5 A test method (simulating 50 machine washings) and the shrinkage is measured. [0073] Shrinkage of the treated material is +1 %, while a comparative untreated material shows a shrinkage of -46% after the 1x5A test (simulating only 10 machine washings). [0074] Treatment of cones [0075] 100% wool cones are treated with 4% on the weight on goods of
Basolan® DC and dyed with reactive dyes in a OBEM vertical laboratory dyeing machine.
[0076] After dyeing, the fresh bath is regulated to pH 5. [0077] Through the expansion vessel 8% on the weight of goods of Composition
A are added. The product is charged in the bath and homogenised for 5 minutes.
[0078] 2% on the weight of goods of Composition B is added. [0079] After 5 minutes the temperature is raised to 40°C and maintained for 40 minutes. [0080] The bath is discharged and the goods is centrifuged without any rinse and dried at 80-900C. [0081] The yarn of the cones is used to knit samples which are tested according to the IWS TM31 5x5 A test method (simulating 50 machine washings) and the shrinkage is measured. [0082] Shrinkage of the treated material is -17 '.22%, while a comparative untreated material shows a shrinkage of -30% after the 1x5A test
(simulating only 10 machine washings). [0083] Treatment of a knitted fabric [0084] Knitted fabrics (count 2/30) are treated with 4% on the weight on goods of
Basolan® DC and dyed with premetallised dyes in a laboratory "linitest" dyeing machine. [0085] After water has been charged and recirculation has started, the pH is regulated to 8 with 30% technical grade ammonium hydroxide. [0086] 4 g/l of Deterlam SI are introduced in the dyeing machine through the expansion vessel.
[0087] The temperature is raised to 40°C and maintained for 30 minutes. [0088] The bath is discharged and the hanks are accurately rinsed. [0089] The fresh bath is regulated to pH 5. [0090] Through the expansion vessel 15% on the weight of goods of Composition
A are added. The product is charged and homogenised for 5 minutes. [0091] 5% on the weight of goods of Composition B is added. [0092] After 5 minutes the temperature is raised to 40°C and maintained for 40 minutes. [0093] The bath is discharged and the goods is centrifuged without any rinse and dried at 80-900C. [0094] The knitted fabrics are tested according to the IWS TM31 5x5 A test method and the shrinkage is measured. [0095] Shrinkage of the treated material is -8.5%, while a comparative untreated material shows a shrinkage of -40% after the 1x5A test (simulating only 10 machine washings).

Claims

Claims
1. Method for treating wool comprising the following steps: i) an aqueous composition containing a cationic polyurethane, a non-blocked nonionic water- dispersible polyisocyanate and an ethoxylated phosphated alcohol having one or more phosphoric group in acidic form is prepared; ii) wool is impregnated with the obtained aqueous composition; iii) the wool is dried.
2. Method for treating wool according to claim 1 , wherein the aqueous composition comprises from 0.5 to 5 % of cationic polyurethane, from 0.3 to 3 % of non-blocked nonionic water-dispersible polyisocyanate and from 0.03 to 0.3% of ethoxylated phosphated alcohol having one or more phosphoric group in acidic form on the weight of goods.
3. Method for treating wool according to claim 2 in which step ii) is carried out at 20-60° C for from 10 to 60 minutes at a pH form 4 to 6, to reach exhaustion of the composition.
4. Method for treating wool according to claim 3 wherein the polyurethane is a filming polymer forming a film with an elongation to break of 400 to 1 ,000%, as determined according to method ASTM D882-02 obtained by: a) reacting one or more organic diisocyanates with a mixture of an alkyldiethanolamine and at least one linear polyol to obtain a prepolymer having free isocyanate groups; b) cationising the amine groups; c) extending the obtained cationic polyisocyanate with water or amines.
5. Method for treating wool according to any of the preceding claims wherein the aqueous composition is prepared by adding into it the non blocked non-ionic water dispersible polyisocyanate and the ethoxylated phosphated alcohols in acid form in the form of a composition (Composition II) that contains both of them.
6. Method for treating wool according to claim 5 wherein Composition Il comprises I) from 30 to 99% by weight of at least one non-blocked nonionic water-dispersible polyisocyanate obtained by reaction of aliphatic or cycloaliphatic polyisocyanates containing from 3 to 10 isocyanate groups per molecule with polyols; II) from 1 to 20% by weight, and preferably from 5 to 15% by weight, of one or more ethoxylated phosphated alcohols in acid form III) from 0 to 50% by weight, and preferably from 5 to 30% by weight, of a non reactive, water miscible solvent.
PCT/EP2008/063530 2007-10-15 2008-10-09 Method for treating wool WO2009050102A1 (en)

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ITVA20070077 ITVA20070077A1 (en) 2007-10-15 2007-10-15 TREATMENT FOR WOOL

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CN106811973A (en) * 2016-12-23 2017-06-09 句容市申兔工艺针织厂 A kind of finishing technique of the anti-fuzz balls of cashmere knit goods
CN110306348A (en) * 2019-07-12 2019-10-08 常熟市新光毛条处理有限公司 A kind of shrinkproof anti-sticking mixed processing method of wool top
CN110485164A (en) * 2019-08-30 2019-11-22 江苏阳光股份有限公司 A kind of production technology of nice and cool pashm worsted plus material

Citations (2)

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Publication number Priority date Publication date Assignee Title
EP0560161A1 (en) * 1992-03-12 1993-09-15 Bayer Ag Composition and process for the treatment of textiles
EP1437437A2 (en) * 2003-01-10 2004-07-14 Bayer Chemicals AG Anti-felting treatment of keratinous fibres

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Publication number Priority date Publication date Assignee Title
CN1304461C (en) * 2004-10-19 2007-03-14 东华大学 Polyurethane wool anti-felting finish agent and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0560161A1 (en) * 1992-03-12 1993-09-15 Bayer Ag Composition and process for the treatment of textiles
EP1437437A2 (en) * 2003-01-10 2004-07-14 Bayer Chemicals AG Anti-felting treatment of keratinous fibres

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