WO2024012662A1 - Extender compounds for durable water repellence - Google Patents

Extender compounds for durable water repellence Download PDF

Info

Publication number
WO2024012662A1
WO2024012662A1 PCT/EP2022/069458 EP2022069458W WO2024012662A1 WO 2024012662 A1 WO2024012662 A1 WO 2024012662A1 EP 2022069458 W EP2022069458 W EP 2022069458W WO 2024012662 A1 WO2024012662 A1 WO 2024012662A1
Authority
WO
WIPO (PCT)
Prior art keywords
isocyanate
compound
dwr
poly
water
Prior art date
Application number
PCT/EP2022/069458
Other languages
French (fr)
Inventor
Andreas Fuchs
Isabella Rettenbacher
Edeltraud Schidek
Original Assignee
Huntsman Textile Effects (Germany) Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huntsman Textile Effects (Germany) Gmbh filed Critical Huntsman Textile Effects (Germany) Gmbh
Priority to PCT/EP2022/069458 priority Critical patent/WO2024012662A1/en
Publication of WO2024012662A1 publication Critical patent/WO2024012662A1/en

Links

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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8029—Masked aromatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8041—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3271
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • 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
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters 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
    • 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
    • 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
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention relates to the use of compounds that are the reaction product of a di- or poly-isocyanate and an aromatic compound as a non-reactive extender for durable water-repellence in textile fabrics, as well as a durable water-repellence system (DWR) comprising said non-reactive extender and a water-repellent compound, their use in water- repellent finishing of fibre materials, and a process for treating textile fabrics using said non- reactive extender or DWR system.
  • the non-reactive extenders and the DWR systems according to the present invention are free of fluorochemicals and endow natural and synthetic textile fabrics with water-repellent properties.
  • Blocked isocyanate extenders are typically delivered as emulsions in water.
  • An example of such extender for oil- and water-repellent products is PHOBOL® XAN extender (Huntsman Corp.), which is a dispersion of an oxime-blocked isocyanate, requiring at least 150°C curing temperature for safety and performance reasons.
  • blocked isocyanate encompasses mono-, di- and poly-isocyanates in which an isocyanate group has been reacted with blocking agents which, upon heating, release the isocyanate and the blocking agent.
  • Blocking agents are e.g. amines, amides, compounds having an active hydrogen atom or alcohols. If said heating is carried out in the presence of a compound having a functional group that can react with said isocyanate group, such as a hydroxyl or an amino group of a suitable substrate such as a fibre, an improved adhesion may result.
  • These blocked isocyanates are thus called extenders of the reactive-type, having as drawbacks the need of a curing temperature above 150°C and the release of the blocking agent, which is usually harmful for the environment.
  • aqueous systems to obtain water-repellent properties on textiles which comprise paraffin wax and/or acrylic polymers.
  • An ultimate goal is to reduce the amount of chemicals used in and energy consumed during the process.
  • Such substances and processes are described, for example, in WO2010115496 A1 , WO2018054712 A1 and WO2011035906 A2.
  • the present invention also provides a process for obtaining excellent water-repellent properties on said fabrics.
  • the present invention relates to the use of a compound, which is the reaction product of:
  • R 1 , R 2 , R 3 , R 4 and R 5 are independently selected from the group consisting of H and Ci-4 alkyl;
  • Y is OH, NH 2 or SH
  • X is O, N or S
  • non-reactive extender in the context of the present disclosure means that the respective compounds do not react with functional group(s) of the textile fibres.
  • the non-reactive extenders and the durable water- repel I ence (DWR) systems according to the present invention do neither contain any fluorochemicals nor styrenes.
  • the non-reactive extenders and the DWR systems according to the present invention do not release any potentially toxic compound upon curing of the textile fabrics. Accordingly, the present invention further limits the number of ingredients used in the preparation of extenders and DWR systems for textile applications which are potentially harmful to health and environment.
  • the at least one di- or poly-isocyanate (i) is preferably at least one, for example one, two or three aromatic isocyanates, aliphatic isocyanates, pre-condensates or condensates thereof.
  • the aromatic isocyanate is methylene diphenyl isocyanate (MDI) or toluene diisocyanate (TDI)
  • the pre-condensate or condensate is a methylene diphenyl isocyanate (MDI)-based pre-condensate or a hexamethylene diisocyanate (HDI)-based condensate.
  • pre-condensate and “pre-polymer” are herein used interchangeably and mean a stable, usually partially polymerized chemical intermediate that is still reactive, i.e. can be fully polymerized at a later time (e.g. MDI pre-condensate Suprasec® 2021 or 2010 from Huntsman Corp.).
  • the at least one aromatic compound (ii) is preferably benzyl alcohol or furfuryl alcohol.
  • the aliphatic compound of formula (III) is stearyl alcohol.
  • the further reactant(s) (iii) is/are selected from the group consisting of one or more di- or polyols, N-methyl diethanolamine (NMDEA), 2,2,6,6-tetramethylpiperidine (TMP), and mixtures thereof.
  • Suitable diols according to the present invention include ethylene glycol, diethylene glycol, triethyleneglycol, 1 ,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,5-heptanediol, or a combination thereof.
  • Suitable polyols according to the present invention comprise three or more hydroxyl groups and include glycerol, trimethylol ethane, trimethylol propane, 1 ,2,6-hexanetriol, pentaerythritol, tri pentaerythritol, di pentaerythritol, trimethylol propane, propoxylated pentaerythritol, ethoxylated pentaerythritol, ethoxylated trimethylol propane, xylitol, sorbitol, glucose, fructose and sucrose.
  • glycerol trimethylol ethane
  • trimethylol propane 1 ,2,6-hexanetriol
  • pentaerythritol tri pentaerythritol
  • di pentaerythritol trimethylol propane
  • propoxylated pentaerythritol ethoxylated pentaeryth
  • M DI methylene diphenyl isocyanate
  • the compound according to the present invention may be formulated as an aqueous dispersion, preferably comprising from about 20 weight% to about 35 weight% dry content including surfactants.
  • Suitable surfactants according to the present invention are dispersants including known commercially available surface-active compounds such as nonionic ethoxylated compounds, for example ethoxylated alcohols or ethoxylated carboxylic acids, cationic surfactants such as quaternary ammonium salts, or fatty amines.
  • the fatty amines are applied in combination with a suitable acid, for example, an organic acid such as acetic acid.
  • the present invention also relates to a durable water-repellence (DWR) system, comprising (a) at least one non-fluorinated water-repellent compound; and (b) at least one non- reactive extender compound according to the present invention.
  • DWR durable water-repellence
  • the at least one non-fluorinated water-repellent compound (a) is preferably selected from the group consisting of polyurethane, acrylic copolymer, wax, melamine condensates, silicone repellents, hyperbranched/dendrimeric repellents, and mixtures thereof.
  • the ratio of the at least one non-fluorinated water-repellent compound (a) to compound (b) is from about 90:10 to about 10:90, preferably from about 80:20 to about 20:80, more preferably from about 70:30 to about 30:70, and most preferably from about 60:40 to about 40:60.
  • compound (a) is a polyurethane, an acrylic copolymer or a mixture thereof, and the ratio of (a) to (b) is from about 5:1 to about 1 :2, preferably from about 3:1 to about 1 :1.
  • the DWR system according to the present invention may further comprise one or more substances selected from the group consisting of additives, solvents and surfactants.
  • Suitable additives are wetting agents (e.g. INVADINE® PBN, from Huntsman Corp.), pH control agents (e.g. acetic acid, citric acid, hydrochloric acid, propionic acid, benzoic acid and sodium salts thereof), resins, catalysts (e.g. Knittex® types from Huntsman Corp.) and cosolvents for stabilization (e.g. glycols).
  • wetting agents e.g. INVADINE® PBN, from Huntsman Corp.
  • pH control agents e.g. acetic acid, citric acid, hydrochloric acid, propionic acid, benzoic acid and sodium salts thereof
  • resins e.g. Knittex® types from Huntsman Corp.
  • cosolvents for stabilization e.g. glycols
  • Suitable solvents are any type of substance that can dissolve the compounds of the present DWR system to form a solution, e.g. alkyl acetates (such as ethyl acetate, n-propyl acetate, butyl acetate), methyl ethyl ketone (MEK), methyl /so-butyl ketone (MiBK), and dimethylformamide (DMF).
  • alkyl acetates such as ethyl acetate, n-propyl acetate, butyl acetate
  • MEK methyl ethyl ketone
  • MiBK methyl /so-butyl ketone
  • DMF dimethylformamide
  • the non-reactive extender and the DWR system according to the present invention are useful in the water-repellent finishing of fiber materials.
  • the present invention further relates to a process for treating a textile fabric composed of fiber materials, comprising the steps of padding the fabric with the present non-reactive extender or DWR system, and subsequently drying.
  • the process according to the present invention may further comprise the step of curing.
  • the maximum curing temperature is equal or below 180°C, preferably equal or below 150°C, more preferably equal or below 110°C, even more preferably equal or below 100°C, and most preferably equal or below 80°C.
  • Textile fabrics to be treated with the compound or DWR system according to the present invention are, for example, polyester, polyamide, cotton, blends or variations thereof.
  • the fabric is polyester or polyamide, or blends or variations thereof.
  • Such fabrics are wovens, knits or nonwovens.
  • the concentration of the compound according to the present invention is from about 2 to about 20 g/L, preferably from about 5 to about 15 g/L, and most preferably about 10 g/L to about 200 g/L, in a pad bath.
  • the compound and DWR system according to the present invention are particularly useful for conferring water-repellent properties on natural and synthetic textile fabrics.
  • the desired water-repellence effect level is achieved on synthetic textile fabrics, such as polyester fabrics or mixed fabrics of cotton and polyester, but is also visible in cotton fabrics.
  • the textile fabrics treated with the compounds and DWR system according to the present invention are especially suitable for outerwear.
  • Suprasec® 2021 pre-polymerised diphenyl methane diisocyanate (MDI) - functionality of 2.5 NCO groups per unit (Huntsman Corp.)
  • MiBK methyl-/so-butyl ketone
  • BuAc butyl acetate trimethylolpropane
  • TMP 2,2,6,6-tetramethylpiperidine furfuryl alcohol benzyl alcohol stearyl alcohol
  • Ethoquad HT/25 ethoxylated tallow methyl ammonium chloride propylene glycol
  • HAc acetic acid IVADINE® PBN: wetting agent (Huntsman Corp.)
  • Neoseed® NR-7080 polyacrylate based repellent (Nicca Textile Chemicals)
  • Zelan® R3 polyurethane based repellent (Chemours/Huntsman Corp.)
  • UXN Phobol Extender® UXN Reactive extender (Huntsman Corp.)
  • NonREx 2 benzyl alcohol alone
  • NonREx 3 a mixture of furfuryl alcohol and stearyl alcohol
  • Table 1 shows the non-reactive extender compounds obtained according to the invention (NonREx 1-3), as well as the composition of a comparative extender (Comp. 1), using 2-HEA instead of one or more aromatic/aliphatic alcohols. These compositions have been used for the preparation of the aqueous dispersions in Example 2.
  • Table 1 Non-reactive extender compounds (NonREx 1-3) according to the invention and comparative extender (Comp. 1).
  • NMDEA /V-methyl diethanolamine
  • MiBK methyl-fso-butyl ketone
  • BuAc butyl acetate
  • Table 2 illustrates the different aqueous dispersions obtained with the non- reactive extender compounds according to the invention (Non-REx 1-3) and comparative extender (Comp. 1).
  • Table 2 Aqueous dispersions according to the invention and comparative aqueous dispersion.
  • NonREx 1 NonREx 2 NonREx 3 Comp. 1 organic solution ex. 1 g 150 150 145 150
  • All loadings in g/L refer to a standard solids content of 25% and are corrected in the reports to match this level.
  • Standard recipes on synthetics contain 1 g/L HAc 60% and 5 mL/L IVADINE® PBN as wetting agent.
  • the typical curing conditions for extender-containing formulations, as required by for product safety reasons for blocked isocyanates, are drying for 10 minutes at 110°C and curing at least 5 minutes at 150°C in a drying cupboard or equivalent conditions on a Mathis lab dryer. Application is done by padding in a manual lab foulard.
  • able 3 Comparison of performance of the repellents alone (Standard) and different DWR systems subjected to Bundesmann test.
  • the recipe cured at 80°C (DWR system 4) instead of 150°C kept the performance level or was improved, saving energy, removing the need for high curing temperatures and eliminating residual blocking agent on the fabric and in the exhaust compared to standard extender types.
  • NR7080 (Standard 3) at 30 g/L achieved about 30% water absorbency for all curing times at 80°C, while the combination of 30g/L NR7080 with 10 g/L NonREx 1 (DWR System 4) absorbed about 21 % water absorbency, reaching or surpassing the 150°C level of the NR7080 (Standard 1) alone.
  • Non-REx 1-type furan
  • phenyl Non-REx 2-type
  • DWR System 4 DWR System 4
  • Blending the furfuryl-type extender (Non-REx 1) with a polyurethane wax (oligofunctional isocyanate reacted with stearyl alcohol) was also effective as an extender system, exhibiting a similar performance compared to Non-REx 1. Adding the stearyl component directly to the recipe improves the effect even more.
  • the DWR systems according to the invention offer a strongly improved effect concerning the Bundesmann rain test before laundry, even at lower levels of repellent applied, thus lowering the cost of the recipes and reduce total amount of chemicals applied to the textile. After 5 laundry cycles (HL) the effect is reduced but still visible. After 20 laundry cycles no differences are observable, i.e. the product does not impar performance here. Main effect measure is the amount of water absorbed by the fabric in mass% during the test, the lower the better.
  • the NonREx compounds according to the invention alone may contribute to water- repellence on its own, although not shown in the above results.
  • the DWR systems according to the present invention perform already at 80°C delivering effect levels otherwise only seen above 120°C (e.g. Phobol® Extender XAN or UXN, which require a curing temperature of at least 150°C) reducing again cost and environmental impact, making them also applicable to fabrics requiring special treatment conditions.
  • Phobol® Extender XAN or UXN which require a curing temperature of at least 150°C
  • MDI methylene diphenyl diisocyanate
  • HDI hexamethylene diisocyanate
  • AATCC American Association of Textile Chemists and Colorists

Abstract

The present invention relates to the use of a compound, which is the reaction product of: (i) at least one di- or poly-isocyanate; (ii) at least one aromatic compound selected from the group consisting of: (I) and (II) wherein R1, R2, R3, R4 and R5 are independently selected from the group consisting of H and C1-4 alkyl; Y is OH, NH2 or SH; X is O, N or S; and (iii) optionally one or more further reactants; as a non-reactive extender for durable water-repellence in textile fabrics. The present invention further relates to a durable water-repellence (DWR) system comprising at least one non-fluorinated water-repellent compound and at least one non-reactive extender compound as above, their use in water-repellent finishing of fibre materials, as well as a process for treating a textile fabric composed on fibre materials.

Description

EXTENDER COMPOUNDS FOR DURABLE WATER REPELLENCE
[1] The present invention relates to the use of compounds that are the reaction product of a di- or poly-isocyanate and an aromatic compound as a non-reactive extender for durable water-repellence in textile fabrics, as well as a durable water-repellence system (DWR) comprising said non-reactive extender and a water-repellent compound, their use in water- repellent finishing of fibre materials, and a process for treating textile fabrics using said non- reactive extender or DWR system. The non-reactive extenders and the DWR systems according to the present invention are free of fluorochemicals and endow natural and synthetic textile fabrics with water-repellent properties.
[2] Over the past years, many countries have committed to improve the quality of the environment by saving natural resources and reducing the emission of substances which are harmful to the climate. Funds are provided by the governments to support the industry in achieving these goals. The consumer is asking for environmentally friendly textile products which are produced in accordance with highest ecological standards. Brands and retailers are conveying these demands into real requirements and textile manufacturers are continuously improving their production excellence by investing in modern equipment and selecting environmentally friendly chemical substances.
[3] It is known to furnish textile fabrics, such as wovens, knits or nonwovens, with certain properties, for example, water-repellence, by treating the fabrics with aqueous dispersions containing particular chemical ingredients. Water-repellent properties on textiles are usually achieved by using fluorine-containing products as such chemical ingredients. However, fluorine-containing products are costly and their use has been restricted due to the developing regulatory framework for chemicals.
[4] Fluorochemical treatments are relatively expensive and are often used in combination with less expensive non-fluorinated "extenders". Among known extenders, blocked isocyanates are a desirable class, since they are inexpensive, easy to prepare, and very effective. Blocked isocyanate extenders are typically delivered as emulsions in water. An example of such extender for oil- and water-repellent products is PHOBOL® XAN extender (Huntsman Corp.), which is a dispersion of an oxime-blocked isocyanate, requiring at least 150°C curing temperature for safety and performance reasons.
[5] The term "blocked isocyanate" encompasses mono-, di- and poly-isocyanates in which an isocyanate group has been reacted with blocking agents which, upon heating, release the isocyanate and the blocking agent. Blocking agents are e.g. amines, amides, compounds having an active hydrogen atom or alcohols. If said heating is carried out in the presence of a compound having a functional group that can react with said isocyanate group, such as a hydroxyl or an amino group of a suitable substrate such as a fibre, an improved adhesion may result. These blocked isocyanates are thus called extenders of the reactive-type, having as drawbacks the need of a curing temperature above 150°C and the release of the blocking agent, which is usually harmful for the environment.
[6] Alternatively, aqueous systems to obtain water-repellent properties on textiles have been suggested which comprise paraffin wax and/or acrylic polymers. An ultimate goal is to reduce the amount of chemicals used in and energy consumed during the process. Such substances and processes are described, for example, in WO2010115496 A1 , WO2018054712 A1 and WO2011035906 A2.
[7] It is an object of the present invention to provide non-reactive extenders and systems that help provide excellent water-repellent properties on all textile fabrics including polyester- containing fabrics and reducing energy consumed and amount of chemical used in the process. The present invention also provides a process for obtaining excellent water-repellent properties on said fabrics.
[8] Accordingly, the present invention relates to the use of a compound, which is the reaction product of:
(i) at least one di- or poly-isocyanate;
(ii) at least one aromatic compound selected from the group consisting of:
Figure imgf000003_0001
(I) (H) wherein
R1, R2, R3, R4 and R5 are independently selected from the group consisting of H and Ci-4 alkyl;
Y is OH, NH2 or SH;
X is O, N or S; and
(iii) optionally one or more further reactants; as a non-reactive extender for durable water-repellence in textile fabrics. [9] The term “non-reactive extender” in the context of the present disclosure means that the respective compounds do not react with functional group(s) of the textile fibres.
[10] The non-reactive extenders and the durable water- repel I ence (DWR) systems according to the present invention do neither contain any fluorochemicals nor styrenes. In addition, as there is no reaction with functional group(s) of the textile fibres, the non-reactive extenders and the DWR systems according to the present invention do not release any potentially toxic compound upon curing of the textile fabrics. Accordingly, the present invention further limits the number of ingredients used in the preparation of extenders and DWR systems for textile applications which are potentially harmful to health and environment.
[11] The at least one di- or poly-isocyanate (i) is preferably at least one, for example one, two or three aromatic isocyanates, aliphatic isocyanates, pre-condensates or condensates thereof.
[12] In a preferred aspect, the aromatic isocyanate is methylene diphenyl isocyanate (MDI) or toluene diisocyanate (TDI), and the pre-condensate or condensate is a methylene diphenyl isocyanate (MDI)-based pre-condensate or a hexamethylene diisocyanate (HDI)-based condensate.
[13] The terms “pre-condensate” and “pre-polymer” are herein used interchangeably and mean a stable, usually partially polymerized chemical intermediate that is still reactive, i.e. can be fully polymerized at a later time (e.g. MDI pre-condensate Suprasec® 2021 or 2010 from Huntsman Corp.).
[14] The at least one aromatic compound (ii) is preferably benzyl alcohol or furfuryl alcohol.
[15] In one embodiment of the present invention, 50 mol% of the at least one aromatic compound (ii) is replaced with an aliphatic compound of formula (III) 'Y
, ' -21
(III), wherein Y is OH, NH2 or SH.
[16] In a preferred aspect, the aliphatic compound of formula (III) is stearyl alcohol.
[17] In one aspect, about 40% or more, and preferably about 60% or more, of the -N=C=O groups of the at least one di- or poly-isocyanate (i) reacts with the aromatic compound (ii). [18] The further reactant(s) (iii) is/are selected from the group consisting of one or more di- or polyols, N-methyl diethanolamine (NMDEA), 2,2,6,6-tetramethylpiperidine (TMP), and mixtures thereof.
[19] Suitable diols according to the present invention include ethylene glycol, diethylene glycol, triethyleneglycol, 1 ,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,5-heptanediol, or a combination thereof.
[20] Suitable polyols according to the present invention comprise three or more hydroxyl groups and include glycerol, trimethylol ethane, trimethylol propane, 1 ,2,6-hexanetriol, pentaerythritol, tri pentaerythritol, di pentaerythritol, trimethylol propane, propoxylated pentaerythritol, ethoxylated pentaerythritol, ethoxylated trimethylol propane, xylitol, sorbitol, glucose, fructose and sucrose.
[21] In one aspect, the further reactant(s) (iii) react(s) with about 60% or less, or preferably about 40% or less of the -N=C=O groups of the at least one di- or poly-isocyanate (i). In another aspect, the further reactant(s) (iii) reacts with about 10% to about 30% of the -N=C=O groups of the at least one di- or poly-isocyanate (i).
[22] In a preferred aspect, the compound according to the present invention is the reaction product of (i) methylene diphenyl isocyanate (M DI)- based pre-condensate having a functionality of equal or above 2, (ii) furfuryl alcohol or benzyl alcohol, which reacts with about 60% or more of the -N=C=O groups of the at least one di- or poly-isocyanate (i); and N-methyl diethanolamine (NMDEA) (iii), which reacts with about 10% of the -N=C=O groups of the at least one di- or poly-isocyanate (i), or 2,2,6,6-tetramethylpiperidine (TMP) (iii), which reacts with about 30% of the -N=C=O groups of the at least one di- or poly-isocyanate (i).
[23] The compound according to the present invention may be formulated as an aqueous dispersion, preferably comprising from about 20 weight% to about 35 weight% dry content including surfactants.
[24] Suitable surfactants according to the present invention are dispersants including known commercially available surface-active compounds such as nonionic ethoxylated compounds, for example ethoxylated alcohols or ethoxylated carboxylic acids, cationic surfactants such as quaternary ammonium salts, or fatty amines. Appropriately, the fatty amines are applied in combination with a suitable acid, for example, an organic acid such as acetic acid.
[25] If desired, further ingredients which are known to be useful as constituents of textiletreating compositions may be added to the resulting aqueous dispersion of the present invention. [26] The present invention also relates to a durable water-repellence (DWR) system, comprising (a) at least one non-fluorinated water-repellent compound; and (b) at least one non- reactive extender compound according to the present invention.
[27] The at least one non-fluorinated water-repellent compound (a) is preferably selected from the group consisting of polyurethane, acrylic copolymer, wax, melamine condensates, silicone repellents, hyperbranched/dendrimeric repellents, and mixtures thereof.
[28] In one aspect, the ratio of the at least one non-fluorinated water-repellent compound (a) to compound (b) is from about 90:10 to about 10:90, preferably from about 80:20 to about 20:80, more preferably from about 70:30 to about 30:70, and most preferably from about 60:40 to about 40:60.
[29] In a preferred aspect, compound (a) is a polyurethane, an acrylic copolymer or a mixture thereof, and the ratio of (a) to (b) is from about 5:1 to about 1 :2, preferably from about 3:1 to about 1 :1.
[30] The DWR system according to the present invention may further comprise one or more substances selected from the group consisting of additives, solvents and surfactants.
[31] Suitable additives are wetting agents (e.g. INVADINE® PBN, from Huntsman Corp.), pH control agents (e.g. acetic acid, citric acid, hydrochloric acid, propionic acid, benzoic acid and sodium salts thereof), resins, catalysts (e.g. Knittex® types from Huntsman Corp.) and cosolvents for stabilization (e.g. glycols).
[32] Suitable solvents are any type of substance that can dissolve the compounds of the present DWR system to form a solution, e.g. alkyl acetates (such as ethyl acetate, n-propyl acetate, butyl acetate), methyl ethyl ketone (MEK), methyl /so-butyl ketone (MiBK), and dimethylformamide (DMF).
[33] The non-reactive extender and the DWR system according to the present invention are useful in the water-repellent finishing of fiber materials.
[34] The present invention further relates to a process for treating a textile fabric composed of fiber materials, comprising the steps of padding the fabric with the present non-reactive extender or DWR system, and subsequently drying.
[35] The process according to the present invention may further comprise the step of curing. The maximum curing temperature is equal or below 180°C, preferably equal or below 150°C, more preferably equal or below 110°C, even more preferably equal or below 100°C, and most preferably equal or below 80°C.
[36] Textile fabrics to be treated with the compound or DWR system according to the present invention are, for example, polyester, polyamide, cotton, blends or variations thereof. Preferably, the fabric is polyester or polyamide, or blends or variations thereof. Usually, such fabrics are wovens, knits or nonwovens.
[37] In the process according to the present invention, the concentration of the compound according to the present invention is from about 2 to about 20 g/L, preferably from about 5 to about 15 g/L, and most preferably about 10 g/L to about 200 g/L, in a pad bath.
[38] The compound and DWR system according to the present invention are particularly useful for conferring water-repellent properties on natural and synthetic textile fabrics. Surprisingly, the desired water-repellence effect level is achieved on synthetic textile fabrics, such as polyester fabrics or mixed fabrics of cotton and polyester, but is also visible in cotton fabrics. The textile fabrics treated with the compounds and DWR system according to the present invention are especially suitable for outerwear.
[39] The following Examples serve to illustrate the invention. Unless otherwise indicated, the temperatures are given in degrees Celsius, and concentration is in g/L.
Chemicals
Suprasec® 2021 : pre-polymerised diphenyl methane diisocyanate (MDI) - functionality of 2.5 NCO groups per unit (Huntsman Corp.)
MiBK: methyl-/so-butyl ketone
BuAc: butyl acetate trimethylolpropane
NMDEA: /V-methyl diethanolamine
TMP: 2,2,6,6-tetramethylpiperidine furfuryl alcohol benzyl alcohol stearyl alcohol
2-HEA: 2-hydroxyethyl acrylate
Marlipal 013/100: ethoxylated isotridecyl alcohol 10EO
Ethoquad HT/25: ethoxylated tallow methyl ammonium chloride propylene glycol
HAc: acetic acid IVADINE® PBN: wetting agent (Huntsman Corp.)
Neoseed® NR-7080: polyacrylate based repellent (Nicca Textile Chemicals) Zelan® R3: polyurethane based repellent (Chemours/Huntsman Corp.) UXN: Phobol Extender® UXN Reactive extender (Huntsman Corp.)
Examples
Example 1 - Synthesis of a Non-Reactive Extender Compound of the Present Invention (NonREx 1)
[40] In a 500 mL three-neck round bottom flask, equipped with a mechanical stirrer, internal thermometer, and a reflux condenser, 90.5 g of Suprasec® 2021 (0.500 eq NCO, assumed mol weight 362 g/mol) and 96 g MiBK were added under inter atmosphere. After several minutes of stirring at room temperature, a clear, low viscous solution was obtained. Then, 6.70 g (50mmol; 0.150 eq) of trimethylolpropane was added and temperature was raised to 50°C while continuously stirring the solution. Reaction progress was followed using IR spectroscopy, monitoring the peak area at 2260 cm-1 (NCO valence vibration). After 90 min at 50°C, 2.98 g (25 mmol; 0.050 eq) of NMDEA in 5.75 g of MiBK was added; a temperature increase of 7°C indicated a strong exothermic reaction. After 1 h of continued stirring at 50°C, 50.0 g of MiBK was used to dilute the reaction mass. An amount of 29.40 g (300 mmol; 0.3 eq) of furfuryl alcohol was prepared and added dropwise. During addition an exothermal reaction raised the internal temperature by 9°C. After another 90 minutes of continued stirring at 50°C, the reaction mass was allowed to cool to room temperature overnight. As viscosity increased during that period, another 46 g of MiBK was added. 370 g of reaction at 35% dry content mass were obtained.
[41] Further non-reactive extender compounds were prepared with benzyl alcohol alone (NonREx 2) and a mixture of furfuryl alcohol and stearyl alcohol (NonREx 3), synthesized from multivalent isocyanate prepolymers according to the same reaction scheme.
[42] Table 1 shows the non-reactive extender compounds obtained according to the invention (NonREx 1-3), as well as the composition of a comparative extender (Comp. 1), using 2-HEA instead of one or more aromatic/aliphatic alcohols. These compositions have been used for the preparation of the aqueous dispersions in Example 2. Table 1 : Non-reactive extender compounds (NonREx 1-3) according to the invention and comparative extender (Comp. 1).
Figure imgf000009_0001
* S. 2021 = Suprasec® 2021
FFA = furfuryl alcohol
BZA = benzyl alcohol
SA = stearyl alcohol
2-HEA = 2-hydroxyethyl acrylate
TMP = 2,2,6,6-tetramethylpiperidine
NMDEA = /V-methyl diethanolamine MiBK = methyl-fso-butyl ketone BuAc = butyl acetate
Example 2 - General Procedure for Aqueous Dispersion preparation
[43] 150 g of the organic solution obtained in Example 1 (organic solution ex. 1 , 35.0% dry content) were kept at 60°C for 45 min. A solution of 2.1 g Marlipal 013/100, 1.05 g Ethoquad HT/25, 7.87 g propylene glycol and 243.75 g water were prepared at 55-60°C, then 6.3 g of HAc 60% were added to achieve a pH of about 3. The organic solution was added to the surfactant mixture while using a high-speed shear force stirrer. The resulting mass was passed through a high-pressure homogenizer four times at 200 bar (2x107 Pa) and 54-62°C. The organic solvent was removed from the resulting emulsion under reduced pressure. Water was added to obtain a white emulsion with a dry content of 25% (1 h at 120°C under infrared drying conditions).
[44] Table 2 below illustrates the different aqueous dispersions obtained with the non- reactive extender compounds according to the invention (Non-REx 1-3) and comparative extender (Comp. 1). Table 2: Aqueous dispersions according to the invention and comparative aqueous dispersion.
Component Unit NonREx 1 NonREx 2 NonREx 3 Comp. 1 organic solution ex. 1 g 150 150 145 150
Surfactants Marlipal 013/100 g 2.1 2.1 1.74 2.1
Ethoquad HT/25 g 1.05 1.05 0.87 1.05 diol propylene glycol g 7.87 7.87 6.52 7.87
HAc 60% g 6.3 6.3 0.44 5.2 water g 243.75 243.75 253.75 243.75
Aqueous yield g 194.6 266 168 185.3 Dispersion dry content % 25 17.3 21 .9 25 pH 3.2 3.2 4.2
[45] The following examples describe - as a representative example - the treatment of PES textile fabrics (blue polyester, ID004) with DWR systems using the aqueous dispersions prepared as per the general procedure of Example 2.
Example 3 - Application Examples (Finishing)
General conditions
- Application
[46] All loadings in g/L refer to a standard solids content of 25% and are corrected in the reports to match this level. Standard recipes on synthetics contain 1 g/L HAc 60% and 5 mL/L IVADINE® PBN as wetting agent. The typical curing conditions for extender-containing formulations, as required by for product safety reasons for blocked isocyanates, are drying for 10 minutes at 110°C and curing at least 5 minutes at 150°C in a drying cupboard or equivalent conditions on a Mathis lab dryer. Application is done by padding in a manual lab foulard.
Laundry
[47] Samples are tested before and after laundry/one final tumble dryer cycle (LTD, laundry tumble dry). Here, laundry type 4N at 40°C, a typical home laundry simulation, is used. The fabrics are washed together with a certain amount of additional load to meet a certain stress level for the samples.
[48] The finished fabrics obtained as per the application examples were subjected to the following tests:
[49] (I) Spray test as per AATCC
Result: droplets falling of the fabric, Spray rating 100 (best), 50 (worst); 0 (complete wetting)
[50] (II) Bundesmann test (BM) as per AATCC
Results: Bundesmann rating after 1, 5 and 10 minutes, like Spray rating 5 (no water remains on the surface, i.e. best result) to 1 (complete surface wetting)
- Water absorbency: relative weight gain of fabric sample after test in percent leakage; amount of water penetrating the sample, in mL
[51] The different DWR systems according to the invention have been prepared and compared with repellents alone (Standard) in different concentrations, as well as with comparative DWR systems. The results are summarized below in Table 3.
able 3: Comparison of performance of the repellents alone (Standard) and different DWR systems subjected to Bundesmann test.
Figure imgf000012_0001
NR-7080: Neoseed® NR-7080 FA = Furfuryl alcohol A = Stearyl alcohol ZA = Benzyl alcohol -HEA = 2-Hydroxyethyl Acrylate XN: Phobo® Extender UXN L: Home Laundry Cycles
[52] As it can be seen from Table 3 above, the DWR systems according to the present invention (i.e. NonREx 1-3 in combination with repellent acrylates - Neoseed® NR7080 and Zelan R3), a strong reduction in water absorbency on PES fabrics in different scenarios is visible. Spray rating is not impacted, it is 100 for all samples, unless otherwise mentioned.
[53] Importantly, the recipe cured at 80°C (DWR system 4) instead of 150°C kept the performance level or was improved, saving energy, removing the need for high curing temperatures and eliminating residual blocking agent on the fabric and in the exhaust compared to standard extender types.
[54] In addition, NR7080 (Standard 3) at 30 g/L achieved about 30% water absorbency for all curing times at 80°C, while the combination of 30g/L NR7080 with 10 g/L NonREx 1 (DWR System 4) absorbed about 21 % water absorbency, reaching or surpassing the 150°C level of the NR7080 (Standard 1) alone.
[55] Reducing the amount of repellent NR-7080 to 10 g/L (Standard 3) and comparing it with a recipe with additional 5 g/L of Non-REx 2 or 3 (DWR System 4) yielded again absorbency around 21 % with at 80°C. Leakage and Bundesmann ratings were restored to the levels of 30 g/L repellent alone, i.e. the combinations of 10g/L NR-7080 and 5g/L NonREx 2 or 3 at 80°C achieve similar results of 30g/L NR-7080 at 150°C. Changing the functional group in the polyurethane from furan (Non-REx 1-type) to phenyl (Non-REx 2-type) affected the performance in a similar way, i.e. they are exchangeable (DWR System 4), so that the NonREx 1 can be replaced at 150°C or 80°C with Non-REx 2 at 5 and 10 g/L usage amount of the NonREx, achieving comparable results.
[56] When lowering the amount of repellent even further to 5 g/L which is below the effective level for NR7080-type (Spray: 80/75/70; 41 % Abs.), adding a minimum of 5 g/L Non-REx 1 restores the effect (Spray 100/100/90; 21 % Abs.) - see Standard 1 versus DWR System 1. For the sake of comparison, around 21% water absorbance by the fabric (Bundesmann test) and Spray rating 100/100/100 (Spray test) is the base line effect of the repellent NR7080 alone at higher loadings.
[57] Blending the furfuryl-type extender (Non-REx 1) with a polyurethane wax (oligofunctional isocyanate reacted with stearyl alcohol) was also effective as an extender system, exhibiting a similar performance compared to Non-REx 1. Adding the stearyl component directly to the recipe improves the effect even more. [58] The DWR systems according to the invention offer a strongly improved effect concerning the Bundesmann rain test before laundry, even at lower levels of repellent applied, thus lowering the cost of the recipes and reduce total amount of chemicals applied to the textile. After 5 laundry cycles (HL) the effect is reduced but still visible. After 20 laundry cycles no differences are observable, i.e. the product does not impar performance here. Main effect measure is the amount of water absorbed by the fabric in mass% during the test, the lower the better. The NonREx compounds according to the invention alone may contribute to water- repellence on its own, although not shown in the above results.
[59] The DWR systems according to the present invention perform already at 80°C delivering effect levels otherwise only seen above 120°C (e.g. Phobol® Extender XAN or UXN, which require a curing temperature of at least 150°C) reducing again cost and environmental impact, making them also applicable to fabrics requiring special treatment conditions.
Abbreviations:
PUR = polyurethane
PES = polyester
TDI = toluene diisocyanate
MDI = methylene diphenyl diisocyanate
HDI = hexamethylene diisocyanate
DWR = durable water-repellence system
BM = Bundesmann rain test
AATCC = American Association of Textile Chemists and Colorists

Claims

Claims
1. Use of a compound, which is the reaction product of:
(i) at least one di- or poly-isocyanate;
(ii) at least one aromatic compound selected from the group consisting of:
Figure imgf000015_0002
(I) (H) wherein
R1, R2, R3, R4 and R5 are independently selected from the group consisting of H and Ci-4 alkyl;
Y is OH, NH2 or SH;
X is O, N or S; and
(iii) optionally one or more further reactants; as a non-reactive extender for durable water-repellence in textile fabrics.
2. Use according to claim 1 , wherein the at least one di- or poly-isocyanate (i) is an aromatic isocyanate, an aliphatic isocyanate, a pre-condensate or a condensate thereof.
3. Use according to claim 2, wherein the aromatic isocyanate is chosen from methylene diphenyl isocyanate (MDI) or toluene diisocyanate (TDI), and the pre-condensate or condensate is a methylene diphenyl isocyanate (MDI)- based pre-condensate or a hexamethylene diisocyanate (HDI)-based condensate.
4. Use according to any of claims 1 to 3, wherein the at least one aromatic compound (ii) is benzyl alcohol or furfuryl alcohol.
5. Use according to any of claims 1 to 4, wherein up to about 50 mol% of the at least one aromatic compound (ii) is replaced with an aliphatic compound of formula (III)
Figure imgf000015_0001
wherein
Y is OH, NH2 or SH. Use according to claim 5, wherein the aliphatic compound of formula (III) is stearyl alcohol. Use according to any of claims 1 to 6, wherein about 40% or more, and preferably about 60% or more, of the -N=C=O groups of the at least one di- or poly-isocyanate (i) reacts with the aromatic compound (ii). Use according to any of claims 1 to 7, wherein the at least one further reactant (iii) is selected from the group consisting of one or more di- or polyols, N-methyl diethanolamine (NMDEA), 2,2,6,6-tetramethylpiperidine (TMP) and mixtures thereof. Use according to any of claims 1 to 8, wherein the at least one further reactant (iii) reacts with about 60% or less, and preferably about 40% or less, of the -N=C=O groups of the at least one di- or poly-isocyanate (i) or with about 10% to about 30% of the -N=C=O groups of the at least one di- or poly-isocyanate (i). Use according to any of claims 1 to 9, wherein the at least one di- or poly-isocyanate (i) is methylene diphenyl isocyanate (M DI)- based pre-condensate having a functionality of equal or above 2; the at least one aromatic compound (ii) is furfuryl alcohol or benzyl alcohol, which reacts with about 60% or more of the -N=C=O groups of the at least one di- or poly-isocyanate (i); and the further reactant (iii) is N-methyl diethanolamine (NMDEA), which reacts with about 10% of the -N=C=O groups of the at least one di- or poly-isocyanate (i), or 2,2,6,6-tetramethylpiperidine (TMP), which reacts with about 30% of the -N=C=O groups of the at least one di- or poly-isocyanate (i). A durable water-repellence (DWR) system, comprising:
(a) at least one non-fluorinated water-repellent compound; and
(b) at least one compound according to any of claims 1 to 10. The DWR system according to claim 11 , wherein the at least one water-repellent compound (a) is selected from the group consisting of polyurethane, acrylic copolymer, wax, melamine condensate, silicone repellent, hyperbranched/dendrimeric repellents, and mixtures thereof. The DWR system according to claim 11 and 12, wherein the ratio of the at least one non-fluorinated water-repellent compound (a) to compound (b) is from about 90:10 to about 10:90, preferably from about 80:20 to about 20:80, more preferably from about 70:30 to about 30:70, and most preferably from about 60:40 to about 40:60. The DWR system according to any of claims 11 to 13, wherein (a) is a polyurethane, an acrylic copolymer or a mixture thereof, and the ratio of (a) to (b) is from about 5:1 to about 1 :2, preferably from about 3:1 to about 1 :1. The DWR system according to any of claims 11 to 14, further comprising one or more substances selected from the group consisting of additives, solvents and surfactants. Use of the compound according to any of claims 1 to 10 or DWR system according to any of claims 11 to 15 in water-repellent finishing of fibre materials. A process for treating a textile fabric composed of fibre materials, comprising the steps of padding the fabric with the compound according to any one of claims 1 to 10, or the DWR system according to any one of claims 11 to 15, and subsequently drying. The process according to claim 17, further comprising curing, wherein the maximum curing temperature is equal or below 180°C, preferably equal or below 150°C, more preferably equal or below 110°C, even more preferably equal or below 100°C, and most preferably equal or below 80°C. The process according to claim 17 or 18, wherein the fibre material is selected from the group consisting of polyester, polyamide, cotton, blends or variations thereof, preferably polyester or polyamide, or blends or variations thereof. The process according to any of claims 17 to 19, wherein the compound according to any one of claims 1 to 10 is present in a concentration from about 2 to about 20 g/L, preferably from about 5 to 15 g/L, and most preferably about 10 g/L to about 200 g/L, in a pad bath.
PCT/EP2022/069458 2022-07-12 2022-07-12 Extender compounds for durable water repellence WO2024012662A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2022/069458 WO2024012662A1 (en) 2022-07-12 2022-07-12 Extender compounds for durable water repellence

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2022/069458 WO2024012662A1 (en) 2022-07-12 2022-07-12 Extender compounds for durable water repellence

Publications (1)

Publication Number Publication Date
WO2024012662A1 true WO2024012662A1 (en) 2024-01-18

Family

ID=82799776

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2022/069458 WO2024012662A1 (en) 2022-07-12 2022-07-12 Extender compounds for durable water repellence

Country Status (1)

Country Link
WO (1) WO2024012662A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1218670A (en) * 1967-12-15 1971-01-06 Nat Starch Chem Corp Carboxamido-aziridine derivatives, their preparation, and their use as water repellency agents
EP2186839A1 (en) * 2008-11-13 2010-05-19 Bayer MaterialScience AG Polyurethane dispersions for coating with barrier features
WO2010115496A1 (en) 2009-03-28 2010-10-14 Huntsman Textile Effects (Germany) Gmbh Fluorine-free aqueous dispersion for treating textile fabrics
WO2011035906A2 (en) 2009-09-26 2011-03-31 Huntsman Textile Effects (Germany) Gmbh Composition for oil- and/or water-repellent finishing of fiber materials
EP3074437B1 (en) * 2013-11-26 2018-01-17 Rudolf GmbH Finishing agent with blocked polyisocyanates
WO2018054712A1 (en) 2016-09-23 2018-03-29 Huntsman Textile Effects (Germany) Gmbh Fluorine-free aqueous dispersions for the finishing of textile fabrics

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1218670A (en) * 1967-12-15 1971-01-06 Nat Starch Chem Corp Carboxamido-aziridine derivatives, their preparation, and their use as water repellency agents
EP2186839A1 (en) * 2008-11-13 2010-05-19 Bayer MaterialScience AG Polyurethane dispersions for coating with barrier features
WO2010115496A1 (en) 2009-03-28 2010-10-14 Huntsman Textile Effects (Germany) Gmbh Fluorine-free aqueous dispersion for treating textile fabrics
WO2011035906A2 (en) 2009-09-26 2011-03-31 Huntsman Textile Effects (Germany) Gmbh Composition for oil- and/or water-repellent finishing of fiber materials
EP3074437B1 (en) * 2013-11-26 2018-01-17 Rudolf GmbH Finishing agent with blocked polyisocyanates
WO2018054712A1 (en) 2016-09-23 2018-03-29 Huntsman Textile Effects (Germany) Gmbh Fluorine-free aqueous dispersions for the finishing of textile fabrics

Similar Documents

Publication Publication Date Title
JP4741075B2 (en) Blocked oligomeric isocyanates, their production and use
EP2989244B1 (en) Urethane based polymeric extenders for compositions to modify the surface properties of substrates
KR100514532B1 (en) Reaction products of isocyanates and hydroxyl compounds for textile processing and methods of treating textile materials using them
US8993067B2 (en) Composition for oil- and/or water-repellent finishing of fiber materials
US5509939A (en) Soil-release process
US8231802B2 (en) Preparations for making planar structures oil-repellent and water-repellent, and use thereof
US10253450B2 (en) Finishing agent with blocked polyisocyanates
KR101072096B1 (en) Stable aqueous dispersions of non-ionic blocked polyisocyanates
CN100471889C (en) Extender for treatment of fiber materials
WO2024012662A1 (en) Extender compounds for durable water repellence
EP0628102B1 (en) Fluorocarbamate soil-release agents
US6306958B1 (en) Aqueous dispersions for textile finishing
US5481027A (en) Fluorocarbamate soil-release agents
US10005958B2 (en) Polyurethane-based UV absorber
TW202402861A (en) Non-reactive extender compounds for durable water repellence in textile fabrics
WO2001010922A1 (en) Fluorochemical oil and water repellents
US7494511B2 (en) Hydrophilic stain release agents
US20240034840A1 (en) Hydrophobizing agent having a permanent effect
US20070265412A1 (en) Extenders for fluorochemical treatment of fibrous substrates

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22751034

Country of ref document: EP

Kind code of ref document: A1