EP0451665A1 - Behandlung von Geweben - Google Patents

Behandlung von Geweben Download PDF

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Publication number
EP0451665A1
EP0451665A1 EP91105142A EP91105142A EP0451665A1 EP 0451665 A1 EP0451665 A1 EP 0451665A1 EP 91105142 A EP91105142 A EP 91105142A EP 91105142 A EP91105142 A EP 91105142A EP 0451665 A1 EP0451665 A1 EP 0451665A1
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EP
European Patent Office
Prior art keywords
substrate
process according
solution
group
compound
Prior art date
Legal status (The legal status 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 status listed.)
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Application number
EP91105142A
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English (en)
French (fr)
Inventor
Mohsen Zakikhani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay Solutions UK Ltd
Original Assignee
Albright and Wilson Ltd
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Filing date
Publication date
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Publication of EP0451665A1 publication Critical patent/EP0451665A1/de
Withdrawn legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/04—Physical treatment, e.g. heating, irradiating
    • D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
    • 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
    • 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
    • D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives 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
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • 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
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
    • D06M15/431—Amino-aldehyde resins modified by phosphorus compounds by phosphines or phosphine oxides; by oxides or salts of the phosphonium radical
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/34—Ignifugeants

Definitions

  • This invention relates to a fabric treatment process, in particular one rendering fabrics flame retardant with organo phosphorus compounds.
  • THP compounds tetrakis (hydroxymethyl) phosphonium compounds
  • precondensates thereof with urea has been described in USP2983623, 4068026, 4078101, 4145463 and 4494951.
  • the treatment processes involved impregnation of the fabric with an aqueous solution of the chemicals, followed by drying, treatment with ammonia to cure the phosphorus compounds in order to insolubilize the phosphorus onto the fabric, finally with oxidation and washing to leave a treated fabric whose flame resistance is retained even after many washes in use.
  • the cure efficiency which is a measure of the effectiveness of the cure in insolubilizing the phosphorus on the fabric, is not always ideal and a percentage of the expensive phosphorus chemicals applied in the impregnation step is not cured, and is washed off the fabric after the cure and wasted.
  • the cure efficiency for cotton fabrics is higher than for cotton polyester fabrics and especially polyester cotton fabrics and in some cases adequate fire retardant properties cannot be provided to the latter with THP compounds.
  • some techniques enable the necessary fire retardant properties to be provided to the fabric when first cured, those properties often diminish significantly on repeated washing.
  • the present invention provides a process for the flame retardant treatment of an organic fibrous substrate containing reactive groups, which process comprises impregnating said substrate with a silicon compound having at least two active-hydrogen-reactive groups (or precursor therefor), then subsequently with an aqueous solution of an organophosphorus compound, to provide a second impregnated substrate which is dried and cured heat and/or ammonia, to give a cured substrate.
  • the silicon compound is applied in a first step to give a first impregnated substrate and then the organophosphorus compound is applied in a second step.
  • the first impregnated substrate is usually maintained to allow the silicon compound to interact or react in the substrate before the second step.
  • the silicon compound (or a hydrolysis product thereof) contains at least two groups capable of reaction or interaction with active hydrogen groups especially in hydroxyl, amide or amine groups (including ammonia).
  • the silicon compound contains at least one group designated R in the formula below which, as is or after hydrolysis, is capable of reaction or interaction with a hydroxyl group in an insoluble polymer, e.g. cellulosic hydroxy groups or polyester terminal hydroxyl groups or with an amide group in an insoluble polymer, e.g. a polyamide such as a nylon; and at least one group, designated R1 in the formula below, which is capable of reaction or interaction with hydroxymethyl groups e.g.
  • the conditions of the reaction or interaction are usually under the influence of heat, and may be under acid, neutral or basic conditions, and are preferably such that when R (or a group formed by hydrolysis thereof) reacts or interacts, R1 will not so react.
  • the silicon compound is of formula (R) a Si R1 b R2 c wherein each of a and b, which is the same or different, is 0, 1, 2, 3 or 4 c is 0, 1 or 2 and a+b+c is 4.
  • R and R1 are as defined above, while R2 is an inert organic group, e.g. one inert under the conditions of the first and second steps.
  • a is 1, 2 or 3 especially 3
  • b is 3, 2 or 1 especially 1 and c is preferably 0.
  • Group R may be hydrogen, halogen (e.g. chlorine or bromine), hydroxyl or an ether, acetal, ketal or ester thereof.
  • R may together be divalent ether, acetal, ketal or ester groups, or three groups R may together form a trivalent ether or ester group.
  • R is a hydrolyzable group.
  • ether groups for R are alkoxides and alkoxy-alkoxides and aryloxides and aralkoxides e.g. of formula R3O wherein R3 is an alkyl e.g.
  • R3 may also be an aryl group, e.g. an aromatic hydrocarbyl group of 6-19 carbons (such as phenyl, tolyl and xylyl), or an aralkyl group, such as an aralkyl hydrocarbyl group of 7-20 carbon atoms (such as benzyl and naphthylmethyl).
  • ester groups for R are carboxylate ones, e.g.
  • Preferred groups R are hydroxyl and especially alkoxide, such as methoxy, ethoxy, propoxy, isopropoxy and butoxy.
  • the silicon compound is a tri alkoxy silane of formula R1 Si(OR3)3.
  • group R is usually such that the silane is hydrolysed in the impregnation medium or as a prior step to the reaction or interaction, e.g during the first step to a hydroxy silane (or a cyclized product therefrom with the silanol and any amino group in R1).
  • the impregnation medium is usually an aqueous solution, so the silicon compound (as is or after hydrolysis) is usually water soluble, e.g with a solubility of at least 10g/l.
  • Group or groups R1 may be an organic group e.g. of 1-12 carbon atoms (such as 1-6 carbon atoms) containing at least one substituent or group which contains at least one e.g. 1-4 and especially 2-4 active hydrogen atoms attached to one or more nitrogen, sulphur, oxygen, or silicon atoms, or a substituent or group which is an unsaturated or 3 atom ring group formed from a carbon atom and a carbon, nitrogen, sulphur or oxygen atom, said unsaturated group being electrophilic and capable of being attacked by nucleophiles, (such as a -CH2-OH group or ammonia).
  • the substituent may also be a halide (e.g. chloride or bromide).
  • Group R1 preferably contains a basic group or quaternary derivative thereof, so the silicon compound in the impregnation medium is advantageously a Zwitterion.
  • group R1 are ones of formula -R4-X, wherein R4 is an alkylene group e.g. 1-6 carbon atoms (such as methylene, ethylene, 1, 3- propylene), or an arylene group, e.g.
  • R4 may also be a cyclo alkylene-alkylene or cycloalkenylene alkylene group, each of the latter groups being e.g. of 6-10 carbons (such as 2 cyclohexyl ethyl or 2-(cyclohexenyl) ethyl) or cycloalkylene, e.g. of 5-7 carbons such as cyclohexylene.
  • X is one of the above substituents, especially Cl, -NH2, CN, -NHR5 (wherein R5 is an alkyl group of 1-6 carbon atoms, an aromatic or aralkyl group, eg of 6-18 carbons, or of formula -R4NH2.
  • -R4NHR5 e.g. an amino alkylene group, e.g. of 2-10 carbon atoms (such as 2-aminoethyl, 6-aminohexyl), or an optionally substituted (e.g. vinyl substituted) benzylamino alkylene group with 2-6 carbon atoms in the alkylene group, (such as 2[p vinyl benzyl amino] ethyl or an amino carbonyl group).
  • Amino functional silanes e.g. where X is an NH2 or NHR5 group are preferred; such silanes preferably have at least one NH2 group, and especially one NH2 and one or two -NH- groups in the
  • the olefinic substitution or group - which may be an alkenyl or alkenylene group e.g. of 2-8 carbon atoms, (such as vinyl, or propenylene) or an aryl substituted alkenylene group e.g. of 8-14 carbons (such as vinyl-phenyl or 2-phenyl or 2-phenyl ethenylene) or a cycloalkenyl group, e.g. of 5-7 carbons, (such as cyclohexenylene), may be group R1 itself or group X itself or may be part of a group X, as when R1 represents R4X e.g.
  • R1 are 1, 3 propylene with a 3-substituent of formula X which is glycidyloxy, methacryloxy, acryloxy, chlorine, amine, cyano, ureido and 2-(amino ethyl) amino, especially when 3 R groups represent three methoxy or ethoxy groups in a molecule of formula R1 Si (OCH3)3 or R1 Si (OC2H5)3.
  • preferred silicon compounds are N-(2 aminoethyl) - 3-amino propyl trimethoxy silane and 3-amino propyl trimethoxy silane.
  • Vinyl tri alkoxy silanes are also preferred.
  • Group R2 is an inert organic group e.g. one of 1-19 carbon atoms such as one given above in relation to R3, preferably methyl, and is non reactive and non hydrolyzable.
  • the organic fibrous substrate is especially one comprising or consisting essentially of cellulosic fibres.
  • the cellulosic fibres are preferably natural cotton but may be ramie, flax, paper or cardboard or regenerated fibres (e.g. viscose or cuprammonium fibres) or partly etherified or esterified cellulose (e.g. cellulose acetate or propionate).
  • the substrate may be substantially completely cellulosic eg 100% cotton or may contain both cellulosic and non cellulosic organic fibres, or just contain non cellulosic organic fibres.
  • Inorganic fibres such as glass fibres are usually absent.
  • the non cellulosic fibres are preferably polyester or polyamide fibres but may also be acrylic.
  • the polyamide may be an aliphatic one, such as copolymers of a polyamine (such as a diamine) preferably an alkylene diamine, eg of 4-12 carbon atoms and a poly carboxylic acid eg a dicarboxylic acid, of 4-14 carbon atoms such as an alkylene dicarboxylic acid (e.g. Nylon 66), or polylactams such as Nylon 6.
  • the polyamide may be an aromatic one, such as aramids based on aromatic dicarboxylic acids and phenylene diamines.
  • the acrylic polymer may be polyacrylonitrile homopolymer or copolymer with vinyl chloride, as in modacrylic fibres.
  • the substrate can contain at least 20% of cellulosic fibres and up to 80% of coblendable fibres e.g. 10-80% especially 25-80% of coblendable fibres such as polyamides.
  • the substrate comprises cellulosic fibres and polyester fibres.
  • the substrate usually contains up to 80% (e.g up to 70%) polyester fibres and from 20% (e.g. from 30%) upwards of cellulosic fibres, e.g.
  • polyester fibres such as 45-100% polyester
  • the polyester is usually a condensation product containing structural units from an aliphatic alcohol, e.g. dihydric alcohol, especially ethylene glycol or butane diol (or mixtures thereof) and an aromatic dicarboxylic acid, e.g. terephthalic acid, or a mixture thereof with other dicarboxylic acids, such as isophthalic acid, or sebacic acid.
  • the fibrous substrate may be one of the above non cellulosic ones having groups capable of interaction with the silicon compound.
  • the substrate may be a polyester, with the silicon compound reacting with hydroxyl or ester groups, or a polyamide with the silicon compound reacting with amide or amine or carboxyl or a polyacrylonitrile with reaction of the silicon compound with nitrile groups.
  • the polyester may be described above, while the polyamide may be a reaction product of a polyamine e.g. a diamine e.g. 4-12 carbons with a polyarboxylic acid e.g. a dicarboxylic acid of 4-14 carbon atoms.
  • the polyacrylonitrile may be a homopolymer or copolymer with vinyl chloride as in modacrylic fibres.
  • the substrate fibres may be in the form of thread or non woven fabric, but are preferably as woven fabric.
  • Mixtures of fibres e.g. of cellulosic and other fibres may be an intimate or non intimate mixture but the fibres are preferably in the form of blend of cellulosic fibres and the other fibres e.g. polyester fibres, as in cospun blends such as cotton polyester or polyester cotton staple fibre, but may be in the form of core spun yarn with a core of the other fibre e.g. polyester sheathed in cotton fibres.
  • the warp and weft fibres are preferably the same, but may be different e.g. one may be from cotton fibres and the other from e.g. polyester cotton fibres.
  • the term "blend” also includes unions and union/blends as well as core sheath fibres.
  • the substrate is preferably a fabric with a weight of 0.05-1.0kg/m2 , e.g. 0.150-0.40kg/m2, or 0.05-0.20kg/m2, such as polyester cotton shirting or sheeting or curtain fabric.
  • the fabric is substantially free from size or other finishing agents, such as softening agents and resins; thus size that may have been on the fabric is usually removed, eg by washing.
  • the silicon compound may be applied undiluted to the substrate but is preferably applied in aqueous solution, e.g. of 0.1-10%, especially 0.5-7% w/w, and a pH 2-9.
  • a weak acid such as acetic or phosphoric acid may be present also in the solution in amount of 0.1 - 1% by weight, to aid hydrolysis of the silicon compound if required.
  • the solution is at pH 2-4.
  • the weight of silicon compound applied is usually 0.01-10%, e.g. 0.1-5%, especially 0.5-4%, based on the weight of the untreated fabric.
  • the silicon compound is usually impregnated into the fabric with a wet pick up of 40-150% and then, after initial drying if desired, (e.g.
  • the impregnated fabric is then treated by heating at 90-150°C (e.g. 90-130°C) for 0.5-10 minutes (e.g. 1-5 minutes).
  • the impregnated fabric may be kept, e.g at ambient temperature for 10-60 hours (e.g 10-30 hours).
  • the silicon compound may be impregnated by a minimum add-on technique to provide eg a 10-50% wet pick up. Thereafter the fabric may be dried or kept with a dwell time of, eg, 2-24 hours before the second step.
  • a foam minimum add-on technique may be used, with a cationic or amphoteric foaming agent and a stabilizer.
  • the silicon compound may be hydrolysed in the aqueous solution, or may be hydrolysed during the drying or heat treatment step to form a reactive silicon compound.
  • the silicon compound or reactive silicon compound is believed to react with the substrate, especially hydroxyl amide or ester groups thereon, in particular via the reactive group R or a hydrolysed version thereof (e.g. hydroxyl), to give a treated substrate which carries a silicon containing group, especially one with group R1, as defined above, intact.
  • the treated substrate preferably contains pendant -SiR1 b R2 c groups especially SiR1 groups, attached usually to cellulosic hydroxy groups or terminal hydroxy groups of a polyester.
  • active hydrogen containing groups in R1 can react with ester or amide or nitrile groups in polyester or polyamides or polyacrylonitrile respectively.
  • Unsaturated or 3 ring groups in R1 can react with the fibres by addition of hydroxyl or N-H groups on the fibres to the silicon compound.
  • each hydroxyorgano group is preferably an alpha hydroxyorgano group of 1-9 carbons especially one of formula HOC- (R5R6) wherein each of R5 and R6 which is the same or different represents hydrogen or an alkyl group of 1 to 4 carbons e.g. methyl or ethyl.
  • R5 is hydrogen
  • R6 is methyl or especially hydrogen as in tetra kis (hydroxymethyl) phosphonium (THP) compounds.
  • the substrate is treated with an impregnation solution which is an aqueous solution of a THP salt mixed with a nitrogen compound condensable therewith to form a water soluble precondensate, or a solution of a precondensate of said salt and nitrogen compound, or a solution of THP salt, or water soluble self-condensate thereof, or at least partly neutralised THP salt, (e.g. THP hydroxide), with or without the nitrogen compound.
  • an impregnation solution which is an aqueous solution of a THP salt mixed with a nitrogen compound condensable therewith to form a water soluble precondensate, or a solution of a precondensate of said salt and nitrogen compound, or a solution of THP salt, or water soluble self-condensate thereof, or at least partly neutralised THP salt, (e.g. THP hydroxide), with or without the nitrogen compound.
  • the impregnation solution may alternatively comprise a solution of said precondensate and further nitrogen compound (eg urea), as in a solution with a molar ratio of total nitrogen compound (free and combined) to THP group (free and combined) of 0.8-2:1, eg 0.8-1.5:1.
  • the nitrogen compound is preferably one with at least two NH groups (such as 2-4), but advantageously contains two NH or especially two NH2 groups.
  • the nitrogen compound is usually bifunctional and may be an amine but is especially an amide.
  • nitrogen compounds examples include biuret, guanidine, melamine and methylolated melamines, but urea is the preferred species for the purposes of this invention, especially in the absence of melamine or a methylolated melamine.
  • the nitrogen compound is preferably urea whenever it is present in the precondensate.
  • the solution contains a precondensate of THP salt, e.g. chloride or sulphate, and the nitrogen compound in a molar ratio of nitrogen compound to THP of 0.05-0.8:1, e.g. 0.05-0.6:1, or 0.22-0.8:1, such as 0.25-0.6:1, especially 0.4-0.6:1.
  • the pH of said solution is usually 2-7.5, such as 4-6.5, e.g. 4-5.
  • the atom ratio of total N atoms in the nitrogen compound or condensate to the total P atoms from THP salt or condensate in the impregnation solution is usually not greater than 4:1, eg 1-3:1.
  • the concentration of organophosphorus compound in the aqueous solution maybe 5-70%, eg 5-35% or 35-70% (expressed by weight at THP+ion), but is preferably 20-35%.
  • the solution may contain a wetting agent, such as a nonionic one, eg in amount of 0.05-0.5% by weight of the impregnation solution, a fabric softener such as a polyethylene one and in preferred amount of 0.1-2% by weight, and a salt of a strong acid and weak base (such as an ammonium or alkaline earth metal chloride or nitrate or ammonium acid phosphate) as catalyst for the heat cure, and in amount of 0.1-5% by weight.
  • a wetting agent such as a nonionic one, eg in amount of 0.05-0.5% by weight of the impregnation solution
  • a fabric softener such as a polyethylene one and in preferred amount of 0.1-2% by weight
  • a salt of a strong acid and weak base such as an ammonium or alkaline earth metal chloride or nitrate or ammonium acid phosphate
  • the treated substrate is impregnated to give an organo phosphorus pick up of less than 40%, e.g. 10-40%, such as 10-30%, especially 20-30% (as THP ion based on the original weight of the substrate).
  • the substrate can be impregnated with solution and the wet substrate, e.g. fabric, usually squeezed to a wet pick up of 50-130%, e.g. 60-100% (based on the original weight of the substrate).
  • the treated substrate may be impregnated with a concentrated impregnation solution via a minimum add-on, eg foam, technique and a 10-50% wet pick up.
  • the organophosphorus impregnated substrate is then dried e.g. to a moisture content of 0-20%, e.g. 5-15%, (such as about 10%) for subsequent ammonia cure and to substantial dryness for subsequent heat cure, the percentage being derived from the increase in weight of the substrate, eg fabric, and the weight of chemicals impregnated.
  • the drying may be in a stenter oven or over heated cans, e.g. steam cans and may involve heating at 80-120°C for 10 to 1 min.
  • the dried substrate is then cured.
  • the cure may be by treatment with ammonia, usually gaseous ammonia, which diffuses through the substrate and/or is forced through the substrate e.g.
  • the dried organophosphorus impregnated substrate may be heat cured, e.g. at 100-200°C, or 100-180°C, (such as 130-170°C) for 10-0.5 minutes (e.g. 7-1 minutes). Higher temperatures with long curing times should be avoided with substrates containing at least a majority of cellulosic fibres especially 100% cotton.
  • the drying and heat curing steps are combined in a single step with heating under the heat cure conditions.
  • the heat cured fabric is preferably submitted to a humidity equilibration step to allow the fabric to recover its moisture content before the ammoniation.
  • the cured substrate usually has solids add-on (derived from the THP impregnation and cure stages) of 10-50% or 10-40%, e.g. 10-30%, such as 10-25%, or 15-30%, especially 20-30%, (by weight of the original substrate), based on a total organophosphorus compound pick up of 16-36%, e.g. 20-28% (expressed as THP ion on the same basis).
  • the cured substrate is then usually subjected to at least one of the following operations: further insolubilization of the cured resin in the treated substrate, oxidation in order to convert at least some trivalent phosphorus to pentavalent phosphorus in the cured resin, or washing with aqueous base and washing with water.
  • the oxidation is preferably by contact with an aqueous solution of an oxidising agent, preferably a peroxy compound, such as aqueous hydrogen peroxide solution e.g. of 0.5-15% concentration, such as 1-5% strength, or sodium perborate solution, e.g. of 1-10% concentration, usually applied in excess, and usually for 0.1-10 mins at 0-40°C.
  • an oxidising agent preferably a peroxy compound, such as aqueous hydrogen peroxide solution e.g. of 0.5-15% concentration, such as 1-5% strength, or sodium perborate solution, e.g. of 1-10% concentration, usually applied in excess, and usually for 0.1-10 mins at
  • the oxidation may be performed with a gas containing molecular oxygen, preferably air, and particularly with the gas being drawn or blown through the substrate; thus the substrate in the form of fabric can be passed over a vacuum slot or perforated tube though which the gas is blown or sucked.
  • a gas containing molecular oxygen preferably air
  • the substrate in the form of fabric can be passed over a vacuum slot or perforated tube though which the gas is blown or sucked.
  • the cured substrate may be washed with an aqueous medium, preferably an aqueous solution of base, e.g. sodium carbonate solution and/or rinsed with water.
  • an aqueous medium preferably an aqueous solution of base, e.g. sodium carbonate solution and/or rinsed with water.
  • the oxidation preferably reduces the residual content of formaldehyde on the cured substrate.
  • the cured substrate may simply be rinsed with water or submitted to other operations to reduce its content of water soluble materials.
  • the cured fabric is dried, to give a final substrate.
  • the final substrate e.g. fabric can be used for making workwear such as overalls, boiler suits and protective clothing including uniforms, particularly from 30-70% (e.g. 55-70%) cotton and 70-30% (e.g. 45-30%) polyester, and household fabrics such as sheets and curtains particularly from 30-70% (e.g. 30-60%) cotton and 40-70% polyester.
  • workwear such as overalls, boiler suits and protective clothing including uniforms, particularly from 30-70% (e.g. 55-70%) cotton and 70-30% (e.g. 45-30%) polyester, and household fabrics such as sheets and curtains particularly from 30-70% (e.g. 30-60%) cotton and 40-70% polyester.
  • the process of the invention is compared to the corresponding one without the silicon treatment step, the initial uptake of THP compound by the substrate in the impregnation may be increased, the cure efficiency may be increased, and the loss of cured P compound from the final substrate during washing in use may be reduced.
  • the cured substrate of the invention usually has a higher percentage of bound phosphorus, and may also have a better handle than the corresponding cured substrate without the initial treatment with the silicon compound. There is thus less wastage of phosphorus chemical.
  • the flame retardant properties e.g the char length, are usually improved enabling fabrics to pass more severe flammability tests than without the pretreatment.
  • the final substrate obtained by the process of the invention may also have enough cured and bound phosphorus containing resin to enable it to reach exacting flame retardancy standards e.g. BS6249 Part l 1984 Index B, which may not be passed by the same original substrate cured without the initial treatment with silicon compound.
  • the final substrate obtained by the process of the invention may also have less reduction in strength compared to corresponding substrates without the initial treatment.
  • the invention is illustrated in the following Examples in which all the fabrics had been previously submitted to a denizing treatment.
  • the final fabric was then analysed for P and N and tested for flame retardancy before and after washing 40 times at 93°C, the washing being as in the manner described in DIN 53920 procedure 1 with soft water.
  • the test method used was according to BS 5438 (1989) Test 2A. In all cases the fabrics met the flammability requirements of BS 6249 Index B.
  • the analysis results were as follows:
  • the fabric passed the ignition test even after 40 washes.
  • the process of Ex1 was repeated with 2 separate fabrics and 3 types of cure step (c).
  • the fabrics were (A) a 100% print cotton of 0.240 kg/m2 fabric weight (B) the 67:33 polyester cotton fabric of Ex1.
  • step (b) fabric A was then cured by (i) heat cure at 150°C for 4 minutes or (ii) ammonia cured by drying the fabric for 2 minutes at 100°C and then passing ammonia through the fabric in a chamber as described in USP 4145463 or (iii) heat curing at 150°C for 4 minutes followed by ammonia cure by passing ammonia through the fabric in a chamber as described in USP 4145463.
  • the cure step (c) was by (i) or (ii) only.
  • step (d) After cure steps (i), (ii) or (iii) the operations of step (d) were performed.
  • the flame retardancy and analyses test were done on the final fabric and the fabric after 40 washes at 93°C. The results were as follows.
  • step (a) The process of Ex 1 was repeated with 3 different silanes in the aqueous solution in step (a) namely (i) a 2% solution of 3-chloropropyl-trimethoxy silane (ii) a 1% solution of 3-[2-[p-vinylbenzylamino]ethyl]aminopropyl trimethoxy silane. (iii) (iv) a 0.25% solution and a 2% solution of 3-glycidyloxy propyl trimethoxy silane, the silanes being sold by Dow Corning under the trademarks Z6076, Z6032 and Z6040 respectively. All the final fabrics passed the flammability tests.
  • the char lengths in mm for the final fabrics were as follows (ii) 74 mm (iii) 69 mm and (iv) 65 mm respectively.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Silicon Polymers (AREA)
EP91105142A 1990-04-12 1991-04-02 Behandlung von Geweben Withdrawn EP0451665A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB909008423A GB9008423D0 (en) 1990-04-12 1990-04-12 Treatment of fabrics
GB9008423 1990-04-12

Publications (1)

Publication Number Publication Date
EP0451665A1 true EP0451665A1 (de) 1991-10-16

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EP (1) EP0451665A1 (de)
JP (1) JPH04222278A (de)
KR (1) KR920005740A (de)
CN (1) CN1055567A (de)
AU (1) AU7428491A (de)
BR (1) BR9101494A (de)
CA (1) CA2039632A1 (de)
FI (1) FI911743L (de)
GB (2) GB9008423D0 (de)
HU (1) HUT57293A (de)
IE (1) IE911218A1 (de)
NO (1) NO911431L (de)
PL (1) PL289869A1 (de)
PT (1) PT97362A (de)
ZA (1) ZA912554B (de)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0709518A1 (de) * 1994-10-25 1996-05-01 Albright & Wilson Limited Flammhemmende und weichmachende Behandlung von Textilmaterialien
FR2738241A1 (fr) * 1995-09-01 1997-03-07 Vetrotex France Sa Fils de verre de renforcement et composites resistant en milieu corrosif
US6531419B1 (en) 1999-07-01 2003-03-11 R. H. Wyner Associates, Inc. Multi-layer protective fabrics
EP1538261A1 (de) * 2003-12-05 2005-06-08 Ciba Spezialitätenchemie Pfersee GmbH Verfahren zur flammhemmenden Ausrüstung von Faserprodukten
WO2006105833A1 (en) * 2005-04-02 2006-10-12 Huntsman Textile Effects (Germany) Gmbh Process for the flame-retardant treatment of fiber products
CN103572593A (zh) * 2013-10-24 2014-02-12 浙江理工大学 一种糟朽棉织物文物的简易加固方法
WO2021122202A1 (en) * 2019-12-16 2021-06-24 Rhodia Operations Flame-retardant composite material
US11325926B2 (en) * 2019-03-11 2022-05-10 Evonik Operations Gmbh VOC-free, aqueous and storage-stable N-vinylbenzylaminoalkyl-functional siloxanol and process for the production thereof
CN116987263A (zh) * 2022-04-26 2023-11-03 中国科学院化学研究所 一种尼龙、含该尼龙的抗熔滴阻燃材料及制备方法

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CN101381958B (zh) * 2008-11-06 2012-01-11 浙江美欣达印染集团股份有限公司 一种阻燃整理材料及用这种材料整理织物的方法
CN102011308B (zh) * 2010-09-26 2012-03-14 常熟新锦江印染有限公司 一种全棉针织布的环保耐久阻燃整理方法
CN102218826B (zh) * 2010-12-24 2016-08-24 广东新志密封技术有限公司 一种夹织物导向环的制备方法及其制品
US9982096B2 (en) * 2013-10-25 2018-05-29 Milliken & Company Flame retardant precursors, polymers prepared from such precursors, and flame resistant fabrics treated with such polymers
CN107558061A (zh) * 2017-09-05 2018-01-09 绍兴思安阻燃科技有限公司 一种阻燃面料后整理烘干工艺
CN109837774B (zh) * 2019-02-27 2021-09-14 淮安嘉德纺织有限公司 一种多孔纤维素微球改性的染色的棉混纺织物的一步染色方法
CN115305626A (zh) * 2022-09-14 2022-11-08 罗莱生活科技股份有限公司 一种包芯纱柔软面料及其生产方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4052158A (en) * 1973-11-12 1977-10-04 Stauffer Chemical Company Textile finishing process
US4207071A (en) * 1979-02-01 1980-06-10 Dow Corning Corporation Durable modification of fibrous substrates using a polyoxyethylene-containing silane and articles therefrom
EP0313227A2 (de) * 1987-09-30 1989-04-26 Takemoto Yushi Kabushiki Kaisha Wärmebeständiges Schmiermittel zur Behandlung von Kunstfasern

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4052158A (en) * 1973-11-12 1977-10-04 Stauffer Chemical Company Textile finishing process
US4207071A (en) * 1979-02-01 1980-06-10 Dow Corning Corporation Durable modification of fibrous substrates using a polyoxyethylene-containing silane and articles therefrom
EP0313227A2 (de) * 1987-09-30 1989-04-26 Takemoto Yushi Kabushiki Kaisha Wärmebeständiges Schmiermittel zur Behandlung von Kunstfasern

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0709518A1 (de) * 1994-10-25 1996-05-01 Albright & Wilson Limited Flammhemmende und weichmachende Behandlung von Textilmaterialien
FR2738241A1 (fr) * 1995-09-01 1997-03-07 Vetrotex France Sa Fils de verre de renforcement et composites resistant en milieu corrosif
EP0761619A1 (de) * 1995-09-01 1997-03-12 Vetrotex France S.A. Verstärkungsglasfasern und in korrosiver Umgebung beständige Verbundwerkstoffe
US6531419B1 (en) 1999-07-01 2003-03-11 R. H. Wyner Associates, Inc. Multi-layer protective fabrics
US6869900B2 (en) * 1999-07-01 2005-03-22 Shawmut Corporation Multi-layer protective fabrics
EP1538261A1 (de) * 2003-12-05 2005-06-08 Ciba Spezialitätenchemie Pfersee GmbH Verfahren zur flammhemmenden Ausrüstung von Faserprodukten
WO2005054576A1 (en) * 2003-12-05 2005-06-16 Ciba Spezialitätenchemie Pfersee GmbH Process for the flame-retardant of fiber products
WO2006105833A1 (en) * 2005-04-02 2006-10-12 Huntsman Textile Effects (Germany) Gmbh Process for the flame-retardant treatment of fiber products
CN103572593A (zh) * 2013-10-24 2014-02-12 浙江理工大学 一种糟朽棉织物文物的简易加固方法
US11325926B2 (en) * 2019-03-11 2022-05-10 Evonik Operations Gmbh VOC-free, aqueous and storage-stable N-vinylbenzylaminoalkyl-functional siloxanol and process for the production thereof
WO2021122202A1 (en) * 2019-12-16 2021-06-24 Rhodia Operations Flame-retardant composite material
CN116987263A (zh) * 2022-04-26 2023-11-03 中国科学院化学研究所 一种尼龙、含该尼龙的抗熔滴阻燃材料及制备方法

Also Published As

Publication number Publication date
IE911218A1 (en) 1991-10-23
CN1055567A (zh) 1991-10-23
NO911431L (no) 1991-10-14
GB9106833D0 (en) 1991-05-22
HUT57293A (en) 1991-11-28
NO911431D0 (no) 1991-04-11
PL289869A1 (en) 1991-12-02
CA2039632A1 (en) 1991-10-13
GB2242915B (en) 1994-01-05
HU911225D0 (en) 1991-10-28
JPH04222278A (ja) 1992-08-12
FI911743A7 (fi) 1991-10-13
AU7428491A (en) 1991-10-17
FI911743L (fi) 1991-10-13
BR9101494A (pt) 1991-12-03
PT97362A (pt) 1991-12-31
FI911743A0 (fi) 1991-04-11
GB9008423D0 (en) 1990-06-13
GB2242915A (en) 1991-10-16
ZA912554B (en) 1992-03-25
KR920005740A (ko) 1992-04-03

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