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WO1999014422A1 - Composition fluorochimique comprenant un diluant a base d'isocyanate bloque et procede de traitement d'un substrat fibreux a l'aide de celle-ci - Google Patents

Composition fluorochimique comprenant un diluant a base d'isocyanate bloque et procede de traitement d'un substrat fibreux a l'aide de celle-ci Download PDF

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Publication number
WO1999014422A1
WO1999014422A1 PCT/IB1997/001354 IB9701354W WO9914422A1 WO 1999014422 A1 WO1999014422 A1 WO 1999014422A1 IB 9701354 W IB9701354 W IB 9701354W WO 9914422 A1 WO9914422 A1 WO 9914422A1
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Prior art keywords
fluorochemical
diol
fluorochemical composition
group
diols
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PCT/IB1997/001354
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English (en)
Inventor
Frans Albert Audenaert
Pierre Jean-Marie Emmanuel Vander Elst
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3M Co
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Minnesota Mining and Manufacturing Co
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Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to JP2000511950A priority Critical patent/JP4149658B2/ja
Priority to PCT/IB1997/001354 priority patent/WO1999014422A1/fr
Priority to KR10-2000-7002862A priority patent/KR100537881B1/ko
Priority to AU46344/97A priority patent/AU4634497A/en
Priority to DE69723480T priority patent/DE69723480T2/de
Priority to EP97945040A priority patent/EP1017897B1/fr
Priority to BR9714826-1A priority patent/BR9714826A/pt
Priority to IDP981249A priority patent/ID20879A/id
Publication of WO1999014422A1 publication Critical patent/WO1999014422A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • D06M13/398—Isocyanates containing fluorine atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—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
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • 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
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • 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
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/33—Esters containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
    • 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
    • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
    • 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
    • D06M15/653—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain modified by isocyanate compounds
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • 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 a fluorochemical composition for treatment of a fibrous substrate to provide for example oil and/or water repellency properties to that fibrous substrate.
  • the fluorochemical composition of the present invention contains a fluorochemical compound and a blocked isocyanate extender.
  • Organofluorine compounds are substances typically containing portions that are fluorocarbon in nature (e.g., hydrophobic, oleophobic, and chemically inert) and portions that are organic or hydrocarbon in nature (e.g., chemically reactive in organic reactions).
  • fluorochemicals are familiar to the general public, such as SCOTCHGARDTM carpet protector, which imparts oil and water repellency and stain and soil resistance to carpet.
  • Other such substances have various industrial uses, such as reducing the surface tension of liquids, reducing evaporation and inflammability of volatile organic liquids, and improving the leveling of organic polymer coatings.
  • fluorochemicals to provide oil and/or water repellency properties as well as other properties such as anti-soiling or stain release properties to a substrate, in particular fibrous substrates such as textiles and leather, is well known and is of substantial commercial importance.
  • Extenders are relatively inexpensive compared to fluorochemicals and they are a means of increasing the fluorine efficiency of a fluorochemical treatment.
  • Modified synthetic resins, waxes, paraffin emulsions and similar products have been used as extenders.
  • a further well-known class of extenders are those that contain a blocked isocyanate group, so called blocked isocyanate extenders.
  • US 4,834,764 discloses urethane type blocked isocyanate extenders that are obtained by reacting a polyisocyanate with a blocking agent such as an oxime or an alcohol.
  • US 5,466,770 discloses a blocked isocyanate extender that is derived from a polymerization of a blocked isocyanate monomer.
  • US 5,057,377 discloses a blend of a blocked isocyanate and a fluorinated silicon polymer obtained by the polycondensation of a fluorochemical diol and a polysiloxane diol.
  • EP 383 310 discloses blocked isocyanate extenders that are derived from the free radical polymerization of a first vinyl monomer that contains a polysiloxane group and a second monomer that contains a blocked isocyanate group. According to EP 383 310 such blocked isocyanate extenders can be combined with a fluorochemical polymer derived from the polymerization of a fluorochemical monomer. It is however also contemplated in EP 383 310 to prepare a terpolymer of the polysiloxane monomer, the fluorochemical monomer and the monomer containing the blocked isocyanate group. Accordingly, extender and fluorochemical are then combined into a single chemical compound.
  • a fluorochemical composition for treatment of a fibrous substrate comprising at least one fluorochemical compound and a blocked isocyanate extender derived from a condensation of a polyisocyanate, a diol selected from the group consisting of fatty ester diols, polysiloxane diols, polyester diols, polytetramethylene glycol, dimer diols and mixtures thereof and an isocyanate blocking agent.
  • the present invention also provides a fibrous substrate treated with the above composition and the use of the above fluorochemical composition to impart water and/or oil repellency to a fibrous substrate.
  • the present invention further provides a method of treatment of a fibrous substrate comprising providing to at least part of a surface of said fibrous substrate, a fluorochemical composition comprising at least one fluorochemical compound and a blocked isocyanate extender derived from a condensation of a polyisocyanate, a diol selected from the group consisting of fatty ester diols, polysiloxane diols, polyester diols, polytetramethylene glycol, dimer diols and mixtures thereof and an isocyanate blocking agent.
  • the blocked isocyanate extenders of this invention can be obtained by a well-known condensation reaction of a polyisocyanate, a diol selected from the group consisting of fatty ester diols, polysiloxane diols, polyester diols, polytetramethylene glycol, dimer diols and mixtures thereof and an isocyanate blocking agent.
  • the blocked isocyanate extenders preferably contain between 1 and 20 units, more preferably between 2 and 15 units derived from the diol.
  • Suitable polyisocyanates include aliphatic and aromatic di- and tri- isocyanates.
  • aromatic diisocyanates such as 4,4'-methylenediphenylenediisocyanate, 4,6-di- (trifluoromethyl)- 1,3 -benzene diisocyanate, 2,4-toluenediisocyanate, 2,6-toluene diisocyanate, o, m, and p-xylylene diisocyanate, 4,4'-diisocyanatodiphenylether, 3,3'- dichloro-4,4'-diisocyanatodiphenylmethane, 4, 5'-diphenyldiisocyanate, 4,4'- diisocyanatodibenzyl, 3,3'-dimethoxy-4,4'-diisocyanatodiphenyl, 3,3'-dimethyl-4,4'- diisocyanatodiphenyl, 2,2'-dich
  • isocyanates containing internal isocyanate-derived moieties such as biuret- containing tri-isocyanates such as that available from Bayer as DESMODURTM N-100, isocyanurate-containing tri-isocyanates such as that available from Huls AG, Germany, as IPDI- 1890, and azetedinedione-containing diisocyanates such as that available from Bayer as DESMODURTM TT.
  • other di- or tri-isocyanates such as those available from Bayer as DESMODURTM L and DESMODURTM W, and tri-(4-isocyanatophenyl)- methane (available from Bayer as DESMODURTM R) are suitable.
  • fatty ester diols examples include glycerol mono- oleate, glycerol mono-stearate, glycerol mono-ricinoleate, glycerol mono-tallow, long chain alkyl di-esters of pentaerythritol having at least 5 carbon atoms in the alkyl group.
  • Suitable fatty ester diols are commercially available under the brand RJLANIT® from Henkel and examples include RILANIT® GMS, RILANIT® GMRO and RILANIT® HE.
  • the diol used is a polysiloxane diol such as a polydialkylsiloxane diol or a polyalkylarylsiloxane diol. It has been found that a blocked isocyanate containing polysiloxane segments improves the efficiency of the fluorine treatment while increasing the soft feel of the fibrous substrate.
  • Particularly preferred polysiloxane diols include polydialkylsiloxanes having an alkyl group of 1 to 4 carbon atoms and polyalkylarylsiloxanes.
  • the polymerization degree of the polysiloxane diol is preferably between 10 and 50 and more preferably between 10 and 30.
  • Especially preferred polysiloxane diols correspond to one of the following two formulas: R J R 3 R '
  • R 1 and R 2 independently represent an alkylene having 1 to 4 carbon atoms
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 independently represent an alkyl group having 1 to 4 carbon atoms or an aryl group
  • L represents a trivalent linking group
  • m represents a value of 10 to 50.
  • L is for example a linear or branched alkylene that may contain one or more catenary hetero atoms such as oxygen or nitrogen.
  • polyester diols are suitable for use in this invention.
  • polyester diols include linear polyesters available under the brand UNTFLEX from Union Camp and polyesters derived from dimer acids or dimer diols. Dimer acids and dimer diols are well-known and are obtained by dimerisation of unsaturated acids or diols in particular of unsaturated long chain aliphatic acids or diols (e.g. at least 5 carbon atoms). Examples of polyesters obtainable from dimer acids and/or dimer diols are those available under the brand PRIPLAST from Unichema Chemicals Inc..
  • Isocyanate blocking agents for use in this invention are compounds that upon reaction with an isocyanate group yields a group that is unreactive at room temperature with compounds that at room temperature normally react with an isocyanate but which group at elevated temperature reacts with isocyanate reactive compounds.
  • a single compound or a mixture of different masking or blocking agents may be used.
  • Particularly preferred isocyanate blocking or masking agents include C 2 to C 8 alkanone oximes, e.g., 2-butanone oxime, monofunctional alcohols such as 2-ethylhexanol and (iso)stearylalcohol.
  • the condensation reaction to prepare the blocked isocyanate extender can be carried out under conventional conditions well-known to those skilled in the art.
  • the reaction is run in the presence of a catalyst.
  • Suitable catalysts include tin salts such as dibutyltin dilaurate, stannous octanoate, stannous oleate, tin dibutyldi-(2-ethyl hexanoate), stannous chloride; and others known to those skilled in the art.
  • the amount of catalyst present will depend on the particular reaction, and thus it is not practical to recite particular preferred concentrations. Generally, however, suitable catalyst concentrations are from about 0.001 percent to about 10 percent, preferably about 0.1 percent to about 5 percent, by weight based on the total weight of the reactants.
  • fluorochemical compounds useful in this invention include any of the known fluoroaliphatic radical-containing agents useful for the treatment of fabrics to obtain oil and water repellency.
  • the fluoroaliphatic radical, called Rf for brevity is stable, inert, non- polar, preferably saturated, monovalent and both oleophobic and hydrophobic.
  • the R f group preferably contains at least about 3 carbon atoms, more preferably 3 to about 20 carbon atoms, and most preferably about 6 to about 14 carbon atoms.
  • Rf can contain straight chain, branched chain, or cyclic fluorinated alkylene groups or combinations thereof with straight chain, branched chain, or cyclic alkylene groups.
  • Rf is preferably free of polymerizable olefinic unsaturation and can optionally contain catenary heteroatoms such as oxygen, divalent or hexavalent sulfiir, or nitrogen. It is preferred that R f contains about 40% to about 80% fluorine by weight, more preferably about 50% to about 78% fluorine by weight.
  • the terminal portion of the Rf group is fully fluorinated preferably containing at least 7 fluorine atoms, e.g., CF 3 CF 2 CF 2 ⁇ , (CF 3 ) 2 CF ⁇ , ⁇ CF 2 SF 5 , or the like.
  • Perfluorinated aliphatic groups i.e., those of the formula C n F 2n + ⁇ are the most preferred embodiments of Rf.
  • useful fluorochemical agents include, for example, Rf -containing urethanes, ureas, esters, amines (and salts thereof), amides, acids (and salts thereof), carbodiimides, guanidines, allophanates, biurets, oxazolidinones, and other substances containing one or more R f groups, as well as mixtures and blends thereof.
  • Rf -containing urethanes ureas, esters, amines (and salts thereof), amides, acids (and salts thereof), carbodiimides, guanidines, allophanates, biurets, oxazolidinones, and other substances containing one or more R f groups, as well as mixtures and blends thereof.
  • Such agents are well known to those skilled in the art, see e.g., Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol. 24, pp. 448-451 and many (e.g.,
  • the amount of fluorochemical compound and blocked isocyanate extender in the fluorochemical composition is selected such as to obtain the desired properties, for example oil and/or water repellency, on the fibrous substrate.
  • the amount of blocked isocyanate extender is between 15 parts by weight and 45 parts by weight for 100 parts by weight of the fluorochemical compound used.
  • the fluorochemical composition of this invention can be applied using conventional application methods but is preferably used as an aqueous emulsion. Alternatively it can be used as a treatment composition in solvent.
  • An aqueous emulsion will generally contain water, an amount of fluorochemical composition effective to provide repellent properties to a substrate treated therewith, and a surfactant in an amount effective to stabilize the emulsion.
  • Water is preferably present in an amount of about 70 to about 2000 parts by weight based on 100 parts by weight of the fluorochemical composition of the invention.
  • the surfactant is preferably present in an amount of about 1 to about 25 parts by weight, preferably about 2 to about 10 parts by weight, based on 100 parts by weight of the fluorochemical composition.
  • Conventional cationic, nonionic, anionic, and zwitterionic surfactants are suitable.
  • the amount of the treating composition applied to a substrate in accordance with this invention is chosen so that a sufficiently high level of the desired properties are imparted to the substrate surface, said amount usually being such that 0.01% to 5% by weight, preferably 0.05% to 2% by weight, based on the weight of the substrate, of fluorochemical composition is present on the treated substrate.
  • the amount which is sufficient to impart desired properties can be determined empirically and can be increased as necessary or desired.
  • the fibrous substrates treated by the fluorochemical composition of this invention are not especially limited and include textile fabrics, wood, non-wovens and paper.
  • the fluorochemical composition of the present invention is particularly suitable to provide oil and/or water repellency to textile.
  • the substrate can be immersed in a diluted emulsion.
  • the saturated substrate can then be run through a padder/roller to remove excess emulsion, dried and cured in an oven at a temperature and for a time sufficient to provide a cured treated substrate.
  • This curing process is typically carried out at temperatures between about 50°C and about 190°C depending on the particular system or application method used. In general, a temperature of about 120°C to 170°C, in particular of about 150°C to about 170°C for a period of about 20 seconds to 10 minutes, preferably 3 to 5 minutes, is suitable.
  • Treatment baths were formulated containing a defined amount of the fluorochemical composition according to the invention. Treatments were applied to the test substrates by padding at a concentration of 0.4% solids (based on fabric weight and indicated as SOF (solids on fabric)) unless otherwise indicated, and drying and curing at 150°C to 170°C for 1.5 to 3 minutes. Substrates used for the evaluation of treatments of this invention are all commercially available and are listed below :
  • PES/CO Grey polyester/cotton 65/35, style No. 2681 , obtained through
  • PA Polyamide microfiber, style No. 7819, obtained from Sofinal, Belgium
  • Respective data of water and oil repellency shown in the Examples and Comparative Examples are based on the following methods of measurement and evaluation criteria :
  • the treated substrates were subjected to a simulated rainfall, while the back of the substrate was being rubbed.
  • the appearance of the upper exposed surface was checked visually after 1, 5 and 10 minutes and was given a rating between 1 (complete surface wetting) and 5 (no water remains on the surface).
  • the water absorption (% abs) after 10 min rain test was measured. The lower the % absorption, the better the treatment.
  • the spray rating of a treated substrate is indicative of the dynamic repellency of the treated substrate to water that impinges on the treated substrate.
  • the spray rating was measured by Standard Test Number 22, published in the 1985 Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists (AATCC), and was expressed in terms of 'spray rating' (SR) of the tested substrate.
  • the spray rating was obtained by spraying 250 ml water on the substrate from a height of 15 cm.
  • the wetting pattern was visually rated : using a 0 to 100 scale, where 0 meant complete wetting and 100 meant no wetting at all.
  • the water repellency (WR) of a treated substrate was measured using a water-isopropyl alcohol test liquid, and was expressed in terms of the "WR" rating of the treated substrate.
  • Other intermediate values were determined by use of other water-isopropyl alcohol test liquids, in which the percentage amounts of water and isopropyl alcohol were each multiples of 10.
  • the WR rating corresponded to the most penetrating test liquid which did not penetrate or wet the substrate after 15 seconds contact. In general, a water repellency rating of 2 or greater is desirable.
  • the oil repellency of a treated substrate was measured by the American Association of Textile Chemists and Colorists (AATCC) Standard Test Method No. 118-1983, which test was based on the resistance of a treated substrate to penetration by oils of varying surface tensions. Treated substrates resistant only to Nujol®, mineral oil (the least penetrating of the test oils) were given a rating of 1, whereas treated substrates resistant to heptane (the most penetrating of the test oils) were given a rating of 8. Other intermediate values were determined by use of other pure oils or mixtures of oils, as shown in the following table.
  • a 230 g sample of generally square, 400 cm 2 to about 900 cm 2 sheets of treated substrate was placed in a washing machine along with a ballast sample (1.9 kg of 8 oz fabric in the form of generally square, hemmed 8100 cm 2 sheets).
  • Conventional detergent 46 g "Sapton", available from Henkel
  • the substrate and ballast load were washed several times (indicated as x HL) using a 12-minute normal wash cycle followed by five rinse cycles and centrifuging. The samples were not dried between repeat cycles.
  • Ironing procedure (indicated as x HL Iron): After drying, the samples were pressed using an iron at a temperature set for the fiber of the substrate.
  • Tumble dry procedure (x HL TD) : the substrate and ballast were dried together in a conventional tumble drier at 70-75°C, at a setting for "normal dry". The machine turned itself off when the environmental humidity dropped below a given value. This generally took 15-20 minutes depending upon the load in the machine. Materials tested after a tumble dry cycle were labeled x HL TD.
  • Treated fabrics were rated for their 'hand', i.e., their softness, smoothness, pliability and fluffiness to the touch, as this feature is important for the comfort and aesthetic appeal of repellent textile substrates.
  • a scale of 10 to 1 was used, where a rating of 10 was given to those treatments which left the fabric the softest, while a rating of 1 was given to those treatments which gave the fabric the harshest hand (i.e., provided a rough, stiff, cardboard-like feel).
  • the ratings in between were assigned to intermediate hand values. The ratings were an average of the evaluation by a test panel (4-7 persons).
  • MIBK Methyl isobutyl ketone
  • MEFOSEA N-methyl perfluorooctyl sulfonamidoethyl (meth)acrylate
  • EHMA ethylhexyl methacrylate
  • HOEMA hydroxyethylmethacrylate
  • PAPI VoranateTM M220 : polymethylene polyphenyl isocyanate, available from Dow
  • Cynthane® 3160 aliphatic polyisocyanate resin, available from Cyanamid
  • AtpolTM E5721 alkytethoxylate, available from ICI
  • RewoponTM IM/OA imidazoline type surfactant, available from Rewo, Germany
  • EthoquadTM 18/25 methyl polyoxyethylene(15) octadecyl ammonium chloride, available from Akzo
  • IM11TM, VP1610 and SLM 50400 alpha, omega-hydroxy organofunctional polydimethylsiloxanes, available from Wacker
  • PDMS 2000-MA polydimethylsiloxane methacrylate with number average molecular weight 2000, available from Shin Etsu
  • T650 TerathaneTM 650 : polytetramethylene oxide, available from Dupont de Nemours
  • PripolTM 2033 (P2033) : dimer acid ester diol, available from Unichema PriplastTM 3193 : dimer based polyester diol, available from Unichema RilanitTM HE : dicarbonic acid ester diol, available from Henkel RilanitTM GMS : glycerine mono tallow fatty acid ester, available from Henkel RilanitTM GMRO : glycerine mono ricinoleate, available from Henkel RadiamulsTM MG 2900 : glycerol monostearate, available from Fina Chemicals UniflexTM 313 : polyester diol, available from Union Camp X-22-176B : Polydimethylsiloxane, available from Shin Etsu DBTDL : dibutyltin dilaurate
  • a reaction flask equipped with a reflux condenser, a mechanical teflon blade stirrer, a thermometer, a nitrogen inlet and vacuo outlet, was charged with 0.15 moles (55 g) PAPI, 0.1 moles (35.7 g) RadiomulsTM MG 2900, 0.25 moles (21.7 g) 2-butanone oxime and 261 g MIBK. After addition of 2 drops DBTDL, the mixture was stirred at 75°C during 7 hours after which FTIR analysis indicated that all isocyanate was reacted.
  • the product obtained above was added to a mixture of water (250g), RewoponTM IM OA (6.7 g) and ATPOLTM E5721 (2.2 g). After homogenisation with an ultrasonic probe (Branson 250 sonifier) the organic solvent was removed by evaporation and a 20% emulsion in water was obtained. Following the same procedure, different blocked isocyanates as given in table 1 have been synthesized.
  • Comparative extender CE-1 was made according to the same procedure. Comparative extender CE-2 was prepared according to the teaching of EP 383 310. Table 1 : Composition of blocked isocyanate extenders (E)
  • FC Fluorochemical agents
  • FC 3542 is a blend of a fluorochemical urethane and a fluorochemical acrylate
  • FC 3548 is a blend of a fluorochemical urethane, a fluorochemical acrylate and a fluorochemical ester
  • FC 3575 is a blend of a fluorochemical urethane and a fluorochemical acrylate
  • FC 251 is a blend of a fluorochemical urethane and a fluorochemical acrylate
  • FC 3551 is a fluorochemical acrylate Further fluorochemical treating agents
  • a polymerization bottle was charged with 150 g MeFOSEA, 38g EHMA, 9.4 g EthoquadTM 18/25, 1.4 g n-octylmercaptan, 0.94 g V-50TM initiator (2,2Xazobis(2- methylpropionamidine)dihydrochloride, available from Wacko, Osaka, Japan), 109 g acetone and 434 g deionized water.
  • the reaction mixture was deaerated and covered with a nitrogen atmosphere.
  • the polymerization bottle was capped and run in a Launder-o- meter at 73°C for 16 hours. Acetone was removed from the resulting transparent dispersion via vacuum distillation.
  • FC-2 a copolymer of MEFOSEA/ODMA/PDMS 2000-MA 80/15/5 was prepared according to US Patent No 5,258,458, Terpolymer A, Column 12.
  • Examples 1 to 19 illustrate the effect the blocked isocyanate extenders have on the fluorine efficiency of a fluorochemical treating agent.
  • Treatment compositions were prepared in which one third of the fluorochemical treating agent was replaced by an extender as given in table 2.
  • Comparative examples C-l, C-3, C-5, C-7 and C-9 were made using a blend of the fluorochemical treating agent and a conventional extender (CE- 1) and comparative examples C-2, C-4, C-6, C-8 and C-10 were made with fluorochemical treating agent alone.
  • the treating compositions were applied to PES/CO so as to give a total of 0.3% SOF (0.2% FC and 0.1% extender or 0.3% FC alone).
  • the substrates were cured at 150°C during 3 minutes. The performance results are given in table 2.
  • Table 2 Performance results of PES/CO treated with a blend of fluorochemical treating agent and blocked isocyanate extender
  • PES/CO substrates were treated with a blend of fluorochemical treating agent and blocked isocyanates so as to give a total add-on of 0.4% SOF (0.3% FC + 0.1% extender).
  • Comparative examples C-l 1, C-l 4 and C-l 2, C-l 5 were made with comparative extenders CE-1 and CE-2 respectively.
  • Comparative examples C-l 3 and C- 16 were made by treating the PES/CO with pure FC (0.4% SOF) The treated fabrics were cured at 150°C during 3 min. The dried substrates were tested for their oil and water repellency and their softness. The results are given in table 3.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition fluorochimique pour le traitement d'un substrat fibreux. Ladite composition fluorochimique comprend au moins un composé fluorochimique et une charge à base d'isocyanate bloqué, dérivée de la condensation d'un polyisocyanate, un diol choisi dans le groupe comprenant des diols d'ester d'acide gras, des diols de polysiloxane, des diols de polyester, du polytétraméthylène glycol, des diols dimères et des mélanges de ceux-ci et un agent bloquant l'isocyanate. L'invention se rapporte également à un substrat fibreux traité à l'aide de ladite composition et à l'utilisation de ladite composition fluorochimique pour rendre un substrat fibreux oléophobe ou hydrophobe.
PCT/IB1997/001354 1997-09-18 1997-09-18 Composition fluorochimique comprenant un diluant a base d'isocyanate bloque et procede de traitement d'un substrat fibreux a l'aide de celle-ci Ceased WO1999014422A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
JP2000511950A JP4149658B2 (ja) 1997-09-18 1997-09-18 ブロックトイソシアネート増量剤を含むフルオロケミカル組成物および前記組成物による繊維ウェブの処理方法
PCT/IB1997/001354 WO1999014422A1 (fr) 1997-09-18 1997-09-18 Composition fluorochimique comprenant un diluant a base d'isocyanate bloque et procede de traitement d'un substrat fibreux a l'aide de celle-ci
KR10-2000-7002862A KR100537881B1 (ko) 1997-09-18 1997-09-18 차단된 이소시아네이트 증량제를 포함하는 플루오로케미컬조성물 및 이것으로 섬유 기재를 처리하는 방법
AU46344/97A AU4634497A (en) 1997-09-18 1997-09-18 Fluorochemical composition comprising a blocked isocyanate extender and method of treatment of a fibrous substrate therewith
DE69723480T DE69723480T2 (de) 1997-09-18 1997-09-18 Fluorierte verbindungen enthaltende zusammensetzung mit einem streckmittel aus blockierten isocyanaten und die methode zur behandlung von fasersubstraten
EP97945040A EP1017897B1 (fr) 1997-09-18 1997-09-18 Composition fluorochimique comprenant un diluant a base d'isocyanate bloque et procede de traitement d'un substrat fibreux a l'aide de celle-ci
BR9714826-1A BR9714826A (pt) 1997-09-18 1997-09-18 Composição fluoroquìmica e processo para tratamento de um substrato fibroso, uso desta composição, e, substrato fibroso
IDP981249A ID20879A (id) 1997-09-18 1998-09-17 Komposisi fluoro kimia terdiri dari bahan pengembang iso sianat diblok dan metoda pengolahan dari bahan dasar berserat di sini

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB1997/001354 WO1999014422A1 (fr) 1997-09-18 1997-09-18 Composition fluorochimique comprenant un diluant a base d'isocyanate bloque et procede de traitement d'un substrat fibreux a l'aide de celle-ci

Publications (1)

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WO1999014422A1 true WO1999014422A1 (fr) 1999-03-25

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Country Status (7)

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EP (1) EP1017897B1 (fr)
JP (1) JP4149658B2 (fr)
KR (1) KR100537881B1 (fr)
AU (1) AU4634497A (fr)
DE (1) DE69723480T2 (fr)
ID (1) ID20879A (fr)
WO (1) WO1999014422A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
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EP1088929A1 (fr) * 1999-09-30 2001-04-04 Ciba Spezialitätenchemie Pfersee GmbH Compositions pour le finissage oléo-et hydrorépulsif de matériaux textiles
WO2001075214A3 (fr) * 2000-04-04 2001-12-13 Ciba Sc Pfersee Gmbh Compositions de silicone permettant de traiter des materiaux laineux
WO2003014180A1 (fr) * 2001-08-09 2003-02-20 Ciba Spezialitätenchemie Pfersee GmbH Compositions de polysiloxanes, fluoropolymeres et extendeurs
WO2003078725A1 (fr) * 2002-03-15 2003-09-25 Rudolf Gmbh & Co. Kg Chemische Fabrik Preparations a base d'eau et/ou de solvants organiques et leur utilisation comme appret sur des produits plats
DE10325094A1 (de) * 2003-06-03 2004-12-30 Rudolf Gmbh & Co. Kg Chemische Fabrik Zubereitungen für die öl- und wasserabweisende Ausrüstung von Flächengebilden und deren Anwendung
US7723414B2 (en) 2006-12-22 2010-05-25 E. I. Du Pont De Nemours And Company Antistatic system for polymers
WO2013085882A1 (fr) 2011-12-06 2013-06-13 Dow Corning Corporation Composition de silicone durcissable, matériau durci, articles fabriqués, procédés et utilisations
CN103966855A (zh) * 2009-09-26 2014-08-06 亨茨曼纺织货品（德国）有限责任公司 用于纤维材料的防油和/或防水整理的组合物
US8828098B2 (en) 2006-12-18 2014-09-09 3M Innovative Properties Company Extenders for fluorochemical treatment of fibrous substrates
WO2014207724A3 (fr) * 2013-06-28 2015-05-14 Tata Motors Limited Composition et procédé pour conférer une étanchéité aux taches et une résistance à la flamme à un tissu
US10960570B2 (en) * 2018-03-01 2021-03-30 Hexion Inc. Additives for lignocellulosic composites

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JP4752197B2 (ja) * 2004-06-04 2011-08-17 ユニマテック株式会社 撥水撥油剤の製造法

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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1088929A1 (fr) * 1999-09-30 2001-04-04 Ciba Spezialitätenchemie Pfersee GmbH Compositions pour le finissage oléo-et hydrorépulsif de matériaux textiles
US6387999B1 (en) 1999-09-30 2002-05-14 Ciba Specialty Chemicals Corporation Compositions for the oil and water repellent finishing of fiber materials
CN100352996C (zh) * 1999-09-30 2007-12-05 西巴特殊化学品普法希股份有限公司 用于纤维材料的抗油和抗水整理的组合物
KR100806530B1 (ko) * 1999-09-30 2008-02-25 훈츠만 텍스틸레 에펙츠 (게르마니) 게엠베하 섬유 재료의 발유 및 발수 가공용 조성물 및 이의 제조방법
WO2001075214A3 (fr) * 2000-04-04 2001-12-13 Ciba Sc Pfersee Gmbh Compositions de silicone permettant de traiter des materiaux laineux
US6783806B2 (en) 2000-04-04 2004-08-31 Ciba Specialty Chemicals Corporation Silicone compositions for treating wool materials
WO2003014180A1 (fr) * 2001-08-09 2003-02-20 Ciba Spezialitätenchemie Pfersee GmbH Compositions de polysiloxanes, fluoropolymeres et extendeurs
US7053148B2 (en) 2001-08-09 2006-05-30 Ciba Specialty Chemicals Corporation Compositions of polysiloxanes, fluoropolymers extenders
DE10211549B4 (de) * 2002-03-15 2004-07-29 Rudolf Gmbh & Co. Kg Chemische Fabrik Zubereitungen auf Basis von Wasser und/oder organischen Lösemitteln und deren Anwendung als Appretur auf Flächengebilden
US7354458B2 (en) 2002-03-15 2008-04-08 Rudolf Gmbh & Co., Kg, Chemische Fabrik Preparations based on water and/or organic solvents and their use as a finish on flat materials
DE10211549B9 (de) * 2002-03-15 2004-11-25 Rudolf Gmbh & Co. Kg Chemische Fabrik Zubereitungen auf Basis von Wasser und/oder organischen Lösemitteln und deren Anwendung als Appretur auf Flächengebilden
DE10211549A1 (de) * 2002-03-15 2003-10-09 Rudolf Gmbh & Co Kg Chem Fab Zubereitungen auf Basis von Wasser und/oder organischen Lösemitteln und deren Anwendung als Appretur auf Flächengebilden
WO2003078725A1 (fr) * 2002-03-15 2003-09-25 Rudolf Gmbh & Co. Kg Chemische Fabrik Preparations a base d'eau et/ou de solvants organiques et leur utilisation comme appret sur des produits plats
DE10325094B4 (de) * 2003-06-03 2006-02-16 Rudolf Gmbh & Co. Kg Chemische Fabrik Zubereitungen für die öl- und wasserabweisende Ausrüstung von Flächengebilden und deren Anwendung
DE10325094A1 (de) * 2003-06-03 2004-12-30 Rudolf Gmbh & Co. Kg Chemische Fabrik Zubereitungen für die öl- und wasserabweisende Ausrüstung von Flächengebilden und deren Anwendung
US8231802B2 (en) 2003-06-03 2012-07-31 Rudolf Gmbh Preparations for making planar structures oil-repellent and water-repellent, and use thereof
US8828098B2 (en) 2006-12-18 2014-09-09 3M Innovative Properties Company Extenders for fluorochemical treatment of fibrous substrates
US7723414B2 (en) 2006-12-22 2010-05-25 E. I. Du Pont De Nemours And Company Antistatic system for polymers
CN103966855A (zh) * 2009-09-26 2014-08-06 亨茨曼纺织货品（德国）有限责任公司 用于纤维材料的防油和/或防水整理的组合物
WO2013085882A1 (fr) 2011-12-06 2013-06-13 Dow Corning Corporation Composition de silicone durcissable, matériau durci, articles fabriqués, procédés et utilisations
WO2014207724A3 (fr) * 2013-06-28 2015-05-14 Tata Motors Limited Composition et procédé pour conférer une étanchéité aux taches et une résistance à la flamme à un tissu
US10960570B2 (en) * 2018-03-01 2021-03-30 Hexion Inc. Additives for lignocellulosic composites

Also Published As

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EP1017897B1 (fr) 2003-07-09
AU4634497A (en) 1999-04-05
JP4149658B2 (ja) 2008-09-10
ID20879A (id) 1999-03-18
KR20010024107A (ko) 2001-03-26
DE69723480T2 (de) 2004-06-09
JP2001516818A (ja) 2001-10-02
DE69723480D1 (de) 2003-08-14
EP1017897A1 (fr) 2000-07-12
KR100537881B1 (ko) 2005-12-21

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