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WO2008063903A1 - Composition fluorochimique destinée au traitement d'un substrat fibreux - Google Patents

Composition fluorochimique destinée au traitement d'un substrat fibreux Download PDF

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Publication number
WO2008063903A1
WO2008063903A1 PCT/US2007/084059 US2007084059W WO2008063903A1 WO 2008063903 A1 WO2008063903 A1 WO 2008063903A1 US 2007084059 W US2007084059 W US 2007084059W WO 2008063903 A1 WO2008063903 A1 WO 2008063903A1
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Prior art keywords
group
isocyanate
fluorochemical composition
groups
fluorinated
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Inventor
Dean M. Moren
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3M Innovative Properties Co
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3M Innovative Properties Co
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • 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
    • D06M13/10—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 oxygen
    • D06M13/165—Ethers
    • D06M13/17—Polyoxyalkyleneglycol ethers
    • 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
    • D06M13/10—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 oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/213—Perfluoroalkyl carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—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 oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D06M13/217—Polyoxyalkyleneglycol ethers with a terminal carboxyl group; Anhydrides, halides or salts thereof

Definitions

  • the present invention relates to a fluoro chemical composition for rendering fibrous substrates oil repellent, water repellent, and/or stain or soil repellent. Additionally, the invention also relates to a method of treating the fibrous substrate with the fluorochemical composition.
  • compositions for making substrates, in particular fibrous substrates, such as textile, oil- and water repellent have been long known in the art.
  • the composition should normally not contain components that would affect the look of the product, i.e., the treatment should be substantially invisible to the unaided human eye.
  • the feel of the substrate should preferably be substantially unaffected. Typically this means that only low amounts of the solids of the composition can be applied. Accordingly, an oil- and/or water repellent composition should be highly effective in rendering a substrate repellent.
  • oil- and/or water repellent compositions are typically based on fluorinated compounds that have a perfluorinated aliphatic group. Such compositions are also described in for example U.S. Patent No. 5,276,175 and EP 435 641. The commercial success of this type of composition can be attributed to their high effectiveness. Fluorinated compounds based on perfluorinated ether moieties have also been described in the prior art for rendering fibrous substrates oil- and/or water repellent. For example, perfluorinated polyether compounds have been disclosed in EP 1 038 919, EP 273 449, JP-A-04-146917, JP-A-10-081873, U.S. Patent Nos. 3,536,710, 3,814,741, 3,553,179, and 3,446,761. It was found that previously disclosed compositions based on perfluorinated polyether compounds may not be very effective in rendering a fibrous substrate oil- and/or water repellent.
  • the fluorochemical composition is capable of providing durable oil- and/or water repellency properties to a fibrous substrate such that a treated fibrous substrate can substantially maintain the repellency properties even after several washing cycles.
  • a fibrous substrate treated with the fluorochemical composition has a soft feel, preferably the feel of a treated fibrous substrate is either the same or softer compared to the untreated fibrous substrate. It is a further desire that the fluorochemical compositions can be easily and efficiently manufactured and used at a low cost. It is further desired to find compositions that have environmentally beneficial properties.
  • the present invention provides fluorochemical compositions for imparting oil repellency, water repellency, stain release, and soil release to fibrous substrates.
  • Compositions of the invention provide a surprising and heretofore unachieved combination of relatively low cost with durable high performance.
  • the present invention provides in one aspect a fluorochemical composition comprising a dispersion or a solution of a fluorinated compound, wherein said fluorinated compound comprises the reaction product of a combination of reactants comprising: (i) one or more fluorinated polyethers according to the formula:
  • R r QT k (I) wherein R f represents a monovalent perfluorinated polyether group having a number average molecular weight of at least 750g/mol, Q represents a chemical bond or a divalent or trivalent organic linking group, T represents a functional group capable of reacting with an isocyanate, and k is 1 or 2; (ii) one or more polyoxyalkylene diols; (iii) one or more short chain perfluoroalkyl alcohols (iv) one or more isocyanate component selected from a polyisocyanate compound that has at least 3 isocyanate groups or a mixture of polyisocyanate compounds wherein the average number of isocyanate groups per molecule is more than 2 (v) optionally one or more isocyanate blocking groups; and (vi) optionally one or more co-reactants capable of reacting with an isocyanate group.
  • R f represents a monovalent perfluorinated polyether group having a number average molecular weight
  • fluorochemical urethanes of the invention less than about about 15%, preferably from about 2 to about 8%, of the isocyanate groups are reacted with perfluorinated polyether; less than about 15%, preferably from 0 to about 10%, of the isocyanate groups are reacted with isocyanate blocking group; more than about 5%, preferably from about 10 to about 40%, of the isocyanate groups are reacted with polyoxyalkylene diol; and more than about 35%, preferably from about 50 to about 75%, of the isocyanate groups are reacted with short-chain perfluoroalkyl alcohol.
  • the invention further provides a method of treatment of a fibrous substrate with the fluorochemical composition whereby oil- and/or water repellent properties are provided to the substrate.
  • the fluorochemical composition of the present invention can provide good to excellent repellency properties to the substrate. Moreover, durable oil- and/or water repellency properties can be obtained.
  • the fluorochemical compositions may further provide soil repellency as well as soil or stain release properties.
  • soil and/or stain release is used to mean that a treated substrate that becomes soiled or stained can be more easily cleaned in for example a home laundering than an untreated substrate that becomes soiled or stained. Soil/stain repellency on the other hand refers to the ability of the treated substrate to repel soil thereby reducing soiling or staining of the substrate.
  • the fibrous substrate will retain a soft feel after treatment with the fluorochemical composition.
  • the fluorochemical compositions of the present inventions are generally environmentally friendly in that compositions can be obtained that are substantially free of fluorochemical components that eliminate slowly from the body of living organisms.
  • fluorochemical degradation products that may form likewise eliminate well from the body of living organisms.
  • indications show that the fluorinated polyether compounds that have a perfluorinated polyether moiety having a molecular weight of at least 750g/mol and perfluorinated polyether degradation products that may form therefrom would eliminate more effectively from the body of living organisms.
  • fluorinated polyether compounds having a fluorinated polyether moiety derivable from a polycondensation of hexafluoropropylene oxide and having a molecular weight of at least 750 g/mol would more effectively eliminate from the body of living organisms compared to long chain perfluoroaliphatic compounds.
  • the fluorochemical composition of the invention comprises a dispersion or a solution of a fluorinated compound, wherein said fluorinated compound comprises the reaction product of a combination of reactants comprising: (i) one or more fluorinated polyethers according to the formula:
  • R represents a monovalent perfluorinated polyether group having a number average molecular weight of at least 750g/mol
  • Q represents a chemical bond or a divalent or trivalent organic linking group
  • T represents a functional group capable of reacting with an isocyanate
  • k is 1 or 2;
  • one or more isocyanate component selected from a polyisocyanate compound that has at least 3 isocyanate groups or a mixture of polyisocyanate compounds wherein the average number of isocyanate groups per molecule is more than 2; (v) optionally one or more isocyanate blocking group; and (vi) optionally one or more co-reactants capable of reacting with an isocyanate group.
  • the fluorinated compound used in the fluorochemical composition is obtainable by reacting an isocyanate component and optional co-reactants with a fluorinated polyether according to formula (I) that has an isocyanate reactive group:
  • R f QT k (I) wherein R f represents a monovalent perfluorinated polyether group, Q represents a chemical bond or a divalent or trivalent non-fluorinated organic linking group, T represents a functional group capable of reacting with an isocyanate, and k is 1 or 2. From about 2% to about 15%, preferably from about 2% to about 8%, of the isocyanate groups will be reacted with perfluorinated polyether. If lesser isocyanate is so reacted, the resultant coating may tend to be too stiff and to be deficient in performance. If more isocyanate is so reacted, the resultant composition will tend to be more expensive.
  • the perfluorinated polyether moiety R f of the fluorinated polyether of formula (I) preferably corresponds to the formula:
  • R fl OR ⁇ (R ⁇ ) q (II) wherein R fI represents a perfluorinated alkyl group, R ⁇ represents a perfluorinated polyalkyleneoxy group consisting of perfluorinated alkyleneoxy groups having 1, 2, 3, or 4 carbon atoms or a mixture of such perfluorinated alkylene oxy groups, R ⁇ represents a perfluorinated alkylene group, and q is 0 or 1.
  • the perfluorinated alkyl group R fl in formula (II) may be linear or branched and may comprise 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
  • a typical perfluorinated alkyl group is CF 3 CF 2 CF 2 -.
  • R is a linear or branched perfluorinated alkylene group that will typically have 1 to 6 carbon atoms, for example, -CF 2 - or -CF(CF 3 )-.
  • perfluoroalkylene oxy groups of perfluorinated polyalkyleneoxy group R ⁇ include: -CF 2 CF 2 O-, -CF(CF 3 )CF 2 O-, -CF 2 CF(CF 3 )O-, -CF 2 CF 2 CF 2 O-,
  • the perfluoroalkyleneoxy group may be comprised of the same perfluoroalkylene oxy units or of a mixture of different perfluoroalkylene oxy units.
  • the perfluoroalkyleneoxy group can be present in a random configuration, alternating configuration or they can be present as blocks.
  • Typical examples of perfluorinated polyalkylene oxy groups include:
  • a preferred perfluorinated polyether group that corresponds to formula (II) is CF 3 CF 2 CF 2 O[CF(CF 3 )CF 2 O] n CF(CF 3 )- wherein n is an integer of 3 to 25.
  • This perfluorinated polyether group has a molecular weight of 783 when n equals 3 and can be derived from an oligomerization of hexafluoropropylene oxide. Such perfluorinated polyether groups are preferred in particular because of their benign environmental properties.
  • linking groups Q include organic groups that comprise aromatic or aliphatic groups that may be interrupted by O, N, or S and that may be substituted, alkylene groups, oxy groups, thio groups, urethane groups, carboxy groups, carbonyl groups, amido groups, oxyalkylene groups, thioalkylene groups, carboxyalkylene, and/or an amidoalkylene groups.
  • fluorinated polyether corresponds to the following formula (III):
  • R represents a perfluorinated alkyl group, e.g., a linear or branched perfluorinated alkyl group having 1 to 6 carbon atoms, n is an integer of 3 to 25, A is a carbonyl group or CH 2 , Q 1 is a chemical bond or an organic divalent or trivalent linking group, for example, as mentioned for the linking group Q above, k is 1 or 2, and T represents an isocyanate reactive group, and each T may be the same or different. Particularly preferred compounds are those in which R ⁇ represents CF 3 CF 2 CF 2 -.
  • the moiety -AQ 1 T k is a moiety of the formula - COXR a (OH) k wherein k is 1 or 2, X is O or NR b with R b representing hydrogen or an alkyl group of 1 to 4 carbon atoms, and R a is an alkylene of 1 to 15 carbon atoms.
  • Compounds according to formula (III) can for example be obtained by oligomerization of hexafluoropropylene oxide which results in a perfluoropolyether carbonyl fluoride.
  • This carbonyl fluoride may be converted into an acid, ester, or alcohol by reactions well known to those skilled in the art.
  • the carbonyl fluoride or acid, ester, or alcohol derived therefrom may then be reacted further to introduce the desired isocyanate reactive groups according to known procedures.
  • EP 870 778 describes suitable methods to produce compounds according to formula (III) having desired moieties -AQ 1 T k .
  • Compounds having group 1 listed above can be obtained by reacting the methyl ester derivative of a fluorinated polyether with 3-amino-2-hydroxy-propanol.
  • Compounds having the group 5 listed above can be obtained in a similar way by reacting with an amino-alcohol that has only one hydroxy function.
  • 2-aminoethanol would yield a compound having the group 5 listed above with R d being hydrogen and m being 2.
  • Still further examples of compounds according to above formula (I) are disclosed in European Patent No. 870 778 or U.S. Patent No. 3,536,710.
  • a mixture of fluorinated polyethers according to formula (I) may be used to prepare the fluorinated polyether compound of the fluorochemical composition.
  • the method of making the fluorinated polyether according to formula (I) will result in a mixture of fluorinated polyethers that have different molecular weights and such a mixture can be used as such to prepare the fluorochemical component of the fluorochemical composition.
  • such a mixture of fluorinated polyether compounds according to formula (I) is free of fluorinated polyether compounds having a perfluorinated polyether moiety having a molecular weight of less than 750 g/mol or alternatively the mixture contains fluorinated polyether compounds having a perfluorinated polyether moiety having a molecular weight of less than 750 g/mol in an amount of not more than about 10% by weight relative to total weight of fluorinated polyether compounds, preferably not more than about 5% by weight and most preferably not more than about 1% by weight.
  • At least about 5%, preferably from about 10% to about 40%, of the isocyanate groups will be reacted with polyoxyalkylene diol.
  • An illustrative example is polyoxypropylene diol having a number average molecular weight of from about 400 to about 2200. If less isocyanate is so reacted, the resultant coating may tend to have deficient durability and be deficient in performance. If more isocyanate is so reacted, the resultant composition will tend to gel making it more difficult to apply.
  • the short chain perfluoroalkyl alcohol has from 3 to 6 perfluorinated carbon atoms. In a preferred embodiment it comprises a C 4 F 9 - group.
  • perfluoroalkyl alchohols which are suitable for use herein include: C 4 F 9 SO 2 N(R)CH 2 CH 2 OH;
  • the isocyanate component for making the fluorinated compound of the fluorochemical composition is selected from a polyisocyanate having at least 3 isocyanate groups or a mixture of polyisocyanate compounds that on average has more than 2 isocyanate groups per molecule such as, for example, a mixture of a diisocyanate compound and a polyisocyanate compound having 3 or more isocyanate groups
  • the polyisocyanate compound may be aliphatic or aromatic and is conveniently a non-fluorinated compound. Aliphatic isocyantes are typically preferred as resultant compositions of the invention will be less subject to yellowing and will typically yield a softer finish on treated fibrous substrates.
  • the molecular weight of the polyisocyanate compound will be not more than 1500 g/mol.
  • examples include hexamethylenediisocyanate, 2,2,4-trimethyl-l,6- hexamethylenediisocyanate, 1 ,2-ethylenediisocyanate, dicyclohexylmethane-4,4'- diisocyanate, aliphatic triisocyanates such as 1,3,6-hexamethylenetriisocyanate, cyclic trimer of hexamethylenediisocyanate, and cyclic trimer of isophorone diisocyanate (isocyanurates); aromatic polyisocyanate such as 4,4'-methylenediphenylenediisocyanate, 4,6-di-(trifluoromethyl)- 1 ,3 -benzene diisocyanate, 2,4-toluenediisocyanate, 2,6-toluene diisocyanate, o, m, and p-x
  • Still further isocyanates that can be used for preparing the fluorinated compound include alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate; aromatic tri-isocyanates such as polymethylenepolyphenylisocyanate (PAPI); cyclic diisocyanates such as isophorone diisocyanate (IPDI).
  • alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate
  • aromatic tri-isocyanates such as polymethylenepolyphenylisocyanate (PAPI)
  • cyclic diisocyanates such as isophorone diisocyanate (IPDI).
  • 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 HuIs 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 tri-(4- isocyanatophenyl)-methane (available from Bayer as DESMODURTM R) and DDI 1410 (available from Henkel) are suitable.
  • the optional co-reactant may include an isocyanate blocking agent.
  • the isocyanate blocking agent can be used alone or in combination with one or more other co- reactants described above. Up to about 15%, preferably up to about 10%, of the isocyanate groups will be reacted with blocking agent.
  • Isocyanate blocking agents are compounds that upon reaction with an isocyanate group yield 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. For example, at elevated temperature the blocking group may be released from the blocked (poly)isocyanate compound thereby generating the isocyanate group again which can then react with an isocyanate reactive group.
  • Blocking agents and their mechanisms have been described in detail in "Blocked isocyanates III. : Part. A, Mechanisms and Chemistry" by Douglas Wicks and Zeno W. Wicks Jr., Progress in Organic Coatings, 36 (1999), pp. 14-172.
  • Preferred blocking agents include arylalcohols such as phenols; lactams such as ⁇ - caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam; and oximes such as formaldoxime, acetaldoxime, , cyclohexanone oxime, acetophenone oxime, benzophenone oxime, 2- butanone oxime; or diethyl glyoxime.
  • Further suitable blocking agents include bisulfite and triazoles.
  • the organic compound will include one or more water solubilising groups or groups capable of forming water solubilising groups so as to obtain a fluorinated compound that can more easily be dispersed in water. Additionally, by including water solubilising groups in the fluorinated compound, beneficial stain release properties may be obtained on the fibrous substrate.
  • Suitable water solubilising groups include non-ionic water solubilising groups.
  • organic compounds that have only one functional group capable of reacting with NCO-group and that further include a non-ionic water- solubilising group are used.
  • Typical non-ionic water solubilising groups include polyoxyalkylene groups.
  • Preferred polyoxyalkylene groups include those having 2 to 3 carbon atoms such as polyoxyethylene, polyoxypropylene, and copolymers thereof such as polymers having both oxyethylene and oxypropylene units.
  • the polyoxyalkylene containing organic compound may include one functional group such as hydroxy or amino groups.
  • Examples of polyoxyalkylene containing compounds include alkyl ethers of polyglycols such as, e.g., methyl or ethyl ether of polyethyleneglycol, hydroxy terminated methyl or ethyl ether of a random or block copolymer of ethyleneoxide and propyl eneoxide, amino terminated methyl or ethyl ether of polyethyleneoxide.
  • the perfluoroaliphatic group included in the fluorinated compound and the co- reactant may then comprise a perfluoroaliphatic compound having one or more isocyanate reactive groups.
  • perfluoroaliphatic groups are meant groups that consist of carbon and fluorine without however including perfluorinated end groups of the perfluorinated moiety.
  • the perfluoroaliphatic group contains 3 to 18 carbon atoms, preferably 3 to 6 carbon atoms, and most preferably is a C 4 F 9 - group.
  • perfluoroaliphatic groups, in particular C 4 F 9 - groups in the fluorinated polyether compound one can improve the solubility and/or dispersibility of the fluorinated polyether compound in the fluorochemical composition.
  • Preferred fluorinated co-reactants will correspond to the formula:
  • R represents a perfluoroaliphatic group having 3 to 5 or 6 carbon atoms
  • L represents a non-fluorinated organic divalent or multivalent linking group such as, for example, organic groups that comprise alkylene, carboxy, sulfonamido, carbonamido, oxy, alkyleneoxy, thio, alkylenethio, and/or arylene.
  • Y represents a functional group having a Zerewitinoff hydrogen such as, for example, hydroxy, amino, or thiol
  • x is an integer of 1 to 20, for example, between 2 and 10
  • y is 1 or 2.
  • R f4 is C 4 F 9 -, x is 1, and y is 1.
  • the condensation reaction to prepare the fluorinated compound of the fluorochemical composition can be carried out under conventional conditions well-known to those skilled in the art. Preferably the reaction is run in the presence of a catalyst and typically, the reaction will be carried out such that all isocyanate groups have been reacted and the obtained reaction product is free of isocyanate groups.
  • 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.
  • the condensation reaction is preferably carried out under dry conditions in a common organic solvent that does not contain Zerewitinoff hydrogens such as ethyl acetate, acetone, methyl isobutyl ketone, toluene, and fluorinated solvents such hydrofluoroethers and trifluorotoluene.
  • Suitable reaction temperatures will be easily determined by those skilled in the art based on the particular reagents, solvents, and catalysts being used. While it is not practical to enumerate particular temperatures suitable for all situations, generally suitable temperatures are between about room temperature and about 120 0 C.
  • Fluorochemical urethanes of the invention are prepared from aliphatic polyisocyanate, wherein less than about 15%, preferably from about 2 to about 8%, of the isocyanate groups are reacted with perfluorinated polyether alcohol, less than about 15%, preferably from 0 to about 10%, of the isocyanate groups are reacted with isocyanate blocking group, more than about 5%, preferably from about 10 to about 40%, of the isocyanate groups are reacted with polyoxyalkylene diol, and more than about 35%, preferably from about 50 to about 75%, of the isocyanate groups are reacted with short- chain perfluoroalkyl alcohol.
  • the fluorochemical composition may contain additionally a non-fluorinated organic compound, wherein the non-fluorinated organic compound is capable of improving relative to the fluorochemical composition without the non-fluorinated organic compound, the oil repellency or water repellency that can be achieved by the fluorochemical composition on a fibrous substrate or the durability of one or both of the repellency properties.
  • a non-fluorinated organic compound is sometimes called extenders.
  • Suitable extenders for use in the fluorochemical composition include non-fluorinated organic compounds that have one or more blocked isocyanate groups, so called blocked isocyanate compounds, or a carbodiimide compound.
  • Preferred blocked isocyanate extenders are blocked polyisocyanates that at a temperature of less than about 150 0 C are capable of reacting with an isocyanate reactive group, preferably through deblocking of the blocking agent at elevated temperature.
  • Preferred blocking agents include arylalcohols such as phenols; lactams such as ⁇ -caprolactam, ⁇ - valerolactam, ⁇ -butyro lactam; oximes such as formaldoxime, acetaldoxime, methyl ethyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, 2- butanone oxime, or diethyl glyoxime.
  • Further suitable blocking agents include bisulfite and triazoles.
  • the blocked polyisocyanate may comprise the condensation product of a polyisocyanate, for example, a di- or triisocyanate, and a blocking agent.
  • the carbodiimide compound can be an aromatic or aliphatic carbodiimide compound and may include a polycarbodiimide.
  • Carbodiimides that can be used have been described in, for example, U.S. Patent Nos. 4,668,726, 4,215,205, 4,024,178, and 3,896,251, WO 93/22282, U.S. Patent Nos. 5,132,028, 5,817,249, 4,977,219, 4,587,301, 4,487,964, 3,755,242, and 3,450,562.
  • Particularly suitable carbodiimides for use in this invention include those corresponding to the formula (VII):
  • the aliphatic carbodiimide extenders of formula VII can be synthesized in a 1-step process by reacting aliphatic diisocyanates with an aliphatic mono-isocyanate as a chain terminator at about 130 to about 170°C in the presence of a phospholine oxide or other suitable carbodiimide formation catalyst.
  • the reaction is carried out in the absence of solvents under inert atmosphere, but high-boiling non-reactive solvents such as methyl isobutyl ketone can be added as diluents.
  • the mole ratio of diisocyanate to mono- isocyanate can be varied from about 0.5 to 10, preferably about 1 to 5.
  • Examples of aliphatic diisocyanates for the preparation of the carbodiimide compounds of formula (VII) include isophorone diisocyanate, dimer diacid diisocyanate, 4,4' dicyclohexyl methane diisocyanate.
  • Examples of mono-isocyanates are n. butyl isocyanate and octadecyl isocyanate.
  • suitable carbodiimide formation catalysts are described in, e.g., U.S. Patent Nos. 2,941,988, 3,862,989, and 3,896,251.
  • Examples include l-ethyl-3-phospholine, l-ethyl-3-methyl-3 -phospholine- 1- oxide, 3-methyl-l-phenyl-3-phospholine-l -oxide, and bicyclic terpene alkyl or hydrocarbyl aryl phosphine oxide.
  • the particular amount of catalyst used depends on the reactivity of the catalyst and the isocyanates being used. A concentration of about 0.2 to about 5 parts of catalyst per 100 g of diisocyanate is suitable.
  • the aliphatic diisocyanates can be first reacted with monofunctional alcohols, amines, or thiols followed by carbodiimide formation in a second step.
  • the fluorochemical urethane is preferably delivered in combination with blocked isocyanate extender.
  • the fluorochemical urethane and blocked isocyanate extender may be synthesized separately or, preferably, in the same reactor and may be applied to the textile yarns from organic solvent or, preferably, as aqueous emulsion.
  • the fluorochemical urethane and blocked isocyanate extender may be emulsified separately and then blended or, preferably, their organic solutions may be combined and co-emulsified.
  • the fluorinated compound of the fluorochemical composition typically will have a molecular weight such that it is readily dissolved or dispersed in water or an organic solvent. Generally, the molecular weight of the fluorinated compound is not more than 100,000 g/mol, with a typical range being between 1500 g/mol and 60,000 g/mol. When a mixture of fluorinated compounds is used, the aforementioned molecular weights represent weight average molecular weights.
  • the fluorochemical composition comprises a dispersion or solution of the fluorinated compound in water or an organic solvent.
  • the term "dispersion” refers to both solid-in-liquid dispersions as well as liquid-in-liquid dispersions which are also called emulsions.
  • the fluorochemical compositions will be diluted before treating fibrous substrates such that the amount of fluorinated compound contained in the treating composition is from about 0.01 to about 7% by weight, preferably from about 0.05 to about 3% by weight based on the total weight of the fluorochemical composition. Higher amounts of fluorinated compound, for example up to about 10% by weight may be used as well, particularly if the uptake of the fluorochemical composition by the substrate is low.
  • the fluorochemical treating composition will be prepared by diluting a more concentrated fluorochemical composition to the desired level of fluorinated compound in the treating composition.
  • the concentrated fluorochemical composition can contain the fluorinated compound in an amount of up to about 70% by weight, typically from about 10% by weight to about 50% by weight.
  • the weight average particle size of the fluorinated compound particles is preferably not more than about 400 nm, more preferably is not more than about 300 nm.
  • the fluorochemical composition is an aqueous dispersion of the fluorinated compound.
  • Such dispersion may be non-ionic, anionic, cationic, or zwitterionic.
  • the dispersion is preferably stabilised using non-fluorinated surfactants, such as non-ionic polyoxyalkylene, in particular polyoxyethylene surfactants, anionic non- fluorinated surfactants, cationic non-fluorinated surfactants, and zwitterionic non- fluorinated surfactants.
  • non-fluorinated surfactants that can be used are nonionic types such as EMULSOGENTM EPN 207 (Clariant) and TWEENTM 80 (ICI), anionic types such as lauryl sulfate and sodium dodecyl benzene sulfonate, cationic types such as ARQU ADTM 12-50 (Akzo), ETHOQU ADTM 18-25 (Akzo) or amphoteric types such as lauryl amineoxide and cocamido propyl betaine.
  • the non-fluorinated surfactant is preferably present in an amount of about 1 to about 25 parts by weight, preferably about 1 to about 50 parts by weight, based on 100 parts by weight of the fluorochemical composition.
  • a solution or dispersion of the fluorinated compound in an organic solvent can be used as the fluorochemical treating composition.
  • Suitable organic solvents include alcohols such as isopropanol, methoxy propanol, and t.butanol, ketones such as isobutyl methyl ketone and methyl ethylketone, ethers such as isopropyl ether, esters such ethylacetate, butylacetate or methoxypropanol acetate, or (partially) fluorinated solvents such as HCFC-HIb, HFC-4310mee and hydro fluoro ethers such as HFE-7100 or HFE- 7200 available from 3M Company.
  • the fluorochemical composition may contain further additives such as buffering agent, agents to impart fire proofing or antistatic properties, fungicidal agents, optical bleaching agents, sequestering agents, mineral salts, and swelling agents to promote penetration.
  • the fluorochemical composition will be free of or substantially free of perfluorinated polyether moieties having a number average molecular weight of less than 750 g/mol and/or perfluoroaliphatic groups of more than 5 or 6 carbons.
  • perfluoroaliphatic groups is meant groups consisting of carbon and fluorine without including perfluorinated end groups of the perfluorinated polyether moieties.
  • the particular perfluorinated polyether moieties are present in amounts of not more than about 10% by weight, preferably not more than about 5% by weight, and most preferably not more than about 1% by weight based on the total weight of perfluorinated polyether moieties in the composition and that the particular perfluoroaliphatic groups having more than 5 or 6 carbons are present in amounts of not more than about 10% by weight, preferably not more than about 5% by weight, and most preferably not more than about 1 % by weight based on the total weight of perfluoroaliphatic groups in the composition.
  • Compositions that are free of or substantially free of these moieties or groups are preferred because of their beneficial environmental properties.
  • the fibrous substrate is contacted with the fluorochemical composition of the invention.
  • the substrate can be immersed in the fluorochemical treating composition.
  • the treated substrate can then be run through a padder/roller to remove excess fluorochemical composition and dried.
  • the treated substrate may be dried at room temperature by leaving it in air or, preferably, be subjected to a heat treatment, for example, in an oven.
  • This heat treatment is typically carried out at temperatures from about 50 0 C to about 19O 0 C depending on the particular system or application method used. In general, a temperature of about 120 0 C to about 170 0 C, in particular of about 150 0 C to about 170 0 C for a period of about 20 seconds to 20 minutes minutes, is suitable.
  • the chemical composition can be applied by spraying the composition on the fibrous substrate.
  • the amount of the treating composition applied to the fibrous substrate is chosen so that a sufficiently high level of the desired properties are imparted to the substrate surface preferably without substantially affecting the look and feel of the treated substrate. Such amount is usually such that the resulting amount of the fluoropolymer on the treated fibrous substrate will be from about 0.05% to about 3% by weight, preferably from about
  • the treatment is carried out with a composition and under conditions such that the total amount of perfluorinated polyether groups having a number average molecular weight of less than 750 g/mol and/or perfluoroaliphatic groups of more than 6 carbon atoms is not more than about 0.1%, preferably not more than about 0.05% by weight based on the weight of the fibrous substrate.
  • Fibrous substrates that can be treated with the fluorochemical composition include in particular textile and carpet.
  • the fibrous substrate may be based on synthetic fibers, e.g., polyester, polyamide and polyacrylate fibers or natural fibers, e.g., cellulose fibers as well as mixtures thereof.
  • the fibrous substrate may be a woven as well as a non-woven substrate.
  • the water repellency (WR) of a substrate was measured using a series of water/isopropyl alcohol test liquids and was expressed in terms of the WR rating of the treated substrate.
  • the WR rating corresponded to the most penetrating test liquid that did not penetrate or wet the substrate surface after 10 seconds exposure, according to the WR rating scale and the test liquid compositions summarized in the table below. Substrates which were penetrated by a 2%/98% isopropyl alcohol/water blend, the least penetrating test liquid, were given a rating of 0, a treated substrate resistant to a 30%/70% isopropyl alcohol/water blend, but not to an 40%/60% blend, would be given a rating of 5, and so on.
  • the oil repellency of a substrate was measured by the American Association of Textile Chemists and Colorists (AATCC) Standard Test Method No. 1 18-2002, which test was based on the resistance of a treated substrate to penetration by oils of varying surface tensions. Treated substrates resistant only to NUJOLTM mineral oil (the least penetrating of the test oils) were given a rating of 1, whereas treated substrates resistant to n-decane (the most penetrating of the test liquids) were given a rating of 6. Other intermediate values were determined by use of other pure oils or mixtures of oils, as shown in the following table. Standard Oil Repellency Test Liquids
  • 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 (SEARS KENMORETM Model No.
  • ballast sample 1.9 kg of 8 oz wash-load ballast fabric, from Textile Innovators/SDL Atlas, Windsor, NC, in the form of generally square, hemmed 8100 cm 2 sheets.
  • a commercial detergent 75 g of TIDETM Ultra Liquid deep cleaning formula, from Proctor and Gamble, Cincinnati, OH was added and the washer was filled to high water level with hot water (41 0 C ⁇ 2°C). The substrate and ballast load were washed 5 times using a 12-minute normal wash cycle.
  • the substrate and ballast were dried together in a conventional tumble drier at 65 ⁇ 5°C during 45 ⁇ 5 minutes. Before testing, the substrates were conditioned at room temperature during about 4 hours. "20 Launderings” or “30 Launderings” indicated that the substrate was washed for
  • Textile Substrate 1 Tan 100% cotton woven fabric, BRITISH KHAKI SUPER HIP, from Avondale Mills, Graniteville SC;
  • Textile Substrate 2 Olive polyester/cotton (65/35) woven fabric, EQUESTRIAN TWILL, from Avondale Mills, Graniteville SC; and • Textile Substrate 3: White 100% cotton jersey knit fabric, from Fruit of the Loom, Bowling Green, KY.
  • CF 3 CF 2 CF 2 O(CF(CF 3 )CF 2 O) n CF(CF 3 )CONHCH 2 CH 2 OH consisting of a mixture of oligomers with different chain lengths.
  • the (HFPO) 7 7 -alc was prepared essentially according to the same procedure as that for CF 3 CF 2 CF 2 O(CF(CF 3 )CF 2 O) 6 8 CF(CF 3 )CONHCH 2 CH 2 OH, or (HFPO) 8 8 -alc, as described in U.S. Patent Publication No. 2004/0077238, paragraph [0140] through paragraph [0145].
  • a l liter 3-necked reaction flask was equipped with a stirrer, a condenser, a dropping funnel, a heating mantle and a thermometer.
  • the flask was charged with 1000 g CF 3 CF 2 CF 2 O(CF(CF 3 )CF 2 O) 6 ⁇ CF(CF 3 )COOCH 3 .
  • the mixture was heated to 4O 0 C. and 43.4 g ethanolamine was added via the dropping funnel, over a period of 30 minutes.
  • the reaction mixture was kept at 65 0 C. during 3 hours. FTIR analysis indicated complete conversion.
  • the end product could be purified as follows: 500 ml ethylacetate were added and the organic solution was washed with 200 ml HCL (IN), followed by 2 washings with 200 ml brine. The organic phase was dried over MgSO 4 . Ethylacetate was evaporated with waterjet vacuum, using a Buchi rotary evaporator. The product was dried at 5O 0 C. during 5 hours, using oil pump vacuum ( ⁇ 1 mbar).
  • HFPO-oligomer alcohol (HFPO) 8 8 -alc obtained, was a yellow coloured oil, with medium viscosity. The structure was confirmed by means of NMR. HFPO-oligomer alcohols with other chain lengths were prepared essentially according to the same procedure.
  • MeFBSE N-2-hydroxyethyl-N-methylperfluorobutylsulfonamide, C 4 F 9 SO 2 N(CH 3 )CH 2 CH 2 OH, was prepared according to PCT Publication Number WO 01/30873, Example 2 Part A.
  • HFPO HFPO oligomer alcohol
  • MeFBSE 77.84 grams, 218.03 mmole
  • ARCOLTM POLYOL PPG-1025 62.26 grams, 124.77 meq hydroxyl
  • CARBOW AXTM MPEG-750 20.80 grams, 27.73 meq hydroxyl
  • DESMODURTM N3300 (77.87 grams, 401.42 meq isocyanate), ethyl acetate (EA, 30 grams), and dibutyltin dilaurate (DBDTL, 0.06 grams) were added sequentially, and then heated for 6 hours at 75 0 C.
  • FC Urethane Mixture A solids comprised 80 weight percent aliphatic fluorochemical urethane and 20 weight percent blocked aromatic isocyanate extender. Of the aliphatic isocyanates of FC Urethane Mixture A's fluorochemical urethane, 2.9% were reacted perfluorinated polyether alcohol, 4.8% with MEKO, 31.1% with polyoxyalkylene diol, 54.3% with short-chain perfluoroalkyl alcohol, and 6.9% with polyethylene glycol monomethyl ether. FC Urethane Mixture A contained 14.8% fluorine versus urethane solids and the fluorochemical urethane portion contained 18.5% fluorine versus urethane solids. Preparation of Fluorochemical Emulsion A
  • Three textile treatment baths were prepared by sequentially adding deionized water, WETAIDTM NRW wetting agent (0.50 grams) and Fluorochemical Emulsion A in the amounts shown below in Table 1.
  • Textile Substrate 1 (tan 100% cotton woven) and Textile Substrate 2 (olive 65/35 polyester/cotton woven) were dipped in the padding baths and then squeezed between rubber rollers to wring out the excess.
  • the damp swatches were dried for ten minutes 100°C and then cured for two minutes at 160°C.
  • the calculated grams solids of FC Urethane Mixture A per 100 grams fabric (solids on fabric or SOF) are indicated below in Table 1.
  • Example 2 The treated woven fabric substrates (Examples 1 to 6 in Table 2) were then tested for initial oil repellency, initial water repellency and initial stain release, and also tested after 20 and 30 launderings as described in the above test methods. The results are summarized in Table 2.
  • Textile Treatment Bath 4 was prepared by sequentially combining deionized water (141.89 grams), WETAIDTM NRW wetting agent (0.30 grams), and FIuorochemicaI Emulsion A (7.81 grams).
  • Textile Substrate 3 (white 100% cotton jersey knit) was dipped in the padding bath and then squeezed between rubber rollers to wring out the excess. The damp swatch was dried for ten minutes 100°C and then cured for two minutes at 160 0 C. The calculated SOF was 1.33.
  • the treated knit fabric substrate (Example 7 in Table 2) was then tested for initial oil repellency, initial water repellency, and initial stain release, and also tested after 5 and 20 launderings as described in the above test methods. The results are summarized in Table 3.
  • FC Urethane Mixtures B to J were prepared according to the procedure described above for FC Urethane Mixture A.
  • the compositions are summarized in Table 4.
  • Weight percent aliphatic fluorochemical urethane, weight percent blocked aromatic isocyanate extender, equivalent percent aliphatic isocyanate reactant, and weight percent fluorine versus FC Urethane Mixture solids, and weight percent fluorine versus aliphatic Fluorochemical Urethane solids are summarized in Table 5.
  • FC Urethane Mixtures K to U were prepared according to the procedure described above for FC Urethane Mixture A except substituting different molecular weight polypropylene oxide-based diol materials for PPG- 1025 (PPG-425, -725, and -2025), or excluding perfluorinated polyether (FC Urethane Mixture U).
  • the compositions are summarized in Table 6.
  • Weight percent aliphatic fluorochemical urethane, weight percent blocked aromatic isocyanate extender, equivalent percent aliphatic isocyanate reactant, and weight percent fluorine versus FC Urethane Mixture solids, and weight percent fluorine versus aliphatic Fluorochemical Urethane solids are summarized in Table 7.
  • FC Urethane Mixtures C-A to C-D were prepared according to the procedure described above for FC Urethane Mixture A, optionally substituting PPG-2025 molecular weight PPG for PPG-1025.
  • the compositions are summarized in Table 8.
  • Aliphatic fluorochemical urethane weight percent, blocked aromatic isocyanate extender weight percent, equivalent percent aliphatic isocyanate reactant, and weight percent fluorine versus FC Urethane Mixture solids, and weight percent fluorine versus aliphatic FC Fluorochemical Urethane solids are summarized in Table 9.
  • Emulsions C-A to C-D Fluorochemical Emulsions B-U and Comparative Fluorochemical Emulsions C-A to C-D were prepared according to the Preparation of Fluorochemical Emulsion A procedure described above, except using Fluorochemical Emulsions B-U or Comparative Fluorochemical Emulsions C-A to C-D, respectively.
  • Textile Treatment Baths 5 to 20 and C-I to C-3 were prepared and applied to Textile Substrate 3 (white 100% cotton jersey knit) as described for Textile Treatment Bath 4, except using mixtures of Fluorochemical Emulsion B to U or Comparative Fluorochemical Emulsions C-A to C-D, as indicated in Table 10.
  • Applied SOF and weight percent fluorine versus urethane blend solids are also indicated in Table 10.
  • the treated knit fabric substrates (Examples 8 to 23 and Comparative Examples Cl to C3 in Table 1 1) were then tested for initial oil repellency, initial water repellency, and initial stain release, and also tested after 5 and 20 launderings as described in the above test methods. The results are summarized in Table 1 1.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne une composition fluorochimique permettant de rendre des substrat fibreux oléophobes, hydrophobes et/ou résistants aux taches et/ou aux salissures. La composition comprend une dispersion ou une solution d'un composé fluoré qui renferme le produit de réaction de : (1) un ou plusieurs polyéthers fluorés représentés par la formule: RfQTk (I), dans laquelle Rf représente un groupe polyéther perfluoré monovalent présentant une masse moléculaire moyenne en nombre d'au moins 750g/mol, Q représente une liaison chimique ou un groupe de liaison organique divalent ou trivalent, T représente un groupe fonctionnel pouvant réagir avec un isocyanate, et k égale 1 ou 2; (2) un ou plusieurs diols de polyoxyalkylène; (3) un ou plusieurs alcools perfluoroalkylés à chaîne courte; (4) un ou plusieurs composants d'isocyanate sélectionné(s) à partir d'un composé de polyisocyanate comportant au moins 3 groupes isocyanate ou d'un mélange de composés de polyisocyanate, le nombre moyen de groupes isocyanate par molécule étant supérieur à 2; (5) éventuellement un ou plusieurs groupes formant des séquences d'isocyanate; et (6) éventuellement un ou plusieurs coréactifs pouvant réagir avec un groupe isocyanate. L'invention concerne aussi un procédé d'application d'une telle composition sur des substrats, p. ex. des substrats fibreux.
PCT/US2007/084059 2006-11-22 2007-11-08 Composition fluorochimique destinée au traitement d'un substrat fibreux Ceased WO2008063903A1 (fr)

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