Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F14/18—Monomers containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment 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
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/395—Isocyanates
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/402—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
• • 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
  • D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
  • D06M15/353—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes 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
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
  • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
• • 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
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
  • D06M15/3566—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing sulfur
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
  • D06M15/568—Reaction products of isocyanates with polyethers
• • 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 the use of organofunctional perfluorinated polymers and/or fluorinated ionomers as surfactant emulsifiers in emulsion polymerization of fluorinated monomers.
• Emulsion polymerization of fluorinated and perfluorinated monomers are typically carried out in the presence of fluorinated surfactants such as ammonium perfluorooctanoate and other salts of fluorotelomer or sulfonamido acids.
• fluorinated surfactants such as ammonium perfluorooctanoate and other salts of fluorotelomer or sulfonamido acids.
• These low molecular weight surfactants persist in the environment and may also tend to bio-eliminate from the body undesirably slowly. As a result, use of these materials is considered by some to be undesirable.
• compositions for making substrates, in particular fibrous substrates, such as textile, oil- and water repellent have been long known in the art.
• fibrous substrates and in particular textile such as apparel
• the composition used for treating the substrates need to be effective at low application levels.
• Fluorochemical compounds have been well known as being highly effective in providing oil and water repellency to substrates and in particular textile substrates.
• the commercially available fluorochemical compositions can be applied at low levels and are generally effective in providing the desired oil and water repellency properties at these low levels.
• Commercially available fluorochemical compositions however have the disadvantage of being based on low molecular weight fluorochemical products or, if based on polymeric products, will generally contain residual low molecular weight fluorochemical compounds that may be present as contaminants from the manufacturing process and/or that may be formed over time from partial decomposition of compounds in the composition. From an environmental aspect, it would be desirable to eliminate such low molecular weight fluorochemical products from the fluorochemical treatment composition.
• Fluorochemicals taught for treating textile include polymers based on vinyl ethers that have a perfluoroalkyl group.
• the aforementioned fluorochemical compositions are all based on fluorine containing polymers that do not have a fluorinated backbone.
• Fluoropolymers having a fluorinated backbone such as for example polytetrafluoroethylene (PTFE) and copolymers of tetrafluoroethylene (TFE), have been known for coating substrates to provide various properties to the substrate including repellency properties. Fluoropolymers have for example been coated on cookware to provide desired release properties thereto. Fluoropolymers having a fluorinated backbone are disclosed in US 4,546,157, US 4,619,983, US 4,766,190, US 5,110,385, US 5,969,066, US 3,450,684, US 4,035,565, US 4,368,308, US 4,418,186, US 4,654,394, US 4,840,998, US 5,639,838 and US 3,136,745.
• PTFE polytetrafluoroethylene
• TFE tetrafluoroethylene
• EP 969 055 discloses an aqueous dispersion containing PTFE and a copolymer of TFE and a perfluorovinyl ether (PNE) for coating substrates such as ceramics or to impregnate textile.
• PNE perfluorovinyl ether
• the amount of fluoropolymer in the treatment solution is at least 25% by weight resulting in a fairly thick coating.
• the coating is subjected to a sintering step at a temperature of 420°C which would destroy many fibrous materials used for apparel.
• US 4,670,328 discloses aqueous dispersions of certain copolymers of TFE and PNE for the impregnation of textiles. Again, the level of fluoropolymer applied in the impregnation is so large that the look and feel of the textile is substantially affected.
• impregnated materials are generally only useful in specialized applications such as dust free clothes or chemical resistant clothes where the appearance of the clothes is of secondary consideration.
• EP 186186 discloses a curable fluoroolefm polymer for making coatings that have high weatherability and good repellency properties such as water repellency, oil repellency and/or stain repellency. However, a thick coating is apparently required to achieve these properties.
• fluorochemical compositions that do not display many of the disadvantages of the fluorochemical compositions in the prior art.
• fluorochemical compositions that are effective in providing oil and water repellency to a fibrous substrate, in particular a textile substrate, without substantially adversely affecting the appearance of the textile, i.e. such that the fibrous substrate is suitable for use in apparel.
• the fluorochemical compositions are also capable of providing soil repellency and soil release properties to the fibrous substrate.
• the fluorochemical compositions will be more environmental friendly and are substantially free of low molecular weight fluorinated substances.
• the fluorochemical compositions are preferably sufficiently stable to substantially avoid formation of low molecular weight fluorinated substances.
• the fluorochemical compositions are preferably also compatible with commonly used textile treatments and are preferably easy to apply by a customer in a reproducible and reliable way.
• the desired fluorochemical compositions are preferably capable of providing durable repellency properties to a fibrous substrate.
• the present invention provides a method for emulsion polymerizing monomers, e.g., fluorinated monomers, using a fluorinated surfactant having a molecular weight of at least 1000 g/mol.
• the present invention provides a fluorochemical composition for rendering a fibrous substrate oil and/or water repellent.
• the fluorochemical composition comprises a solution or dispersion of a fluoropolymer having a partially or fully fluorinated backbone and comprising one or more repeating units corresponding to the general formula: -CF 2 -CF-
• R f represents a perfluorinated organic group having a chain length of at least 2 atoms and having at least one carbon atom.
• the amount of the fluoropolymer will typically be selected in order to achieve the desired level of fluoropolymer on the substrate to be treated.
• the amount of the fluoropolymer in the fluorochemical composition is not more than 4% by weight (based on the total weight of the composition), for example between 0.01% by weight and 4% by weight, preferably between 0.05% and
• the fluorochemical composition of the present invention has been found to be effective for providing oil repellency and/or water repellency properties to a fibrous substrate without substantially affecting the appearance thereof. Furthermore, the fluorochemical composition can be produced such that the amount of low molecular weight (less than lOOOg/mol) in the composition is low, e.g. not more than 0.5% by weight, preferably not more than lOOOppm, or is even free of such substances. Also, the compositions generally will have a high chemical stability such that the compositions generally do not form low molecular weight fluorinated substances over a long period of time. The fluorochemical composition may further provide soil repellency as well as soil or stain release properties.
• soil and stain release is meant 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 refers to the ability to repel soil thereby reducing soiling or staining of the substrate.
• the present invention relates to a treatment of fibrous substrates with the above fluorochemical compositions.
• the substrates so obtained generally have good repellency properties such as oil repellency, water repellency, soil repellency.
• treated substrates may exhibit good or improved soil/stain release properties as well.
• fibrous substrates in particular textiles that have on at least part of at least one major surface, the fluoropolymer of the fluorochemical composition.
• the amount of the fluoropolymer on such a treated fibrous substrate should generally be less than 3% by weight based on the weight of the fibrous substrate so as to preserve the general look and feel of the substrate although the amount that can be applied without adversely affecting the look and feel of the substrate will depend on the nature of both the substrate as well as the fluorochemical composition used in the treatment.
• the invention relates to the use of a fluorochemical composition to impart oil repellency, water repellency, soil repellency and/or soil/stain release to a fibrous substrate without substantially affecting the look and feel of said fibrous substrate, the fluorochemical composition comprising a solution or dispersion of a fluoropolymer having a partially or fully fluorinated backbone and comprising one or more repeating units corresponding to the general formula: -CF 2 -CF-
• R f represents a perfluorinated organic group having a chain length of at least 2 atoms and having at least one carbon atom.
• the treated substrate does not differ substantially in appearance from the untreated substrate such that the treated substrate can be used without objection in applications such as for example apparel, where the look and feel of the fibrous substrate are a major consideration for its use.
• the invention relates to a fluoropolymer mixture that comprises a first and a second fluoropolymer each having a partially or fully fluorinated backbone.
• the first fluoropolymer comprises one or more repeating units corresponding to the general formula:
• R f represents a perfluorinated organic group having a chain length of at least 2 atoms and having at least one carbon atom.
• the one or more repeating units according to the general formula (I) are present in said first fluoropolymer in an amount of at least 20 mole %.
• the second fluoropolymer is free of repeating units according to general formula (I) or contains them in a total amount of not more than 18 mole %.
• Such fluoropolymer mixture has been found to be particularly effective for the treatment of fibrous substrates.
• the second fluoropolymer contributed to an improvement of the repellency properties often going beyond a mere addition of the oil repellency properties of the fluoropolymers on their own. Accordingly, the cost of a fluorochemical treatment composition may thereby be lowered as the cost of the first fluoropolymer is generally higher than that of the second fluoropolymer.
• the invention relates to fluorochemical compositions that comprise a solution or dispersion of the aforementioned fluoropolymer and further an auxiliary component, generally a non-fluorinated organic compound, that is capable of further improving the water and/or oil repellency and/or the soil/stain release properties of a fibrous substrate treated with the fluorochemical composition.
• auxiliary component generally a non-fluorinated organic compound
• Fluoropolymers for use in the fluorochemical composition are Fluoropolymers for use in the fluorochemical composition
• the fluoropolymers for use in the fluorochemical composition are polymers that have a partially or fully fluorinated backbone, in particular a partially or fully fluorinated carbon backbone.
• the fluoropolymers of this invention will have a backbone that essentially consists of a carbon backbone.
• the term "fully fluorinated” includes polymers in which all hydrogen atoms on the backbone have been replaced by fluorine as well as polymers in which all hydrogen atoms on the backbone have been replaced with fluorine and chlorine or bromine.
• the fluoropolymer has a partially fluorinated backbone, it will generally have a level of fluorination of at least 10% by weight, preferably at least 20% by weight, more preferably at least 30% by weight and most preferably at least 50% by weight.
• the fluoropolymer has one or more repeating units that correspond to the general formula: -CF 2 -CF-
• R f represents a perfluorinated (i.e. all hydrogen atoms have been replaced by fluorine atoms) organic group having a chain length of at least 2 atoms and including at least one carbon atom.
• the chain length of the perfluorinated organic group is at least 3 atoms.
• a particularly preferred R f group has a chain length of at least 4 atoms of which at least 3 are carbon atoms.
• R f groups include perfluorinated aliphatic groups that may optionally contain one or more oxygen atoms.
• the R f group may in particular be a linear or branched perfluoralkoxy group, preferably, the perfluoroalkoxy group will have between 1 and 6 carbon atoms and specific examples include methoxy, ethoxy and n-propoxy groups.
• the R f group may further be a linear or branched perfluoroalkyl group having between 2 and 8 carbon atoms including for example perfluoroethyl, perfluoropropyl and perfluorohexyl.
• the R f group can be a perfluoropolyether which may be linear or branched. According to a preferred embodiment, the R f group corresponds to the following general formula:
• R 1 ⁇ R 2 f each independently represents a linear or branched perfluoroalkylene group having 1, 2, 3, 4, 5 or 6 carbon atoms
• R 3 f represents a linear, branched or cyclic perfluoroalkyl group having 1,2,3,4, 5 or 6 carbon atoms
• n and m each independently represents an integer of 0 to 10.
• at least one of n and m is different from 0.
• R f groups according to formula (II) include those in which m is 0, n is 1, R' f is -CF 2 CF 2 -, -CF 2 CF(CF 3 )- or -CF 2 CF 2 CF 2 - and R 3 f represents a linear, branched or cyclic perfluoroalkyl group having 1,2,3,4, 5 or 6 carbon atoms, in particular a perfluoromethyl group and those in which both m and n are 0.
• the fluoropolymer of the fluorochemical composition may comprise a mixture of repeating units according to formula (I).
• the fluoropolymer may comprise a mixture of repeating units in which the R f groups correspond to formula (II) above such as for example a mixture of a repeating unit corresponding the formula: -CF 2 -CF-
• the repellency properties that can be achieved by the fluorochemical composition largely depend on the presence in the fluoropolymer of the repeating units according to formula (I).
• the amount required of such repeating units however generally depends on the particular nature and structure of the repeating units according to formula (I).
• a level of at least 1 mole% of repeating units according to formula (I) may be necessary to achieve desirable oil and/or water repellency with the fluorochemical compositions.
• the repellency properties are generally improved by increasing the amount of repeating units of formula (I) and preferably the amount of repeating units of formula (I) is at least 5 mole%, more preferably at least 10 mole%, most preferably at least 15 mole%.
• Typical amounts of the repeating unit are in the range of 10 mole % to 80 mole%, for example between 30 mole% and 50 mole%.
• a fluoropolymer containing only repeating units according to general formula (I) may be used as well and has been found to yield excellent repellency properties on a fibrous substrate treated therewith. Although higher amounts of the repeating units of formula (I) will generally improve performance, the cost of the fluoropolymer thereby also increases as well because the monomers from which these repeating units are derived are generally expensive.
• the fluorochemical composition comprises a fluoropolymer mixture comprising a first and second fluoropolymer each having a partially or fully fluorinated backbone.
• the first fluoropolymer comprises one or more repeating units corresponding to the general formula (I) set forth above. These one or more repeating units according to the general formula (I) are present in the first fluoropolymer in an amount of at least 20 mole %.
• the second fluoropolymer contains the repeating units of formula (I) in a total amount of not more than 18 mole %. The amount of repeating units in the second fluoropolymer may even be less, for example not more than 10 mole % or not more than 5 mole %.
• the second fluoropolymer generally does not (e.g. if it does not contain the repeating units of formula (I)) or only to a limited extent provides repellency properties when used on its own, the second fluoropolymer is nevertheless capable of improving the repellency performance when used in an admixture with the first fluoropolymer.
• the fluoropolymer may contain a mixture of more than two fluoropolymers, i.e. further fluoropolymers differing in content of repeating units maybe comprised in the mixture.
• any ratio of second to first fluoropolymer can be used in the mixture and the optimal ratio will depend on the nature of the fluoropolymers used in the mixture, the nature of the fibrous substrate, amount of the mixture applied and level of repellency desired. The optimal ratio can easily be determined through routine experimentation.
• the weight ratio of second to first fluoropolymer will be between 9:1 and 1 :9, preferably between 8 :2 and 1:1.
• mixtures that are rich (have a weight ratio of second to first fluoropolymer of 1 or more) in the second fluoropolymer, which contains no or little of the repeating units of formula (I) have been found to yield good repellency properties.
• the total amount of repeating units according to the general formula (I) in such mixtures should be at least 1 mole %, preferably at least 5 mole
• the fluoropolymer mixture may be prepared by admixing a first and second fluoropolymer together in the desired ratios or can alternatively be prepared by allowing or providing for a composition drift during the polymerization of the fluorinated monomers. In the latter case, two or more fractions of fluoropolymer differing in their content of the repeating units according to formula (I) can be prepared. Fractions having a low content of repeating units according to formula (I) will generally be soluble in acetone whereas those rich in repeating units are generally insoluble in acetone.
• the fluorochemical composition comprises a copolymer of at least one fluorinated monomer, in particular fluorinated olefinic monomer, selected from the group consisting of tetrafluoroethylene, vinylidene fluoride and trichloroethylene and a monomer corresponding to formula (III) above.
• the fluoropolymer will contain between 0 and 70 mole %, preferably between 0 and 60 mole %, more preferably between 0 and 40 mole % of repeating units derived from tetrafluoroethylene, between 0 and 95 mole %, preferably between 20 and 80 mole %, more preferably between 30 and 75 mole % of repeating units derived from vinylidene fluoride whereby the total amount of repeating units derived from vinylidene fluoride and tetrafluoroethylene is generally between 0 and 95 mole %, preferably between 20 and 90 mole %, more preferably between 30 and 90 mole %.
• the fluoropolymer of the fluorochemical composition may contain further repeating units derived from other fluorinated monomers and/or from non-fluorinated monomers.
• Examples of further fluorinated monomers include hexafluoropropylene and examples of non-fluorinated monomers include ethylene and propylene.
• the amount of such further repeating units may vary widely and can be from 0 mole % to 80 mole % . Preferably, the amount thereof is, when present, between 1 mole % and 50 mole %, more preferably between 5 mole % and 20 mole %.
• the fluoropolymer may also be derived from monomers of formula (III) above and one or more non-fluorinated monomers such as ethylene and/or propylene.
• Fluoropolymers as described above can be produced using emulsion polymerization reactions as are known, e.g., aqueous emulsion polymerization as disclosed in, e.g., US
• the fluoropolymer is produced through aqueous emulsion polymerization.
• the monomers are polymerized in the aqueous phase generally in the presence of a free radical initiator and a fluorinated surfactant or emulsifier, preferably a non-telogenic emulsifier.
• the emulsifier will generally be used in amounts less than 1% by weight, for example from 0.1 to 1% by weight based on the weight of the aqueous phase.
• fluorinated emulsifiers include salts, in particular ammonium salts of linear or branched perfluoro alkyl containing carboxylic and sulphonic acids having 4 to 11 carbon atoms in the alkyl chain. It was found that salts of branched perfluoroalkyl containing carboxylic and sulphonic acids are more effective than their linear counter parts. Specific examples include perfluorooctanoic acid ammonium salt (APFO, described in US 2,567,011) C 8 F ⁇ 7 SO 3 Li which is commercially available from Bayer AG, C 4 F 9 SO 3 Li and C F 9 SO 3 K (described in US 2,732,398). A further example of a perfluoroalkyl containing carboxylic acid salt is C 8 F ⁇ 7 SO 2 N(C 2 H 5 )CH 2 COOK (described in US 2,809,990).
• APFO perfluorooctanoic acid ammonium salt
• Still further emulsifiers that can be used include perfluoropolyethercarboxylate emulsifiers such as disclosed in EP 219065.
• APFO is the preferred emulsifier as it can be more readily removed from the polymerization product at the end of polymerization.
• the emulsion polymerization may be conducted using a fluorinated surfactant having a molecular weight of at least about lOOOg/mol.
• fluorinated polymeric or high molecular weight surfactants include perfluoropolyethers having one or more hydrophilic groups, in particular ionic groups such as carboxylic acid groups or salts thereof.
• perfluoropolyether surfactants include those according to the following formulas (IN) or (N):
• k, p and q each represent a value of 0 to 15, typically 0 to 10 or 12 and the sum of k, p and q being such that the number average molecular weight is at least about lOOOg/mol
• R represents a perfluoroalkyl group of 2 to 4 carbon atoms
• M and Z each independently represent hydrogen or a cation , preferably a monovalent cation such as
• Q and Q each independently represents -CF 2 - or -
• fluorinated surfactants of formula (IN) include those corresponding to the formula:
• fluorinated surfactants are disclosed in EP 219065.
• Commercially available surfactants according to formula (IN) or (V) include FLUOROLI ⁇ KTM C available from Ausimont SpA, KRYTOXTM 157 FSL, KRYTOXTM 157 FSM and KRYTOXTM 157 FSH, all available from Dupont de Nemours and Company.
• fluorinated polymeric surfactants that can be used include the perfluoropolymers that comprise repeating units derivable from a monomer of the formula:
• G is a moiety containing one or more hydrophilic groups, such as a nonionic, anionic or cationic group.
• suitable nonionic groups include: -SO 2 F; hydroxyalkylene, e.g., -(CH 2 ) n OH where n is an integer of 1 to 18; hydroxyarylene; and an ester, e.g., -COOR, wherein R is an alkyl group of 1 to 3 carbon atoms.
• Suitable anionic groups include: carboxyl groups, e.g., -CO 2 M where M may be hydrogen, a mono or divalent metal ion (e.g., sodium, potassium or magnesium), ammonium (e.g., simple ammonium, tetraalkylammonium, tetaarylammonium) or phosphonium (e.g., tetraalkylphosphonium); or sulfonate groups, e.g., -SO 3 M, where M is defined as above.
• suitable cationic groups include alkylammonium groups, (e.g., -(CH 2 ) n ⁇ R 3 + CI " where R may be hydrogen, alkyl or aryl).
• the fluorinated polymeric surfactant is a copolymer of tetrafluoroethylene and a monomer according to formula (Nil).
• Suitable fluorinated polymeric surfactants are available as NationalTM superacid catalysts (e.g., NationalTM SE10172) from E. I duPont de Nemours & Co., Wilmington, DE and are also available as FlemionTM superacid polymers from Asahi Chemical Co., Osaka, Japan and as AcipexTM superacid polymers from Asahi Glass Co., Tokyo, Japan.
• the aqueous emulsion polymerization can be carried out continuously in which, for example, monomers, water, optionally further emulsifiers, buffers and catalysts are fed continuously to a stirred reactor under optimum pressure and temperature conditions while the resulting emulsion or suspension is removed continuously.
• An alternative technique is batch or semibatch (semi-continuous) polymerization by feeding the ingredients into a stirred reactor and allowing them to react at a set temperature for a specified length of time or by charging ingredients into the reactor and feeding the monomers into the reactor to maintain a constant pressure until a desired amount of polymer is formed.
• the polymerization can be carried out in a standard or conventional vessel used for emulsion polymerization of gaseous fluorinated monomers.
• any suitable initiator or any suitable initiator system for example ammonium persulfate (APS), or of redox systems, such as APS/bisulfite and potassium permanganate.
• APS ammonium persulfate
• redox systems such as APS/bisulfite and potassium permanganate.
• oil-soluble initiators are those which have no, or only insufficient, solubility in water. Examples of oil-soluble initiators are substituted dibenzoyl peroxides and cumene hydroperoxides, in particular bisperfluoropropionyl peroxide.
• the polymerization systems may comprise auxiliaries, such as buffers and, if desired, complex-formers or chain-transfer agents.
• the polymerization temperature may be from 10 to 180°C, typically 30°C to 100°C.
• Polymerization pressures may be from 1 to 40 bar, typically 3 to 30 bar.
• any liquid fluorinated monomer such as for example a liquid perfluorovinyl ether monomer used in the polymerization may be pre-emulsified prior to its copolymerization with the other gaseous monomers such as tetrafluoroethylene and vinylidene fluoride.
• gaseous monomers such as tetrafluoroethylene and vinylidene fluoride.
• liquid fluorinated monomer is meant that the monomer is generally present as a liquid at ambient conditions of temperature and pressure, i.e. at a temperature of 20°C and a pressure of 1 atm.
• pre-emulsified in connection with the present invention is meant that the fluorinated monomer is emulsified in water with the aid of the fluorinated emulsifier prior to polymerization of the liquid fluorinated monomer.
• the fluorinated liquid monomer can be emulsified in water with the aid of a fluorinated emulsifier such as described above, prior to its copolymerization with the other monomers.
• the pre-emulsification of the liquid fluorinated monomer results in an emulsion having monomer droplets.
• the pre-emulsion average droplet size can range from an average diameter of more than 1 ⁇ m, down to about 150 mn or even lower. Preferably the average droplet diameter is not more than 500 nm, more preferably not more than 300 nm.
• the aqueous emulsion should preferably have a pot life (settling time) of at least 1 hour, more preferably at least 3 hours. The pot life or settling time is defined as the time required for 10% by weight of the monomer droplets to settle or separate out of the aqueous emulsion.
• Aqueous emulsions of the liquid fluorinated monomer can conveniently be obtained by suitable emulsification equipment such as for example high speed rotor-stator mixers such as an Ultra-Turrax (Ika).
• the stirring rates should be sufficiently high to achieve the desired degree of emulsification and stability. Generally, stirring rates of 24 000 rpm or more can be employed. Air is preferably excluded during the emulsification.
• the pre- emulsion particle size can be further reduced with high pressure homogenizers, available from APN Gaulin or Microfluidics.
• the amount of fluorinated emulsifier used to emulsify liquid fluorinated monomer is generally between 0.01 and 10 % by weight based on the weight of the liquid fluorinated monomer, preferably 0.1 to 4 % by weight. Although higher amounts of emulsifier can be used, they will not necessarily lead to a significant increased pot life of the aqueous emulsion of liquid fluorinated monomer produced. Further, the use of high amounts of emulsifier is not preferred because the emulsifier generally needs to be removed after polymerization, making the process less effective.
• the aqueous emulsion polymerization may be carried out without the addition of a fluorinated surfactant.
• the initiator or initiator system used will typically be selected such that sufficient ionic end groups are generated so as to stabilize the polymer particles in the aqueous emulsion polymerization.
• a thermal initiator such as a persulfate, e.g., ammonium persulfate can be used to initiate the polymerization.
• the persulfate will typically generate sulphate end groups.
• a desired amount of radicals and polymerization particles can be generated. For example selecting a high initial initiator concentration will increase the number of radicals and particles formed. Likewise, by starting at a high temperature a larger number of radicals will be generated. Accordingly, the polymerization may be initiated at a first temperature and this temperature may then be lowered after an initial period of initiation. The initial period will typically be between 1 and 60 minutes, for example between 5 and 20 minutes from the start of the polymerization reaction. If desired, further initiator may be added during the polymerization but this may not be required.
• Amounts of initiator in the initial charge are generally between 0.01 and 2.0% by weight, preferably between 0.1 and 1.8% by weight, more preferably between 0.3% and 1.6% by weight based on the total weight of polymer to be produced.
• the temperature for use at the initial stage is generally between 40°C and 100°C, preferably between 60°C and
• the temperature during the course of polymerization is generally in the range of 30°C to 80°C.
• the optimal conditions can be readily determined by routine experimentation.
• Aqueous emulsion polymerization that is carried out without the addition of a fluorinated surfactant can further be practiced as disclosed in US 5,453,477 and WO 97/17381.
• a radical initiator system of a reducing agent and oxidizing agent is used to initiate the polymerization and the initiator system is added in one or more further charges during the polymerization.
• the ionic end groups formed as a result of the initiator system used in WO 97/17381 are taught to stabilize the fluoropolymer particles in the emulsifier free aqueous emulsion process.
• Suitable oxidizing agents that can be used include persulfates such as potassium persulfate and ammonium persulfate, peroxides such as hydrogen peroxide, potassium peroxide, ammonium peroxide, tertiary butyl hydroperoxide, cumene peroxide and t-amyl hydroperoxide, manganese triacetate, potassium permanganate, ascorbic acid and mixtures thereof.
• persulfates such as potassium persulfate and ammonium persulfate
• peroxides such as hydrogen peroxide, potassium peroxide, ammonium peroxide, tertiary butyl hydroperoxide, cumene peroxide and t-amyl hydroperoxide
• manganese triacetate potassium permanganate
• potassium permanganate ascorbic acid and mixtures thereof.
• Suitable reducing agents include sodium sulfites such as sodium bisulfite, sodium sulfite, sodium pyrosulfite, sodium-m-bisulfite, ammonium sulfite monohydrate and sodium thiosulphate, hydroxylamine, hydrazine, glucose, organic acids such as oxalic acid, malonic acid and citric acid and mixtures thereof.
• the amount of oxidizing agent added in the initial charge is typically between 10 and lOOOOppm.
• the amount of reducing agent in the initial charge is typically also between 10 and lOOOOppm.
• At least one further charge of oxidizing agent and reducing agent is added to the polymerization system in the course of the polymerization.
• the further addition(s) may be done batchwise or the further addition may be continuous.
• the fluorochemical composition comprises a dispersion or solution of the fluoropolymer in water or an organic solvent.
• the amount of fluoropolymer contained in the treating composition is between 0.01 and 4% by weight, preferably between 0.05 and 3% by weight based on the total weight of the fluorochemical composition.
• Higher amounts of fluoropolymer of more than 4% by weight, for example up to 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 fluoropolymer in the treating composition.
• the concentrated fluorochemical composition can contain the fluoropolymer in an amount of up to 70% by weight, typically between 10% by weight and 50% by weight.
• the weight average particle size of the fluoropolymer particles is preferably not more than 300nm, more preferably is not more than 250nm.
• the fluorochemical composition is an aqueous dispersion of the fluoropolymer.
• Such dispersion may be non-ionic, anionic, cationic or zwitterionic.
• the dispersion is preferably stabilized 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 Emulsogen EPN 207 (Clariant) and Tween 80 (ICI), anionic types such as lauryl sulfate and sodium dodecyl benzene sulfonate, cationic types such as Arquad T-50 (Akzo), Ethoquad 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 2 to about 10 parts by weight, based on 100 parts by weight of the fluorochemical composition.
• the dispersion is free of fluorinated surfactants having a molecular weight of less than lOOOg/mol in particular less than 700 g/mol, or the amount thereof is kept to a minimum, for example not more than 0.5% by weight of the fluorochemical composition, preferably not more than lOOOppm.
• a solution or dispersion of the fluoropolymer 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 isopropylether, esters such ethylacetate, butylacetate or methoxypropanol acetate or (partially) fluorinated solvents such as HCFC-141b, HFC-134a, HFE-7100, HFE-7200 or perfluoroketones.
• 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. It is particularly preferred to include one or more auxiliary components other than the fluoropolymer and that are capable of further improving the oil- and/or water repellency properties of a fibrous substrate treated with the fluorochemical composition or that are capable of improving the soil/stain release properties of a fibrous substrate treated with the fluorochemical composition.
• the auxiliary components are capable of improving the durability of the repellency properties and/or soil/stain release properties.
• the auxiliary components are generally non-fluorinated organic compounds and are also called extenders hereinafter.
• Suitable extenders capable of improving the oil- and/or water repellency properties include for example blocked isocyanates including aromatic and aliphatic blocked isocyanates, aliphatic polyisocyanates and aromatic or aliphatic carbodiimides including aromatic or aliphatic polycarbodiimides.
• Auxiliary components that are capable of enhancing the soil stain release properties are generally non-fluorinated organic compounds such as for example blocked isocyanate compounds that include a polyoxyalkylene group, in particular a polyoxyethylene group.
• Auxiliary components that are generally capable of improving durability of the repellency properties or soil/stain release properties include non-fluorinated organic compounds that have one or more groups (or a precursor thereof) capable of reacting with the surface of the fibrous substrate. Examples thereof include compounds that have isocyanate groups or blocked isocyanates.
• the aliphatic polyisocyanate for use as an extender in the fluorochemical composition is preferably a compound having a molecular weight of at least 350g/mol and may be prepared by reacting a low molecular weight aliphatic polyisocyanate and organic compound having groups capable of reacting with an isocyanate.
• the amount of free isocyanate groups in the aliphatic isocyanate is typically at least 10% by weight of the total weight of the compound, preferably at least 20% by weight.
• Suitable low molecular weight aliphatic isocyanates include diisocyanates, triisocyanates and mixtures thereof.
• Examples include hexamethylenediisocyanate, 2,2,4-trimethyl-l,6- hexamethylenediisocyanate, and 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).
• the organic compound is generally reacted with the aliphatic polyisocyanate in the presence of a catalyst such as an organic tin compound and under reaction conditions commonly employed.
• the amount of organic compound will be selected such as to leave a desired amount of isocyanate groups unreacted.
• the resultant reaction mixture can be used in compositions of the invention.
• the organic compound preferably has one or two functional groups that are capable of reacting with an isocyanate group. Such functional groups include hydroxy, amino and thiol groups.
• Examples of organic compounds include alkane diols such as ethylene glycol, mono-alkanols having at least 6 carbon atoms, fatty ester diols, polyester diols, alkane diamines and dimer diols.
• the organic compound will include one or more water solubilising groups or groups capable of forming water solubilising groups so as to obtain a reaction product that is self-emulsifying in water.
• Suitable water solubilising groups include cationic, anionic and zwitter ionic groups as well as non-ionic water solubilising groups.
• Examples of ionic water solubilising groups include ammonium groups, phosphonium groups, sulfonium groups, carboxylates, sulfonates, phosphates, phosphonates or phosphinates.
• groups capable of forming a water solubilising group in water include groups that have the potential of being protonated in water such as amino groups, in particular tertiary amino groups.
• Particularly preferred organic compounds for reacting with the aliphatic polyisocyanate are those organic compounds that have only one or two functional groups capable of reacting with NCO-group and that further include a non-ionic water-solubilising group.
• Typical non-ionic water solubilising groups include polyoxyalkylene groups.
• Preferred polyoxyalkylene groups include those having 1 to 4 carbon atoms such as polyoxyethylene, polyoxypropylene, polyoxytetramethylene and copolymers thereof such as polymers having both oxyethylene and oxypropylene units.
• the polyoxyalkylene containing organic compound may include one or two functional groups 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 propyleneoxide, amino terminated methyl or ethyl ether of polyethyleneoxide, polyethylene glycol, polypropylene glycol, a hydroxy terminated copolymer (including a block copolymer) of ethyleneoxide and propylene oxide, a diamino terminated poly(alkylene oxide) such as JeffamineTM ED, JeffamineTM EDR-148 and poly(oxyalkylene) thiols.
• alkyl ethers of polyglycols such as, e.g., methyl or ethyl ether of polyethylene
• aliphatic polyisocyanates include BaygardTM NP SP 23012, RucoguardTM EPF 1421 and TubicoatTM Fix ICB.
• a further suitable extender is a blocked isocyanate.
• blocked isocyanate is meant a (poly)isocyanate of which the isocyanate groups have been reacted with a 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. Generally, at elevated temperature the blocking group will 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.
• the blocked isocyanate may be aromatic, aliphatic, cyclic or acyclic and is generally a blocked di- or triisocyanate or a mixture thereof and can be obtained by reacting an isocyanate with a blocking agent that has at least one functional group capable of reacting with an isocyanate group.
• Preferred blocked isocyanates are blocked polyisocyanates that at a temperature of less than 150°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, ⁇ -butyrolactam, 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, a blocking agent and an organic compound other than the blocking agent and having one or more isocyanate reactive groups such as a hydroxy, amino or thiol group.
• a polyisocyanate for example a di- or triisocyanate
• a blocking agent for example a blocking agent
• an organic compound other than the blocking agent and having one or more isocyanate reactive groups such as a hydroxy, amino or thiol group.
• organic compounds include those described above.
• Particularly preferred are blocked polyisocyanates that have a self-emulsifying capability in water.
• a polyisocyanate, a blocking agent and an organic compound having a water solubilising group or a group capable of forming a water solubilising group in water are reacted with each other under conditions commonly employed in reacting isocyanate components.
• Suitable organic compounds including such a water solubilising group or group potentially forming a water solubilising group have been described above.
• polyisocyanates for preparing the blocked polyisocyanates include di- or triisocyanates as well as mixtures thereof.
• aromatic diisocyanates such as 4,4'-methylenediphenylenediisocyanate, 4,6-di-(trifluoromethyl)-l,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'-diisocyanate
• Still further isocyanates that can be used for preparing a blocked isocyanate include alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate;
• 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate aliphatic diisocyanates such as 1,6-hexamethylenediisocyanate, 2,2,4-trimethyl-l,6-hexamethylenediisocyanate, and 1,2- ethylenediisocyanate
• aliphatic triisocyanates such as 1,3,6-hexamethylenetriisocyanate
• aromatic tri-isocyanates such as polymethylenepolyphenylisocyanate (PAPI); cyclic diisocyanates such as isophorone diisocyanate (LPDI) and dicyclohexylmethane-4,4'- diisocyanate.
• 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.
• blocked aromatic polyisocyanates include BaygardTM EDW available from Bayer Corp. and HydrophobolTM XAN available from Ciba-Geigy.
• a still further class of extenders suitable for use with the fluorochemical composition of this invention are carbodiimides.
• Suitable carbodiimides have been described in for example US 4,668,726, US 4,215,205, US 4,024,178, US 3,896,251, WO 93/22282, US 5,132,028, US 5,817,249, US 4,977,219, US 4,587,301, US 4,487,964, US 3,755,242 and US 3,450,562.
• Particularly suitable carbodiimides for use in this invention include those corresponding to the formula (VIII) :
• R'-tN ⁇ C-N-R ⁇ u -N ⁇ C ⁇ N-R 2 (VIII) wherein u has a value of 1 to 10, typically 1 or 2, R and R each independently represent a hydrocarbon group, in particular a linear, branched or cyclic aliphatic group preferably having 6 to 18 carbon atoms and R represents a divalent linear, branched or cyclic aliphatic group.
• Particular examples of such polymers include homo- and copolymers of alkyl esters of acrylic and methacrylic acid such as for example Ci to C 0 alkyl esters of acrylic acid.
• Specific examples of such alkyl esters include methyl acrylate, ethyl acrylate, butyl acrylate, octadecyl acrylate and lauryl acrylate.
• suitable polymers include a homopolymer of methyl acrylate and a copolymer of methyl acrylate and octadecyl acrylate.
• 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 may alternatively or additionally be subjected to a heat treatment, for example, in an oven.
• This heat treatment 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.
• 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 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 between 0.05% and 3% by weight based on the weight of the fibrous substrate.
• the amount which is sufficient to impart desired properties can be determined empirically and can be increased as necessary or desired.
• Fibrous substrates that can be treated with the fluorochemical composition include in particular textile.
• 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.
• Treatment baths were formulated containing a defined amount of the fluoropolymer treatment agent with or without the addition of an additive. Treatments were applied to the test substrates by padding to provide a concentration as indicated in the examples (based on fabric weight and indicated as SOF (solids on fabric)). Samples were air dried at ambient temperature for 48 hours followed by conditioning at 21°C and 50% relative humidity for 2 hours (air cure). Alternatively, the samples are dried and cured at a temperature and a time as indicated in the respective examples. Substrates used for the evaluation of treatments of this invention were commercially available and are listed below :
• PES/CO polyester/cotton 65/35 fabric, style no. 2681.4, available from Utexbel N.V.,
• PES/CO-2 polyester/cotton 65/35 fabric, style no. 05461, available from Avondale
• PA ⁇ polyamide microfiber, style no. 7819.4, available from Sofinal, Belgium
• PES ⁇ polyester microfiber, style no. 6145.3, available from Sofinal, Belgium
• PP SMS polypropylene nonwoven fabric, medical grade, approximately 1-2 oz/yd
• the substrates were tested for their repellency properties.
• the spray rating of a treated substrate is a value indicative of the dynamic repellency of the treated substrate to water that impinges on the treated substrate.
• the repellency was measured by Test Method 22-1996, published in the 2001 Technical Manual of the American Association of Textile Chemists and Colorists (AATCC), and was expressed in terms of a 'spray rating' 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 against a standard rating chart : using a 0 to 100 scale, where 0 means complete wetting and 100 means no wetting at all.
• the water repellency (WR) of a substrate was measured using 3M Test Method, Water Repellency Test II: Water/Alcohol Drop Test (Doc. # 98-0212-0721-6), in which a series of water-isopropyl alcohol test liquids are used to determine a "WR" rating of the treated substrate.
• the WR rating corresponded to the most penetrating test liquid which did not penetrate or wet the substrate surface after 10 seconds exposure. Substrates which were penetrated by or were resistant only to 100% water (0% isopropyl alcohol), the least penetrating test liquid, were given a rating of 0, whereas substrates resistant to 100% isopropyl alcohol (0% water), the most penetrating test liquid, were given a rating of 10.
• the oil repellency of a substrate was measured by the American Association of Textile Chemists and Colorists (AATCC) Standard Test Method No. 118-1997, which test was based on the resistance of a treated substrate to penetration by oils of varying surface tensions after contact for 30 seconds.
• Treated substrates resistant only to Kaydol® mineral oil were given a rating of 1
• treated substrates resistant to n-heptane 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.
• Stain Release Test After Launderings The Stain Release Test was also run on treated fabric that had subsequently been washed using 5, 10, or 20, consecutive "home” launderings, followed by tumble drying, as described in the 3M Protective Material Division's "Laboratory Laundering Procedures" (Document # 98-0212-0703-4, available from 3M Co.).
• CF 2 CF-O-CF 2 CF(CF 3 )-O-CF 2 CF 2 CF 3
• HydrophobolTM XA ⁇ aqueous blocked aromatic polyisocyanate extender, available from Ciba Geigy
• TubicoatTM ICB aliphatic isocyanate extender, available from CHT
• DesmodurTM ⁇ -100 aliphatic polyisocyanate, available from Bayer
• IPDI isophorone diisocyanate, available form Merck
• MDI 4,4'-methylene diphenyl diisocyanate, available from Bayer
• EthoquadTM 18/25 methyl polyoxyethylene(15)octadecyl ammonium chloride, available from Akzo ArquadTM 12-50 : dodecyl trimethyl ammonium chloride available from Akzo
• MPEG 750 poly(ethyleneglycol)monomethyl ether, with molecular weight 750, available from Aldrich
• IsofolTM 18T branched long chain alcohol (with average C18 chain) available from
• THN 220 copolymer of TFE/HFP/NDF (mole % : 42/20/38), commercially available from Dyneon
• ⁇ afionTM SE10172 fluorinated ionomer, available from DuPont de Nemours
• KaydolTM mineral oil available from Witco Chemical Corp., Greenwich, CT.
• Fluorochemical vinylether polymers (FNEP) and comparative fluorochemical polymers (C-FC) as given in table 1, were synthesised according to the procedures as given below.
• Table 1 further indicates the emulsifier used (if applicable) in the aqueous emulsion polymerization for producing the fluoropolymers.
• samples FVEP-1 to FVEP-11 and C-FC1 and C-FC2 mole% of repeating units derived from the indicated monomers as measured by NMR analysis.
• samples FNEP- 12 to FNEP-24 theoretic mole% of repeating units derived from the indicated monomers as calculated from monomer charges.
• the vessel was degassed in three subsequent cycles and then charged with nitrogen to assure that all oxygen had been removed.
• the vessel was heated to 70° C and the agitation system was set to 210 rpm.
• the vessel was charged with 55 g dimethylether (Me 2 O), 400 PPNE-2 and 1140 g HFP so as to obtain a pressure of 3.50 bar absolute and with 2332 g NDF to obtain 15.5 bar absolute reaction pressure.
• the polymerization was initiated by the addition of 530 ml of a 30% solution of APS in water. As the reaction started, the reaction pressure of 15.5 bar absolute was maintained by feeding NDF and HFP into the gas phase with a feeding ratio of HFP (kg)/NDF (kg) of 0.203. Additionally, 600 g PPNE-2 were continuously added with a feeding rate of 220 g/h. The reaction temperature was kept at 70° C. After feeding 48.76 kg NDF (265 min polymerisation time), the monomer feed was interrupted and the monomer valves were closed. Within 15 min, the monomer gas phase was reacted down to a vessel pressure of 6.3 bar; then the reactor was vented and flushed with ⁇ 2 in three cycles.
• this dispersion was worked up to agglomerate according to the following procedure: 200 g of the dispersion was charged into a 1000 ml glass cylinder. 100 ml deionized water were added. Under vigorous stirring, 3 ml concentrated hydrochloric acid and 40 ml perfluoro n-heptane agglomeration aid (PF 5070 by 3M) were added. The mixture was stirred vigorously until the solid had fully separated from the aqueous phase. The agglomerate was washed three times with deionized water, the agglomeration aid was distilled off and the polymer was dried in an oven at 70° C for 24 hours.
• PF 5070 perfluoro n-heptane agglomeration aid
• the so-obtained polymer agglomerate showed a melting point maximum of 111 °C° C and a MFI(265/5) of 5.2 g/10'.
• the polymer was evaluated by means of 1 H/ 19 F crosslinlc-NMR indicating a chemical composition of 91.6 mole %> NDF, 8.2 mole % HFP and 0.2 mole % PPNE-2. Synthesis of FNEP-3 (TFE/PMNE/BTFE)
• CH 2 C1 2 dichloromethane
• BTFE bromotrifluoroethylene
• the polymerization was initiated through the addition of 1763 g of a 20% solution of APS in water.
• the reaction temperature of 71° C as well as the reaction pressure of 16.0 bar absolute was maintained by the feeding TFE, PMNE and BTFE into the gas phase.
• a feeding ratio of PMNE (kg)/TFE (kg) of 1.044 and BTFE (kg)/TFE (kg) of 0.015 was used.
• the monomer feed was interrupted and the monomer valves were closed.
• the reactor was vented and flushed with ⁇ 2 in three cycles.
• the so-obtained 158.3 kg polymer dispersion with a solids content 31.0 % was broached at the bottom of the reactor. Latex particles having a diameter of 84 nm, measured by dynamic light scattering, were obtained.
• This pre-emulsion was further pressurised three times under high shear in a M- 110EH Micofluidizer Processor (Microfluidizer Corporation) under 1500 bar pressure. 2400 g of this pre-emulsion with a droplet size of 201 nm (according to dynamic light scattering) was charged into the reaction vessel (the rest of this pre-emulsion was used to be continuously fed into the reaction vessel within the polymerisation). The vessel was further charged with 10.5 g dimethylether, 197 g NDF to 3.86 bar and 192 g TFE to 6.0 bar absolute reaction pressure. The polymerization was initiated by adding 40 g APS dissolved in water.
• the reaction temperature of 70°C as well as the reaction pressure of 6.0 bar absolute was maintained by feeding TFE and NDF into the gas phase with a feeding ratio of NDF (kg)/TFE (kg) of 1.922.
• the rest of the PPNE-2 pre- emulsion was fed into the liquid phase with a feeding ratio of PPNE-2-pre-emulsion (kg)/TFE (kg) of 4.247.
• the monomer feed was interrupted and the monomer valves were closed.
• the monomer gas phase was reacted down to a vessel pressure of 2.1 bar; then the reactor was vented and flushed with ⁇ 2 in three cycles.
• the so-obtained 23.52 kg polymer dispersion with a solid content of 18.4% was broached at the bottom of the reactor. Latex particles having 234 nm in diameter (according to dynamic light scattering) were obtained. A small amount of this dispersion was worked up to raw gum by freeze coagulation over night, subsequent defrosting and washing with demineralised water in three cycles. The raw gum was dried for 15 h at 130°C under vacuum.
• the so-obtained polymer showed a chemical composition of 20 mole % TFE, 60 mole % NDF and 20 mole % PPNE-2 as obtained by ⁇ F crosslink- ⁇ MR.
• the pre-emulsion of PPNE-2 used for the continuous feed was prepared by emulsifying 675 g PPNE-2 and 10 g 30% APFO solution into 680 ml water. In the cases 0.1% aqueous KMnO solution was used as initiator, the amount of KMnO 4 solution was continuously fed into the reaction vessel at such rate that the feed was completed within the polymerisation time as given in the table below.
• the polymerization was initiated through addition of 130 ml of a 30% solution of APS in water. As the reaction started, the reaction pressure of 2.0 bar absolute was maintained by feeding NDF for 3.5 hours. The reaction temperature was maintained at 60° C. After feeding 670 kg NDF, the monomer feed was interrupted and the NDF valve was closed. Then the reactor was vented and flushed with ⁇ in three cycles. The so-obtained 34.2 kg polymer dispersion (solid content 15.4%) was broached at the bottom of the reactor. The polymer dispersion had latex particles with a diameter of 186 nm, as measured by dynamic light scattering. The polymer dispersion was worked up according to the procedure as described for FVEP-1. A highly viscous oil was obtained. The 1H/ 19 F crosslink-NMR analysis indicated a chemical composition of 57 mole % NDF and 43 mole % PPNE-2.
• Fluorochemical vinylether polymer FNEP- 12 was made using polymeric emulsifier, according to the following procedure : A mixture of 280 g DI water, 1 g ⁇ afion SE10172, 55.8 g PPNE2 and 1 g KH 2 PO 4 was homogenized 3 times at 8800 psi using a 2-stage Gaulin 15MR high pressure homogenizer to yield a PPNE2 emulsion in water. 168.9 g of this emulsion was vacuum charged into a 500 ml autoclave, together with 0.1 g dimethyl malonate (DMM) and 5.5 g APS solution (0.5 g APS dissolved in 5 g water). 9.7 g HFP and 12.4 g NDF were then pressured into the reactor. The reaction ran for 16 hours at 71 °C. A 12% solids, milky liquid, with a particle size of 151 nm was obtained.
• DDMM dimethyl malonate
• APS solution 0.5
• Fluorochemical vinylether polymers FNEP- 13 to FNEP- 16 and FNEP-20 to FNEP-23 were made using polymeric emulsifier, according to the following procedure for the synthesis of FNEP-13 (NDF/HFP/PPNE2 : 69.1/18.9/12) :
• a PPNE-2 emulsion, containing 140 g deionised water, 0.5 KH 2 PO , 0.5 g ⁇ afion SE10172 and 15 g PPNE2 was made according to the procedure described for FNEP- 12.0.5 g APS and 0.1 g DMM were dissolved in 10 g deionised water.
• This mixture was added to the homogenized PPNE2 emulsion and vacuum charged into a high pressure reactor.
• the reactor was twice purged with nitrogen and evacuated. About 5 g of a 61/39 weight % mixture of NDF/HFP was charged into the reactor. The reaction mixture was heated to 71 °C during 30 min. Additionally 16 g NDF/HFP mixture were charged into the reactor manually, maintaining the reaction pressure near 150 psi. The reaction was held at 71°C during additional 16 hours.
• FNEP- 14, FNEP-22 and FNEP-23 were made in the same way, but using a monomer ratio as indicated in table 1.
• FNEP-22 was made using KOH instead of KH 2 PO 4 .
• FNEP-23 was made with potassium phosphate monobasic instead of KH 2 PO 4 .
• FNEP- 15 and FNEP- 16 were made in the same way, with monomer ratio's as given in table 1 and using a pressure regulator to add the gaseous monomers.
• 1.5g ⁇ afion SE10172 and 1.5g potassium hydrogenphosphate (buffer) were first dissolved in 480.0g DI water. 45.0g PPNE2 was added and the mixture was sonicated (using a Fisher Scientific 550 Sonic Dismembrator) for 60s to form a coarse emulsion. This coarse emulsion was further homogenized using a Gaulin 15MR for 3 passes at 8800psi to form a fine emulsion. An initiator solution consisting of 20.0g DI water, l.Og APS and 0.2g dimethyl malonate was then added to 312.0g of the homogenized emulsion and mixed using a magnetic stirrer.
• This mixture was vacuum charged into a 500mL high pressure reactor, followed by twice purging with nitrogen and evacuation. When this was completed, the reactor temperature was heated to 71°C while a 61%/39% NDF/HFP mixture was regulated into the reactor at lOOpsi. A total of 34.2g of the gas mixture was fed into the reactor. The entire reaction time took 16 hours after the reaction temperature reached 71°C. The resultant latex was 14.8% solids with a mean particle size of 71nm.
• 2.4 ⁇ afion SE10172 and 1.2g potassium phosphate monobasic (buffer) were first dissolved in 336.
• Og PPNE2 was added and the mixture was sonicated for 60s to form a coarse emulsion.
• This coarse emulsion was further homogenized using a Gaulin 15MR for 3 passes at 8800psi to form 411.6g of a fine emulsion.
• An initiator solution consisting of 20.0g DI water, 2.0g APS and 0.4g dimethyl malonate was added to
• the pre-emulsion was charged into a polymerization bottle and polymerized for 4 hrs in a pre-heated Launderometer at 70°C after adding 6 g of a 10% APS-solution (1% on PPNE-1). Unreacted PPNE-1, remaining as a liquid at the bottom of the flask separated from the upper latex. A milky latex with 4% solids was obtained.
• the polymerization was initiated by the addition of 90 g APS dissolved in water. As the reaction started, the reaction temperature of 71°C as well as the reaction pressure of 10.0 bar absolute was maintained by feeding TFE, NDF and HFP into the gas phase with a feeding ratio of TFE (kgVNDF (kg) of 0.671 and HFP (kgVNDF (kg) of 1.118. After feeding 14.86 kg NDF
• NDF to 12.0 bar absolute reaction pressure The polymerization was initiated by the addition of 64 g potassium peroxodisulfate (KPS) dissolved in water. As the reaction started, the reaction temperature of 71 °C as well as the reaction pressure of 12.0 bar absolute were maintained by the feeding NDF and HFP into the gas phase with a feeding ratio of NDF (kgVHFP (kg) of 0.640. After feeding 7.51 kg HFP (312 min reaction time), the monomer feed was interrupted and the monomer valves were closed. Then the reactor was vented and flushed with ⁇ 2 in three cycles. The so-obtained 41.1 kg polymer dispersion with a solid content of 29.4% was broached at the bottom of the reactor.
• KPS potassium peroxodisulfate
• the composition of the fluorochemical vinylether polymers was evaluated by means of fractionation. Therefore, a sample was frozen by means of Dry Ice. The water was thawed and decanted from the broken emulsion. The sample was vacuum dried at 70°C, during 48 hours, until constant weight was obtained. The solids were dispersed in acetone at 5% by weight. The dispersion was centrifuged at 2000 rpm, during 40 min. This resulted in the separation of a soluble layer and discrete layers of insoluble material. The acetone soluble top layer (indicated as 'soluble') was removed and put into a pre weighed container. The following layer (indicated as 'insoluble') was removed and put into a pre weighed container. Occasionally, a third layer remained at the bottom of the recipient (indicated as 'bottom'). The composition of the different layers was determined by ⁇ F-NMR. The mole percentages are given in the table below.
• the fluorochemical vinylether polymers could be applied to substrates as an aqueous emulsion or in an alternative way, the fluorochemical vinylether polymers could be applied out of solvent.
• the fluorochemical vinylether polymers could be applied as aqueous anionic emulsions as prepared above.
• Aqueous cationic emulsion In an alternative way, the fluorochemical vinylether polymer dispersions obtained after preparation of the polymer were first coagulated using MgCl or freeze dried, hi a second step, the solids were dissolved or dispersed in an organic solvent, such as ethyl acetate or MEK.
• a cationic emulsion was obtained using the following method : to 60 g of fluorochemical vinylether polymer solution in solvent, e.g., ethyl acetate, were added a solution of emulsifier (kind and amount given in the examples) in water. The mixture was heated to 65°C and added to 96 g deionized water, preheated to 65°C, whilst stirring.
• the so formed pre-emulsion was then emulsified by immersion of an ultrasound probe (Branson 450-D Sonifier) for 6 minutes (cycle 10" run- 5" stop at 50-60°C).
• the solvent e.g., ethyl acetate, was distilled off with a rotary evaporator at 55°, using waterjet vacuum. Stable milky emulsions of about 20%> solids were obtained.
• the obtained fluoropolymer dispersions were coagulated using MgCl or freeze dried and in a second step, the solids were dissolved or dispersed in an organic solvent, such as ethyl acetate or MEK.
• hydrocarbon extenders as given in table 2, were synthesised according to various methods, depending on their structure :
• a reaction flask equipped with a reflux condenser, a mechanical teflon blade stirrer, a thermometer, a nitrogen inlet and vacuo outlet, was charged with 60.75 g PAPI, 35.8 g glycerolmonostearate and 177.5 g ethyl acetate. After addition of 2 drops DBTDL, the mixture was stirred at 70°C during 7 hours. In a second step, 21.75 g 2-BO was added and the reaction continued at 50°C, until FTIR analysis indicated that all isocyanate had reacted. A clear amber colored solution was obtained.
• a reaction flask equipped with a reflux condenser, a mechanical teflon blade stirrer, a thermometer, a nitrogen inlet and vacuo outlet, was charged with 36.72 g PAPL 2.4 g EO800 and ethyl acetate (60%). The mixture was stirred until the reagents were dissolved. 25.58 g 2-BO and 2 drops DBTDL were added and the mixture was stirred at 75°C during 4.5 hours after which FTIR analysis indicated that all isocyanate was reacted.
• a reaction flask equipped with a reflux condenser, a mechanical stirrer, thermocouple and nitrogen inlet was charged with 95.5 g Desmodur N-100, 250 g ethyl acetate and 125 g MPEG 750. 0.25 g DBTDL was added and the resulting mixture was heated to 75°C and stirred overnight. The mixture was then cooled to room temperature, and 29.1 g 2-BO was added dropwise with stirring. The mixture was reheated to 75°C and stirred overnight.
• a reaction flask equipped with a reflux condenser, a mechanical teflon blade stirrer, a thermometer, a nitrogen inlet and vacuo outlet, was charged with 85.8 g Isofol 18T and 297.45 g MLBK (dry). 112.5 g MDI and 0.025 g DBTDL were added. The reaction mixture was stirred overnight at about 95°C. In a second step, 2.25 g camphene phenyl phosphine oxide (CPPO) catalyst was added (2% based on the amount of MDI). The reaction was run to completion at 110°C during 8 hours. An amber colored solution was obtained.
• CPPO camphene phenyl phosphine oxide
• a 250 ml 3 necked reaction flask, equipped with a thermometer, a nitrogen flow, a reflux condenser, a mechanical stirrer and a heating mantle was charged with 0.2 moles IPDI, 0.1 moles ODI and a camphene phenyl phosphine oxide (CPPO) catalyst (2% based on IPDI).
• CPPO camphene phenyl phosphine oxide
• reaction mixture was gradually heated to 160°C.
• the reaction was run at 160°C during 20 hours.
• FTIR analysis indicated that all isocyanate groups had reacted.
• a slightly hazy, brown, viscous mixture was obtained.
• 74 g ethyl acetate was added via a dropping funnel, while cooling the mixture.
• Another 37 g ethyl acetate was added to obtain a 40% solids solution.
• the ethyl acetate was distilled off with a rotary evaporator at 60-65 °C, using waterjet vacuum.
• the emulsion was filtered through cheesecloth and the final solids were measured at 14.1% by weight loss on drying.
• anionic emulsions of fluorochemical vinylether polymers were applied to 100% cotton US so as to give 1 % SOF FNEP. After treatment the fabrics were dried at room temperature (air dry) or dried and cured at 150°C for 10 minutes (150°C cure). Comparative examples C-l and C-2 was made with comparative fluorochemical polymers C-FCl and C-FC2 respectively. The treated fabrics were tested for oil and water repellency. The results are given in table 4.
• the treated fabrics had good oil and/or water repellency, in most cases even without the need for high temperature cure.
• Examples 14 to 22 and comparative examples C-3 and C-4 In examples 14 to 22, and comparative examples C-3 and C-4 the same kind of experiment was repeated on a nylon (US) substrate. The results of oil and water repellency are given in table 5.
• perfluorovinylether copolymer FVEP-7 and FVEP-9 in MEK were used to treat PES/CO, PA ⁇ and cotton fabrics, so as to give 1 % SOF. After treatment the fabrics were dried at room temperature (air cure) or dried and cured at 160°C for 1.5 minutes. The treated fabrics were tested for oil and water repellency. The results are given in table 6.
• fluorochemical vinylether polymer FVEP-9 anionic emulsion was used to treat 100% cotton fabric and PA ⁇ , so as to give 1 % SOF.
• Examples 30 and 32 were made by treating the same substrates with a blend of FVEP-9 (1% SOF) and extender
• an anionic emulsion of FVEP-7 was coagulated using MgCl.
• the solids were dissolved in ethyl acetate and postemulsified with a 3% solution of Arquad 12-50 according to the general procedure.
• the emulsion was used to treat cotton (US) and polyamide (US) fabrics.
• the treated fabrics were tested for oil repellency after air dry and after drying and curing at 150°C during 10 min. The results are given in table 14.
• cotton fabric US was treated with FVEP- 17 at 1% SOF, alone or in combination with Ext-6 so as to give SOF as indicated in table 17. After treatment, the fabrics were dried and cured at 150°C during 10 minutes. The treated fabrics were tested for oil and water repellency, initially and after home launderings. The results are given in table 17.
• an anionic emulsion of fluorochemical vinylether polymer FVEP-6 was pad applied to polypropylene SMS nonwoven fabric so as to give 1%> SOF. 1% alcohol
• the wet nonwoven fabric was dried by placing the fabric in a 46 cm x 51 cm sheet dryer (available from Williams Apparatus Co., Watertown, NY) set at a temperature of 127 ⁇ 3°C with the fabric face side down (i.e., face side in contact with metal and reverse side in contact with canvas) and drying/curing for 2.5 minutes, followed by tuniing over the fabric and curing in reverse for 0.5 minutes at the same temperature.
• the treated nonwoven fabric gave an oil repellency of 1. This indicated that oil repellency could be imparted to the normally oleophilic polypropylene SMS nonwoven fabrics by treating with a fluorochemical vinylether polymer.
• anionic emulsions of fluorochemical vinylether polymers as shown in table 18, were pad applied to cellulose/polyester nonwoven fabrics so as to give from
• the wet nonwoven fabrics were dried by placing each fabric in the 46 cm x 51 cm Williams sheet dryer set at a temperature of 127 ⁇ 3°C with the fabric face side down (i.e., face side in contact with metal and reverse side in contact with canvas) and drying/curing for 2.5 minutes, followed by turning over the fabric and curing in reverse for 0.5 minutes at the same temperature.
• the treated nonwoven fabrics were then tested for oil and water repellency. The results are given in table 18.
• Table 19 cotton and nylon fabric treated with a blend of fluorochemical vinylether polymer and THV-220
• Table 20 cotton fabric treated with a blend of fluorochemical vinylether polymer and THV-220
• Examples 95 to 108 In examples 95 to 108 shown in Tables 21 and 22, 65/35 PES/CO-2 and 100% cotton US-
• examples 109 and 111 65/35 PES/CO-2 fabric samples were treated with various fluorochemical vinylether polymers so as to give 0.6% SOF.
• examples 110 and 112 also shown in Table 23
• All of the above-mentioned treating compositions additionally contained by weight: 10% glyoxal-type permanent press resin (PermafreshTM ULF, available from Omnova Solutions, Chester, SC) to give 1.6% SOF, 2.5% buffered magnesium salt catalyst (FreecatTM MX, available from B. F.
• Table 24 Oil and water repellency of 100% cotton US treated with fluorochemical vinylether polymers, initially and after 5 launderings.
• Table 25 Oil and water repellency of 100% cotton US-3 freated with fluorochemical vinylether polymers, initially and after 5 launderings.
• Table 26 Oil and water repellency of 100% nylon US treated with fluorochemical vinylether polymers, initially and after 5 launderings.

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