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
  • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
  • D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
  • D06M10/025—Corona discharge or low temperature plasma
• • 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
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
  • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
  • D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2262—Coating or impregnation is oil repellent but not oil or stain release
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]

Definitions

• the invention relates to materials of polyolefin fibers, which have been given oleophobic properties by a special treatment.
• Polyolefin fibers in particular polyethylene or polypropylene fibers, are very non-polar materials, and therefore have no oil-repellent properties. However, for certain uses of such fibers, oleophobic properties are desired or required. This applies, for example, if textile fabrics made from these fibers are to be used in the medical field; Corresponding articles include drapes or fleeces for operations or garment items for surgical personnel requiring good oil / soil repellency in addition to good water / alcohol repellency. In addition, fiber materials made of polyolefin fibers are superior to many other fiber materials in the field of inexpensive "disposables" because of their ready availability and cost-effective production.
• the object of the present invention was to provide textile fabrics of 90-100% by weight of polyolefin fibers which have oil-repellent or oleophobic properties.
• the polyolefin fiber materials are treated only with plasma and with polyorganosiloxane according to process steps a) and b), but without treatment with RF polymers according to process step c), no oil-repellent properties result. If, on the other hand, one waives process step b), after plasma treatment (step a)) and treatment with RF polymers (step c)), although a certain oleophobicity of the fiber material results, this is not sufficient for a number of purposes. Only through the additional implementation of process step b) is an excellent level of oil-repellent properties achieved.
• textile fabrics which consist of 90 to 100% by weight of polyolefin fibers.
• they consist of 100% by weight of polyolefin fibers, however, up to a maximum of 10% by weight of other fibers may be included.
• the textile fabrics are preferably fleeces (nonwovens), but may also be woven, depending on the intended use.
• the preferred polyolefin fibers are polypropylene fibers, but polyethylene fibers or blends of polypropylene fibers and polyethylene fibers may also be used.
• the good oil-repellent properties of the fiber materials can already be achieved by drying the fiber materials in a relatively low temperature range, e.g. from 80 to 120 ° C, obtained. This is important in polyolefin materials, because these fibers can suffer damage at temperatures above 130 ° C.
• Inventive fabrics made of polyolefin fibers can be produced by the process steps a), b) and c) mentioned above and in claim 1. All 3 steps are essential to achieve the desired oil-repellent effects. Step a) must be carried out before steps b) and c). Subsequent to step a), the method steps b) and c) must be carried out either in such a way that step b) and then step c) are carried out first or in such a way that steps b) and c) are carried out simultaneously.
• steps b) and c) can be carried out, for example, by treating the fiber material after carrying out step a) with a mixture containing the polyorganosiloxane to be used in step b) and additionally the polymer to be used in step c) Perfluoroalkyl groups (RF) contains.
• a suitable mixture is, for example, a stable aqueous dispersion which is applied by means of a padding process and which contains said polyorganosiloxane and said RF polymer and optionally one or more dispersants.
• Process step b) can be carried out earlier than process step c) or simultaneously with process step c). However, step c) may not take place earlier than step b).
• step c) is carried out in such a way that the treatment with the polymer which contains perfluoroalkyl groups takes place only on one surface of the textile fabric, for example by spray application, articles can be produced which only have one surface have very good oil repellency properties.
• the textile fabric is treated from polyolefin fibers in a plasma.
• This has the purpose of activating the surface of the polyolefin fibers in such a way that the subsequent treatments in process steps b) and c) bring about a good anchoring of polyorganosiloxane and RF polymer on the fiber surface.
• the plasma treatment must be carried out so that the textile fabric has a surface tension in the range of 35 to 60, preferably 40 to 55 mN / m after carrying out process step a).
• Suitable process conditions and equipment for the plasma treatment are known in the art.
• the apparatus "AS Corona Star” Ahlbrandt Systems, DE called.
• ambient medium has proven to be particularly suitable for practice as a medium for the plasma treatment in process step a).
• a He / O 2 mixture is also suitable as a medium.
• the plasma treatment is carried out under reduced pressure, for example at a pressure in the range of 0.1 to 1 mbar.
• polar centers are generated on the fiber surface under the action of an electric field. Products can then subsequently be bonded to the fiber material at this polar surface.
• the textile fabric obtained according to process step a) is treated with a polyorganosiloxane.
• This polyorganosiloxane when it is liquid and its viscosity is within a suitable range, can be applied undiluted to the polyolefin sheet, e.g. by foam, spray or by bath application. In other cases, it may be convenient to use the siloxane in dilute form, e.g. in the form of an aqueous solution or dispersion.
• Suitable dispersants are known to the person skilled in the art. These include, but are not limited to, conventional nonionic surfactants such as ethoxylated alcohols or ethoxylated amines.
• Aqueous dispersions of polyorganosiloxanes suitable for step b) are available on the market, e.g. the product ULTRATEX FH new of the company Ciba Spezialitätenchemie Pfersee GmbH.
• Another commercially available product containing a polyorganosiloxane suitable for process step b) is the product MAGNASOFT TLC from General Electric Silicones.
• a mixture which comprises the polysiloxane required for step b) and the polymer with perfluoroalkyl groups required for step c) (RF polymer).
• This mixture may optionally contain only the two polymers mentioned in undiluted form. Usually, however, it additionally contains at least one diluent. Preferred for this purpose is water for environmental and cost reasons.
• the mixture is preferably an aqueous solution or dispersion which contains the two polymers and optionally one or more dispersants.
• Such mixtures can be prepared in a simple manner by combining an aqueous solution or dispersion A with an aqueous solution or dispersion B, where A contains the polyorganosiloxane required for process step b) and B contains the RF polymer required for process step c).
• A contains the polyorganosiloxane required for process step b)
• B contains the RF polymer required for process step c).
• the application of the mixture to the textile fabric of polyolefin fibers can be carried out advantageously by foam application, spraying or by bath application, for example by a tatting or padding process.
• the amount of polyorganosiloxane used in step b) and the amount of polymer having perfluoroalkyl groups applied to the polyolefin fiber material in step c) can vary within larger limits. In individual cases, they depend on the extent of the oil-repellent properties to be achieved.
• a preferred range for the amount of polyorganosiloxane on the textile fabric after application and drying is between 0.1 and 4% by weight of polyorganosiloxane, based on the total weight of the fiber material after carrying out steps b) and c) and after drying.
• the polyorganosiloxane which is used in process step b). From the group of polyorganosiloxanes, only those are suitable which are end groups of the polysiloxane chain units of the formula R 3 Si-O- exhibit.
• all radicals R independently of one another methyl, ethyl or phenyl radicals.
• 80 to 100% of all radicals R present are methyl radicals.
• the polyorganosiloxanes used in step b) are preferably linear, ie they preferably contain no Si atoms in side chains.
• the polyorganosiloxanes must have, within the polyorganosiloxane chain, units of the formula (I) -Si (R) 2 -O- (I) and units of the formula (II) -Si (R) (X) -O- (II) contain.
• all radicals R independently of one another have the abovementioned meaning.
• 80 to 100% of all radicals R present are methyl radicals.
• All radicals X present are a radical of the formula (III)
• t is a number from 1 to 4 and z is a number from 5 to 60.
• one of the radicals R 1 and R 2 is hydrogen and the other is hydrogen or a methyl group.
• Each radical R 3 present stands for H or a radical R of the abovementioned type.
• radicals R 3 present are hydrogen.
• both the radicals R 1 and the radicals R 2 are hydrogen. It is even more advantageous if in 80 to 100% of these units both of the radicals R 1 and R 2 are hydrogen.
• Polyorganosiloxanes containing only polyoxyethylene but no polyoxypropylene radicals are particularly well suited.
• Polyorganosiloxanes which can be used in process step b) can be used, as stated above, either undiluted or in combination with a diluent.
• a particularly preferred diluent is water, optionally containing one or more dispersants, so that in process step b) preferably aqueous dispersions of suitable polysiloxanes are used.
• Polyorganosiloxanes which can be used in process step b) or aqueous dispersions of such polysiloxanes are available on the market and can be prepared by processes known to those skilled in the art. This is the description of the one mentioned at the beginning JP-A 2004/156 163 suitable products and their production.
• process step b) it is preferred to use polyorganosiloxanes of the following formula (IV) or aqueous dispersions of such polyorganosiloxanes.
• n is a number from 15 to 25 and p is a number from 3 to 10.
• step c) which, as mentioned, can be carried out simultaneously with step b) or adjoins step b), the textile fabric of polyolefin fibers is treated with a polymer which contains perfluoroalkyl groups (RF groups).
• This polymer is a polyacrylic polymer or a polyurethane. It is also possible to use mixtures of these two polymers.
• polyacrylic polymers are poly (meth) acrylic acid esters in question, which have in the alcohol-derived component RF groups. They can be prepared by esterification of (meth) acrylic acid or derivatives thereof with alcohols containing RF groups, and subsequent polymerization or corresponding esterification of poly (meth) acrylic acid or its derivatives.
• Polyurethane containing RF groups can be obtained by polyaddition of polyfunctional isocyanates with diols or polyols containing RF groups.
• either a polyacrylic polymer or a polyurethane is applied in step c) to the fiber materials which consist of 80-100% by weight of polyolefin fibers.
• the polymer used contains perfluoroalkyl groups and, if it is a polyurethane, can be prepared by reacting a polyfunctional isocyanate or a mixture of such isocyanates with a polyhydric alcohol containing one or more perfluoroalkyl groups of the formula (V) CF 3 - (CF 2 ) a - (V) contains, or with a mixture of such alcohols.
• divalent isocyanates ie compounds having two -NCO groups and dihydric alcohols, ie diols, are used for the reaction.
• a is a number from 3 to 23, preferably a number from 5 to 15.
• the polyurethanes obtained in the reaction mentioned have a plurality of repeating units of the formula on.
• R 4 and R 5 are those polyvalent organic radicals derived from the polyvalent isocyanates used R 5 (NCO) 2 and alcohols R 4 (OH) 2 , wherein each R 4 contains one or more RF groups.
• R 4 and R 5 are divalent radicals which contain no further NCO or OH groups, ie preferably divalent isocyanates and dihydric alcohols are used.
• the reaction of the polyfunctional isocyanates with the polyhydric alcohols is preferably carried out in proportions such that the resulting polyurethane does not contain free isocyanate groups or only in insubstantial amounts, ie in an amount of less than 5%, based on the NCO groups present before the reaction.
• the reaction of the polyfunctional isocyanates with the polyhydric alcohols can be carried out by methods known from urethane chemistry. Such methods are described, for example in the US 3,968,066 , of the US 4 054 592 and the US 4,898,981 , Preferably This reaction is carried out in an organic solvent, for example in a dialkyl ketone, and using a catalyst or a mixture of catalysts. Suitable catalysts include trialkylamines and metal compounds such as tetraalkyl titanate.
• polyurethanes containing RF groups which are formed in the reaction described, are available on the market, for example from Du Pont, USA or Clariant, DE. Under the designation Phobotex ® 7808 or 7811, the company Ciba Spezi Rundschenchemie Pfersee GmbH provides aqueous dispersions of suitable RF-group-containing polyurethanes.
• a polyurethane which can be prepared by reacting an aliphatic diisocyanate or a mixture of aliphatic diisocyanates with a diol of the formula (VI) or of the formula (VII) C (-CH 2 OH) 2 (-CH 2 -S-CH 2 CH 2 -RF) 2 (VI) [RF-CH 2 -CH (OH) -CH 2 -] 2 S (VII) wherein RF is a radical of formula (V) given above, where a is a number from 5-19, or with a mixture of such diols.
• the application of the perfluoroalkyl-containing polyurethane to the polyolefin fiber material can be carried out by methods which are customary in textile finishing / finishing, for example via a patting or roll application method.
• Preferred for this purpose is an application by means of a padding method with subsequent drying of the fiber material.
• the polyurethane is preferably applied to the fiber material in the form of an aqueous dispersion. This dispersion may contain the polyurethane at a concentration common to the padding process, for example in the range of 0.05 to 50.0% by weight.
• the content of the RF polymers on the finished article may be in a range such that the article has a fluorine content in the range of 0.01 to 2.0% by weight.
• the polyurethane-containing aqueous dispersions normally additionally contain one or more surface-active products as dispersants. Dispersants used are preferably one or more nonionic or cationic dispersants or a mixture of one or more cationic and one or more nonionic dispersants. In individual cases it is also possible to use anionic dispersants or a mixture of an anionic and a nonionic dispersant.
• the amount of dispersant or dispersant mixture may be in the usual, known range, for example in the range from 1 to 10% by weight, based on the total amount of dispersion.
• Known cationic dispersants include, inter alia, known quaternary ammonium salts, ethoxylated long-chain alcohols known as nonionic dispersants.
• the aqueous dispersions of the polyurethanes can be prepared by generally known methods, for example by dissolving one or more dispersants in water, adding the polyurethane and mechanically homogenizing.
• the polyurethane can in this case be added in pure form to the aqueous solution or as a solution or dispersion in an organic solvent. In the latter case, the organic solvent is removed after the homogenization of the aqueous dispersion, advantageously by distillation.
• Suitable organic solvents include dialkyl ketones.
• extenders may be applied to the fiber materials together with the polyurethanes containing RF groups.
• Extenders are products known in the art, e.g. Compounds with blocked by oxime isocyanate groups suitable. Such extenders are capable of enhancing the oil and water repellency properties of the fiber materials.
• extenders with oxime-blocked isocyanate groups must be exposed to higher temperatures, often at temperatures above 130 ° C, so that the blocking is reversed and the extenders exert their effect. For this reason, the additional use of extenders in the process leading to products of the invention is limited to those cases where the fibers are not damaged by the temperatures required for deblocking.
• polyacrylic polymers which contain perfluoroalkyl groups (RF groups). It has been found that, in a number of cases, polyacrylic polymers containing RF groups give even better results than the said RF group-containing polyurethanes.
• Polyacrylate containing RF groups, aqueous dispersions thereof and their preparation are known to the person skilled in the art. Suitable products are in the US 2004/0075074 A1 and the US 2004/0147665 A1 described. Furthermore, suitable acrylic polymers and aqueous dispersions thereof are available on the market for process step c).
• Polyacrylic polymers having perfluoroalkyl groups are preferably esters of polyacrylic acid or methacrylic acid which have RF groups in the alcohol-derived moiety. These polymers are preferably products with the recurring structural unit -CH 2 -C (T) [COO (CH 2 ) w -RF] - wherein T is H or CH 3 , w is a number from 2 to 6 and RF is a radical of the above formula (V).
• Such acrylate polymers can be prepared by esterification or transesterification of poly (meth) acrylic acids or their derivatives with alcohols containing RF groups.
• the speed at which the nonwoven was passed through the apparatus was 10 m / min.
• the residence time was fractions of seconds, the power of the apparatus 600 W, the electrode length 40 cm (Ahlbrandt AS Corona Star as an apparatus).
• (method steps b) and c)) an aqueous dispersion was applied to the nonwoven by means of a padding process.
• the dispersion contained 50 g / l of a polyorganosiloxane (ULTRATEX FH new) and 100 g / l of a polyacrylate, ie, a polyacrylic acid ester containing perfluoroalkyl groups in the alcohol component.
• the liquor pickup was 20% by weight, based on the weight of the nonwovens before application of the aqueous dispersion.
• the nonwoven was dried at 120 ° C for 1 minute.
• Example 2 (noninventive comparative example )
• Example 1 was repeated, but with the difference that the aqueous dispersion contained only 100 g of the polyacrylate having RF groups, but no polysiloxane, i. only process steps a) and c) were carried out, but no step b).
• Example 3 non-inventive comparative example
• Example 2 was repeated, but without previous plasma treatment, i. only one process step c) was carried out, but no steps a) and b).
• a nonwoven polypropylene was treated with plasma as in Example 1. Subsequently, an aqueous dispersion was spray applied to the nonwoven.
• the dispersion contained 100 g / l ULTRATEX FH neu and 500 g / l of an RF group-containing polyurethane (PHOBOTEX 7811). The order after drying (5 minutes / 120 ° C) corresponded to a weight gain of 30%.
• Example (No. 4) of the present invention is superior to Comparative Examples (Nos. 5 and 6).

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• 2006
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