EP0036475B1 - Pile-stabilizing textile impregnant, process for preparing it and textile treated with this composition - Google Patents
Pile-stabilizing textile impregnant, process for preparing it and textile treated with this composition Download PDFInfo
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- EP0036475B1 EP0036475B1 EP81100613A EP81100613A EP0036475B1 EP 0036475 B1 EP0036475 B1 EP 0036475B1 EP 81100613 A EP81100613 A EP 81100613A EP 81100613 A EP81100613 A EP 81100613A EP 0036475 B1 EP0036475 B1 EP 0036475B1
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- Prior art keywords
- pile
- textile
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- silanes
- impregnating agent
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
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- 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
- Y10T428/23907—Pile or nap type surface or component
- Y10T428/23986—With coating, impregnation, or bond
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- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2962—Silane, silicone or siloxane in coating
Definitions
- the present invention relates to a pile stabilizing textile impregnating agent and a method for its production.
- Carpets loaded in this way have pressure points, grooves and an uneven pile (so-called walking streets).
- Furniture upholstery fabrics undergo similar changes in their surface properties, preferably in the most easily accessible and most heavily used areas. The result is a non-uniform appearance of the textile surface.
- silsesquioxane suspensions described there are relatively unstable and are in no way suitable for pole stabilizing equipment.
- this object is achieved in that aqueous methylsilsesquioxane dispersions are used in combination with colloidal silica to finish the textiles.
- the present invention therefore relates to a pile-stabilizing textile impregnating agent containing colloidal suspensions of organosilsesquioxanes and of silica with SiO 2 units.
- the invention further relates to a process for the preparation of such stable, aqueous methylsilsesquioxane / silica dispersions. It is characterized in that silanes of the general formula R-Si (OR ') 3 , together with silanes Si (OR') 4 , in which R is a substituted or unsubstituted hydrocarbon radical having 1 to 7 carbon atoms, the substituents of which are halogen atoms, amino or mercapto - And epoxy groups and up to 95% of the radicals R are methyl and R 'is an alkyl radical having 1 to 4 carbon atoms, to a mixture of water, a buffer substance, a surface-active agent and optionally an organic solvent with agitation and under acid or basic conditions are added.
- silane To achieve a very narrow particle size distribution and a small average particle size of approximately 200 to 500 angstroms, a uniform and slow addition of the amount of silane is required.
- the exact amount of silane that can be added depends on the substituent R and whether an anionic or cationic surfactant is used.
- the simultaneous hydrolysis of the silanes results in copolymers of the silsesquioxanes in which the units can be present in block form or in a random distribution.
- the preferred amount of added silane of the general formula Si (OR ') 4 is 2 to 50 percent, based on the total amount of silanes used, preferably 3 to 20 percent (% by weight).
- the agent according to the invention is composed approximately as follows: wherein about 2 to 9 wt .-% silsesquioxane and about 0.1 - 0.4 wt .-% contains SiO z units.
- the surface-active agents mentioned have the function of stabilizing the particles formed in the colloidal suspensions.
- Suitable anionic surface-active agents are aliphatic and / or aromatic sulfonic acids, for example decyl, dodecyl, cetyl, stearyl, myristyl or oleyl sulfonic acids or their alkali metal salts. If cationic surfactants are used, it is advantageous to use halides and especially chlorides and bromides. Other surfactants, including those of a nonionic and amphoteric nature, can be used in conjunction with the above agents provided they do not interfere with the stability of the colloidal suspension due to their nature or amount.
- the surfactants are used in an amount of about 0.01 to about 15%, based on the amount of silane used.
- the process for the preparation of the colloidal suspensions according to the invention can be carried out at temperatures between room temperature and 80 ° C .; the temperature range between 50 and 70 ° C. is particularly preferred.
- the buffer substances such. B. sodium tetraborate, ammonium bicarbonate, sodium bicarbonate, potassium bicarbonate are used in amounts of 0.05 to 4 wt .-% based on the total mixture.
- the finish is effective on all pile and pile goods made of synthetic, organic and inorganic fibers and natural fibers.
- finishing products can be applied either before, during or after the dyeing of the textile or subsequent further finishing steps, or subsequently after processing as a cover, upholstery or floor covering textile by treatment in the liquor, padding or spraying.
- Another method of applying the colloidal dispersions to the fiber material is to use them together with a cleaning agent, especially if the textile to be treated has been soiled by use or previous processing steps. It is preferable to finish goods that have not been equipped by the manufacturer after wet cleaning by spraying the preparation onto the goods.
- 1.7 g of sodium hydrogen carbonate and 8 g of a cationic surfactant are dissolved in 1700 g of distilled water at room temperature and heated to 70.degree. After this temperature has been reached, 300 g of methyltriethoxysilane and 12 g of tetraethoxysilane are added over the course of 4 hours, the temperature of the reaction mixture being kept at 70.degree. After the addition has ended, the resulting sol is stirred at 70 ° C. for 3 hours and then cooled to room temperature.
- the product obtained is an easily mobile, slightly opaque liquid.
- a tufted fabric with cut pile (100% polyamide) with a pile weight of 350 g / m 2 was, after dyeing, dried with 3% of the preparation according to the invention of Example 2, based on the pile weight, by spraying with the aid of a single-component spraying system equipped and then dried at 120 ° C for 5 minutes on a stenter. The goods were then shaved evenly and the back was coated with a commercially available latex foam.
- Samples were also taken from the goods that had not been treated with the preparation according to the invention (sample A).
- a tufted fabric with cut pile (100% polyamide) with a pile weight of 1200 g / m 2 was, after dyeing, before drying with 3% of the preparation according to the invention of Example 1, based on the pile weight, after the pull-out process on a reel skid after dyeing in last rinse for 15 minutes at 30 ° C. The subsequent drying was carried out on a stenter for 5 minutes at 150 ° C. The goods were then sheared evenly and the back was coated with a commercially available latex foam.
- Samples were taken from this material in accordance with the DIN regulations (sample B). Samples were also taken from the goods that had not been treated with the preparation according to the invention (sample A).
- a tufted fabric with cut pile (100% wool) with a pile weight of 850 g was equipped with 4% of the preparation according to the invention after the pull-out process in the yarn after dyeing in the last rinsing bath (15 '/ 30 ° C.). Drying at 120 ° C. The yarn was then deepened, sheared and coated.
- Pieces of 50 x 30 cm were removed and subjected to a walk test by laying two treated and two untreated samples in a checkered manner in a passenger elevator cabin. In the cabin room, the material is subjected to a more intensive surface stress due to the rotating movements of the people using the elevator than when walking on it. The number of inspections is counted electronically. After every 10,000 inspections, the samples in the fields are exchanged cyclically to ensure an even load. After 30,000 inspections, the samples are removed and visually assessed by 6 different assessors. The surface change of the untreated samples is evaluated (A) compared to the treated samples (B).
- Samples of 30 x 30 cm were taken and laid out on a laboratory table covered with VA steel.
- the load was caused by a steel weight with a support surface coated with polytetrafluoroethylene. (Contact pressure: 78.6 g / cm 2 ; duration of the load: 24 hours).
- Example 6 The mixture was then dried at 150 ° C. for 5 minutes and further treated as indicated in Example 3. The subsequent assessment was carried out as indicated in Example 6:
- the mixture was then dried at 150 ° C. for 5 minutes, shaved evenly, and the back was coated with a commercially available latex sheet foam.
- the samples are first soiled with 10 g of synthetic dirt of the following composition.
- the samples are loaded after the chair roller test, which is described in detail in the DIN regulation 54 324, with a total roller load of 60 kg and a change in the direction of roller rotation after every 50 revolutions.
Abstract
Description
Die vorliegende Erfindung betrifft ein polstabilisierendes Textilimprägniermittel sowie ein Verfahren zu dessen Herstellung.The present invention relates to a pile stabilizing textile impregnating agent and a method for its production.
Von modernen Textilmaterialien, die z. B. als Möbelbezugsstoffe oder als textiler Bodenbelag Verwendung finden, erwartet der Verbraucher günstige Eigenschaften im Hinblick auf ihre mechanische Beanspruchbarkeit, also ihre statische und dynamische Belastbarkeit.Of modern textile materials, e.g. B. find use as upholstery fabrics or as textile flooring, the consumer expects favorable properties in terms of their mechanical strength, so their static and dynamic resilience.
Ein besonderes Problem bei Gegenständen aus Polware, das heißt Textilien, die durch Schlingen oder aufgeschnittene Schlingen (Velour) eine bestimmte Struktur der Oberfläche besitzen, ist die Erhaltung dieser Oberflächenstruktur während ihrer Gebrauchsdauer. Die Erfahrung ist weit verbreitet, daß zum Beispiel Teppichböden aus Polware schon nach relativ kurzer Benutzungszeit durch Begehen, schwere aufliegende Gegenstände wie beispielsweise Möbelstücke oder durch Befahren mit Rollstühlen Schädigungen aufweisen, die sich durch eine Veränderung der Oberflächenbeschaffenheit auszeichnen.A particular problem with articles made of pile goods, that is to say textiles which have a certain structure of the surface due to loops or cut loops (velor), is the preservation of this surface structure during its service life. Experience has shown that carpets made of pile goods, after walking for a relatively short period of time, show damage due to walking on them, heavy objects such as furniture or wheelchairs, which are characterized by changes in the surface properties.
Solcherart belastete Teppichböden haben Druckstellen, Rillen und ungleichmäßig liegenden Flor (sog. Gehstraßen).Carpets loaded in this way have pressure points, grooves and an uneven pile (so-called walking streets).
Möbelbezugsstoffe erleiden gleichartige Veränderungen ihrer Oberflächenbeschaffenheit, vorzugsweise an den am leichtesten zugänglichen und am stärksten belasteten Stellen. Die Folge ist ein ungleichförmiges Aussehen der Textiloberfläche.Furniture upholstery fabrics undergo similar changes in their surface properties, preferably in the most easily accessible and most heavily used areas. The result is a non-uniform appearance of the textile surface.
Es sind bereits an anderer Stelle Verfahren zur Behandlung von Fasermaterialien wie Fäden, Fasern, Gewebe und Teppich beschrieben worden (z. B. DE-OS 1 594 985), um diesen Rutschsicherheit und Widerstandsfähigkeit gegen Trockenschmutz zu verleihen. Bei diesem Verfahren werden kolloidale Suspensionen von Silsesquioxanen aus Einheiten der Formel RSi03/2 mit einer Teilchengröße von 10 bis 1000 Angström verwendet.Processes for treating fiber materials such as threads, fibers, fabrics and carpets have already been described elsewhere (for example DE-OS 1 594 985) in order to give them slip resistance and resistance to dry dirt. In this process, colloidal suspensions of silsesquioxanes from units of the formula RSi0 3/2 with a particle size of 10 to 1000 angstroms are used.
Die dort beschriebenen Silsesquioxansuspensionen sind aber relativ unbeständig und sind in keinem Fall zur polstabilisierenden Ausrüstung geeignet.However, the silsesquioxane suspensions described there are relatively unstable and are in no way suitable for pole stabilizing equipment.
Es war daher Aufgabe der vorliegenden Erfindung, ein Mittel zur polstabilisierenden Ausrüstung von Textilien von Chemie- oder Naturfaserstoffen und deren Mischungen bereitzustellen, welches wirksam, dauerhaft und pflegebeständig ist.It was therefore an object of the present invention to provide an agent for the pile stabilizing finishing of textiles of chemical or natural fiber materials and their mixtures, which is effective, durable and maintenance-resistant.
Erfindungsgemäß wird diese Aufgabe dadurch gelöst, daß zur Ausrüstung der Textilien wäßrige Methylsilsesquioxandispersionen in Kombination mit kolloidaler Kieselsäure verwendet werden.According to the invention, this object is achieved in that aqueous methylsilsesquioxane dispersions are used in combination with colloidal silica to finish the textiles.
Gegenstand der vorliegenden Erfindung ist daher ein polstabilisierendes Textilimprägniermittel enthaltend kolloidale Suspensionen von Organosilsesquioxanen und von Kieselsäure mit Si02-Einheiten.The present invention therefore relates to a pile-stabilizing textile impregnating agent containing colloidal suspensions of organosilsesquioxanes and of silica with SiO 2 units.
Gegenstand der Erfindung ist ferner ein Verfahren zur Herstellung von solchen stabilen, wäßrigen Methylsilsesquioxan-/Kieselsäuredispersionen. Es ist dadurch gekennzeichnet, daß Silane der allgemeinen Formel R-Si (OR')3, zusammen mit Silanen Si(OR')4, worin R ein substituierter oder unsubstituierter Kohlenwasserstoffrest mit 1 bis 7 Kohlenstoffatomen, dessen Substituenten Halogenatome, Amino-, Mercapto- und Epoxygruppen sein können und bis zu 95% der Reste R Methyl sind und R' einen Alkylrest mit 1 bis 4 Kohlenstoffatomen bedeutet, zu einem Gemisch aus Wasser, einer Puffersubstanz, einem oberflächenaktiven Mittel und gegebenenfalls einem organischen Lösungsmittel unter Bewegung und unter sauren oder basischen Bedingungen zugegeben werden.The invention further relates to a process for the preparation of such stable, aqueous methylsilsesquioxane / silica dispersions. It is characterized in that silanes of the general formula R-Si (OR ') 3 , together with silanes Si (OR') 4 , in which R is a substituted or unsubstituted hydrocarbon radical having 1 to 7 carbon atoms, the substituents of which are halogen atoms, amino or mercapto - And epoxy groups and up to 95% of the radicals R are methyl and R 'is an alkyl radical having 1 to 4 carbon atoms, to a mixture of water, a buffer substance, a surface-active agent and optionally an organic solvent with agitation and under acid or basic conditions are added.
Zur Erzielung einer sehr engen Teilchengrößenverteilung und einer geringen durchschnittlichen Teilchengröße von etwa 200 bis 500 Angström ist eine gleichförmige und langsame Zugabe der Silanmenge erforderlich. Die genaue Silanmenge, die zugegeben werden kann, hängt vom Substituenten R ab und davon, ob ein anionisches oder kationisches oberflächenaktives Mittel verwendet wird.To achieve a very narrow particle size distribution and a small average particle size of approximately 200 to 500 angstroms, a uniform and slow addition of the amount of silane is required. The exact amount of silane that can be added depends on the substituent R and whether an anionic or cationic surfactant is used.
Es entstehen durch die gleichzeitige Hydrolyse der Silane Mischpolymerisate der Silsesquioxane, worin die Einheiten in Blockform oder statistisch verteilt vorliegen können. Die bevorzugte Menge an zugesetztem Silan der allgemeinen Formel Si(OR')4 beträgt 2 bis 50 Prozent, bezogen auf die Gesamtmenge der eingesetzten Silane, vorzugsweise 3 bis 20 Prozent (Gew.-%).The simultaneous hydrolysis of the silanes results in copolymers of the silsesquioxanes in which the units can be present in block form or in a random distribution. The preferred amount of added silane of the general formula Si (OR ') 4 is 2 to 50 percent, based on the total amount of silanes used, preferably 3 to 20 percent (% by weight).
Das erfindungsgemäße Mittel ist etwa wie folgt zusammengesetzt:
Die genannten oberflächenaktiven Mittel haben die Funktion, die gebildeten Teilchen der kolloidalen Suspensionen zu stabilisieren.The surface-active agents mentioned have the function of stabilizing the particles formed in the colloidal suspensions.
Bevorzugt werden folgende Silane eingesetzt:
- Methyltrimethoxysilan, Methyltriethoxysilan, Methyltriisopropoxysilan, Ethyltrimethoxysilan, Ethyltriethoxysilan, Propyltrimethoxysilan, Isobutyltrimethoxysilan, Isobutyltriethoxysilan, 2-Ethylbutyltriethoxysilan, Tetraethoxysilan, 2-Ethylbutoxytriethoxysilan.
- Methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, 2-ethylbutyl triethoxysilane, tetraethoxysilane, 2-ethylbutoxytriethoxysilane.
Als anionische oberflächenaktive Mittel kommen aliphatische und/oder aromatische Sulfonsäuren in Betracht, beispielsweise Decyl-, Dodecyl-, Cetyl-, Stearyl-, Myristyl- oder Oleylsulfonsäuren oder deren Alkalisalze. Werden kationische oberflächenaktive Mittel verwendet, ist es vorteilhaft, Halogenide und insbesondere Chloride und Bromide zu verwenden. Andere oberflächenaktive Mittel, einschließlich solche von nichtionogener und amphoterer Natur, können in Verbindung mit den oben genannten Mitteln verwendet werden, sofern dieselben weder auf Grund ihrer Natur noch ihrer Menge einen störenden Einfluß auf die Stabilität der kolloidalen Suspension ausüben.Suitable anionic surface-active agents are aliphatic and / or aromatic sulfonic acids, for example decyl, dodecyl, cetyl, stearyl, myristyl or oleyl sulfonic acids or their alkali metal salts. If cationic surfactants are used, it is advantageous to use halides and especially chlorides and bromides. Other surfactants, including those of a nonionic and amphoteric nature, can be used in conjunction with the above agents provided they do not interfere with the stability of the colloidal suspension due to their nature or amount.
Die oberflächenaktiven Mittel werden in einer Menge von etwa 0,01 bis etwa 15%, bezogen auf die eingesetzte Silanmenge, eingesetzt.The surfactants are used in an amount of about 0.01 to about 15%, based on the amount of silane used.
Das Verfahren zur Herstellung der erfindungsgemäßen kolloidalen Suspensionen kann bei Temperaturen zwischen Raumtemperatur und 80° C durchgeführt werden; besonders bevorzugt ist der Temperaturbereich zwischen 50 und 70°C.The process for the preparation of the colloidal suspensions according to the invention can be carried out at temperatures between room temperature and 80 ° C .; the temperature range between 50 and 70 ° C. is particularly preferred.
Für den beanspruchten Anwendungszweck ist der Zusatz eines den pH-Wert steuernden Puffers von besonderer Wichtigkeit.The addition of a buffer controlling the pH is of particular importance for the claimed application.
Die Puffersubstanzen wie z. B. Natriumtetraborat, Ammoniumhydrogencarbonat, Natriumhydrogencarbonat, Kaliumhydrogencarbonat werden in Mengen von 0,05 bis 4 Gew.-% bezogen auf die Gesamtmischung eingesetzt.The buffer substances such. B. sodium tetraborate, ammonium bicarbonate, sodium bicarbonate, potassium bicarbonate are used in amounts of 0.05 to 4 wt .-% based on the total mixture.
Da bekanntlich das Hydrolyseverhalten von Alkoxysilanen und die Kondensation von Silanolgruppen pH-wertabhängig sind, scheinen durch die erfindungsgemäße Steuerung beider Vorgänge durch puffernde Substanzen besonders günstige Voraussetzungen für die Herstellung polstabilisierender Zusammensetzungen geschaffen zu sein.Since, as is well known, the hydrolysis behavior of alkoxysilanes and the condensation of silanol groups are pH-dependent, the control of both processes according to the invention by buffering substances seems to create particularly favorable conditions for the production of pole-stabilizing compositions.
Die Ausrüstung ist auf jeder Pol- und Florware aus Chemiefaserstoffen auf organischer und anorganischer Basis und auf Naturfaserstoffen wirksam.The finish is effective on all pile and pile goods made of synthetic, organic and inorganic fibers and natural fibers.
Die Applikation der Ausrüstungsprodukte kann entweder vor, während oder nach der Einfärbung des Textils oder anschließender weiterer Veredelungsschritte erfolgen oder nachträglich nach erfolgter Verarbeitung als Bezugs-, Polster- oder Bodenbelagstextil durch Behandlung in der Flotte, Klotzen oder Aufsprühen.The finishing products can be applied either before, during or after the dyeing of the textile or subsequent further finishing steps, or subsequently after processing as a cover, upholstery or floor covering textile by treatment in the liquor, padding or spraying.
Eine weitere Methode zum Aufbringen der kolloidalen Dispersionen auf das Fasermaterial besteht darin, diese zusammen mit einem Reinigungsmittel zu verwenden, besonders dann, wenn das zu behandelnde Textil durch Gebrauch oder vorhergegangene Verarbeitungsschritte verschmutzt wurde. Vorzugsweise erfolgt die Ausrüstung bisher noch nicht vom Hersteller ausgerüsteter Ware nach ihrer Naßreinigung durch Aufsprühen der Zubereitung auf die Ware.Another method of applying the colloidal dispersions to the fiber material is to use them together with a cleaning agent, especially if the textile to be treated has been soiled by use or previous processing steps. It is preferable to finish goods that have not been equipped by the manufacturer after wet cleaning by spraying the preparation onto the goods.
Die nachfolgenden Beispiele sollen die Erfindung näher erläutern, ohne sie dadurch einzuschränken.The following examples are intended to explain the invention in more detail without restricting it.
In 1700 g destilliertes Wasser werden 1,7 g Natriumhydrogencarbonat und 8 g eines kationischen Tensids (quarternäres Alkyl/Aryl-Ammoniumchlorid) bei Raumtemperatur gelöst und auf 70°C erwärmt. Nach Erreichen dieser Temperatur werden 300 g Methyltriethoxysilan und 12 g Tetraethoxysilan innerhalb von 4 Stunden zugegeben, wobei die Temperatur des Reaktionsgemisches auf 70° C gehalten wird. Nach beendeter Zugabe wird das entstandene Sol während 3 Stunden bei 70° C gerührt und anschließend auf Raumtemperatur abgekühlt.1.7 g of sodium hydrogen carbonate and 8 g of a cationic surfactant (quaternary alkyl / aryl ammonium chloride) are dissolved in 1700 g of distilled water at room temperature and heated to 70.degree. After this temperature has been reached, 300 g of methyltriethoxysilane and 12 g of tetraethoxysilane are added over the course of 4 hours, the temperature of the reaction mixture being kept at 70.degree. After the addition has ended, the resulting sol is stirred at 70 ° C. for 3 hours and then cooled to room temperature.
Beim erhaltenen Produkt handelt es sich um eine leicht bewegliche, schwach opake Flüssigkeit.The product obtained is an easily mobile, slightly opaque liquid.
In einem 500 Liter fassenden Kessel werden 430 kg Wasser, 2,1 kg Natriumtetraborat und 0,4 kg eines anionischen Tensids (Na-Dodecylsulfonat) vorgelegt und unter Rühren auf 60° C erwärmt. Dann werden innerhalb von 5 Stunden 70 kg Methyltriethoxysilan und 8 kg Tetraethoxysilan zudosiert, wobei die Reaktionstemperatur auf 60° C gehalten wird. Nach abgeschlossener Zudosierung wird 3 Stunden bei gleicher Temperatur nachgerührt und anschließend auf Raumtemperatur abgekühlt. Das -Sol ist nach anschließender Filtration über ein Haarsieb mit einer lichten Maschenweite von 0,04 mm gebrauchsfertig.430 kg of water, 2.1 kg of sodium tetraborate and 0.4 kg of an anionic surfactant (Na dodecyl sulfonate) are placed in a 500 liter kettle and heated to 60 ° C. with stirring. 70 kg of methyltriethoxysilane and 8 kg of tetraethoxysilane are then metered in over the course of 5 hours, the reaction temperature being kept at 60.degree. After the addition is complete, the mixture is stirred for 3 hours at the same temperature and then cooled to room temperature. After subsequent filtration through a hair sieve, the sol is ready to use with a mesh size of 0.04 mm.
Einer Tufting-Ware mit Schnittflor (100% Polyamid) mit einem Polgewicht von 350 g/m2 wurde nach dem Färben vor dem Trocknen mit 3% der erfindungsgemäßen Zubereitung des Beispiels 2, bezogen auf das Polgewicht, durch Aufsprühen mit Hilfe einer Einstoff-Sprühanlage ausgerüstet und anschließend bei 120°C während 5 Minuten auf einem Spannrahmen getrocknet. Anschließend wurde die Ware gleichmäßig geschoren und der Rücken mit einem handelsüblichen Latex-Planschaum beschichtet.A tufted fabric with cut pile (100% polyamide) with a pile weight of 350 g / m 2 was, after dyeing, dried with 3% of the preparation according to the invention of Example 2, based on the pile weight, by spraying with the aid of a single-component spraying system equipped and then dried at 120 ° C for 5 minutes on a stenter. The goods were then shaved evenly and the back was coated with a commercially available latex foam.
Aus diesem Material wurden gemäß den DIN-Vorschriften Muster entnommen (Probe B).Samples were taken from this material in accordance with the DIN regulations (sample B).
Ebenso wurden Muster aus der Ware entnommen, die nicht mit der erfindungsgemäßen Zubereitung behandelt worden ist (Probe A).
Eine Tuftingware mit Schnittflor (100% Polyamid) mit einem Polgewicht von 1200 g/m2 wurde nach dem Färben vor dem Trocknen mit 3% der erfindungsgemäßen Zubereitung des Beispiels 1, bezogen auf das Polgewicht, nach dem Ausziehverfahren auf einer Haspelkufe nach dem Färben im letzten Spülbad während 15 Minuten bei 30°C behandelt. Die anschließende Trocknung erfolgte auf einem Spannrahmen während 5 Minuten bei 150°C. Anschließend wurde die Ware gleichmäßig geschoren und der Rücken mit einem handelsüblichen Latex-Planschaum beschichtet.A tufted fabric with cut pile (100% polyamide) with a pile weight of 1200 g / m 2 was, after dyeing, before drying with 3% of the preparation according to the invention of Example 1, based on the pile weight, after the pull-out process on a reel skid after dyeing in last rinse for 15 minutes at 30 ° C. The subsequent drying was carried out on a stenter for 5 minutes at 150 ° C. The goods were then sheared evenly and the back was coated with a commercially available latex foam.
Aus diesem Material wurden gemäß den DIN-Vorschriften Muster entnommen (Probe B). Ebenso wurden Muster aus der Ware entnommen, die nicht mit der erfindungsgemäßen Zubereitung behandelt worden ist (Probe A).
Eine Tufting-Ware mit Schnittflor (100% Wolle) mit einem Polgewicht von 850 g wurde nach dem Ausziehverfahren im Garn nach dem Färben im letzten Spülbad mit 4% der erfindungsgemäßen Zubereitung ausgerüstet (15'/30°C). Trocknen 120°C. Anschließend wurde das Garn vertuftet, geschoren und beschichtet.A tufted fabric with cut pile (100% wool) with a pile weight of 850 g was equipped with 4% of the preparation according to the invention after the pull-out process in the yarn after dyeing in the last rinsing bath (15 '/ 30 ° C.). Drying at 120 ° C. The yarn was then deepened, sheared and coated.
Stücke von 50 x 30 cm wurden entnommen und einem Begehtest unterzogen, indem in einer Personenaufzugskabine zwei behandelte und zwei nicht behandelte Proben schachbrettartig verlegt wurden. In dem Kabinenraum wird das Material durch die Drehbewegungen der Personen, die den Aufzug benutzen, einer intensiveren Oberflächenbelastung unterzogen als bei schreitenden Begehungen. Die Zahl der Begehungen wird elektronisch gezählt. Nach je 10 000 Begehungen werden die Proben auf den Feldern cyclisch ausgetauscht, um eine gleichmäßige Belastung zu gewährleisten. Nach 30 000 Begehungen werden die Muster entnommen und von 6 verschiedenen Begutachtern visuell beurteilt. Bewertet wird die Oberflächenveränderung der unbehandelten Proben (A) im Vergleich zu den behandelten Mustern (B).Pieces of 50 x 30 cm were removed and subjected to a walk test by laying two treated and two untreated samples in a checkered manner in a passenger elevator cabin. In the cabin room, the material is subjected to a more intensive surface stress due to the rotating movements of the people using the elevator than when walking on it. The number of inspections is counted electronically. After every 10,000 inspections, the samples in the fields are exchanged cyclically to ensure an even load. After 30,000 inspections, the samples are removed and visually assessed by 6 different assessors. The surface change of the untreated samples is evaluated (A) compared to the treated samples (B).
Möbelbezugsstoffe aus CO-Rücken und PAC-Polmaterial (500 g/m2 Gesamtgewicht) wurden mit der erfindungsgemäßen Zubereitung des Beispiels 2 wie folgt ausgerüstet:
- A 30 g/I beim kontinuierlichen Färben
- B 30 g/l nach dem Färben und Auswaschen, vor dem Trocknen im Klotzverfahren
- C nicht ausgerüstet
- A 30 g / l for continuous dyeing
- B 30 g / l after dyeing and washing, before drying in the padding process
- C not equipped
Muster von 30 x 30 cm wurden entnommen und auf einem mit VA-Stahl abgedeckten Labortisch ausgelegt. Die Belastung erfolgte durch ein Stahlgewicht mit einer mit Polytetrafluorethylen beschichteten Auflagefläche. (Auflagedruck: 78,6 g/cm2; Dauer der Belastung: 24 Stunden).Samples of 30 x 30 cm were taken and laid out on a laboratory table covered with VA steel. The load was caused by a steel weight with a support surface coated with polytetrafluoroethylene. (Contact pressure: 78.6 g / cm 2 ; duration of the load: 24 hours).
Visuell wird nach Entfernung der Belastung die Wiederholung im Vergleich zu einer unbelasteten Ware beurteilt:
Eine PA-Tufting-Velour-Ware (450 g/m2 Polgewicht) wurde nach dem Färben im Sprühverfahren vor dem Trocknen behandelt:
- a) mit 3 % der erfindungsgemäßen Zubereitung des Beispiels 2
- b) mit 3% einer Vergleichszubereitung nach DE-OS 1 594 985
- c) keine Behandlung
- a) with 3% of the preparation according to the invention of Example 2
- b) with 3% of a comparison preparation according to DE-OS 1 594 985
- c) no treatment
Anschließend wurde 5 Minuten bei 150°C getrocknet und weiterbehandelt, wie in Beispiel 3 angegeben. Die anschließende Beurteilung erfolgte wie in Beispiel 6 angegeben:
Eine PA-Tufting-Velour-Ware (450 g/m2 Polgewicht) wurde nach dem Färben im Sprühverfahren vor dem Trocknen behandelt:
- a) mit 3% der erfindungsgemäßen Zubereitung des Beispiels 2
- b) mit 3 % einer Vergleichszubereitung nach DE-OS 1594 985
- c) keine Behandlung
- a) with 3% of the preparation according to the invention of Example 2
- b) with 3% of a comparison preparation according to DE-OS 1594 985
- c) no treatment
Anschließend wurde 5 Minuten bei 150°C getrocknet, gleichmäßig geschoren und der Rücken mit einem handelsüblichen Latex-Planschaum beschichtet.The mixture was then dried at 150 ° C. for 5 minutes, shaved evenly, and the back was coated with a commercially available latex sheet foam.
Aus diesem Material wurden gemäß den DIN-Vorschriften jeweils gleiche Muster entnommen.The same samples were taken from this material in accordance with the DIN regulations.
Die Muster werden zunächst mit je 10 g eines synthetischen Schmutzes folgender Zusammensetzung angeschmutzt.
Die Belastung der Proben erfolgt nach dem Stuhlrollenversuch, der in der DIN-Vorschrift 54 324 ausführlich beschrieben ist, bei einer Rollenbelastung von insgesamt 60 kg und einer Änderung der Rollendrehrichtung nach jeweils 50 Umdrehungen.The samples are loaded after the chair roller test, which is described in detail in the DIN regulation 54 324, with a total roller load of 60 kg and a change in the direction of roller rotation after every 50 revolutions.
Die Beurteilung erfolgte wie in Beispiel 6 angegeben.
Claims (6)
are added, whilst agitating, to a mixture of water and anionic or cationic surface-active agents under acid or basic conditions and with the aid of additives which regulate the pH value, the amount of silanes added being 5 to 22%, relative to the total weight of silane, water and other additives.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT81100613T ATE3217T1 (en) | 1980-02-09 | 1981-01-28 | POLE-STABILIZING TEXTILE IMPREGNATION AGENT, PROCESS FOR ITS PRODUCTION AND TEXTILE MATERIALS FINISHED WITH IT. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3004824 | 1980-02-09 | ||
| DE19803004824 DE3004824A1 (en) | 1980-02-09 | 1980-02-09 | POLESTABILIZING TEXTILE IMPREGNANT |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0036475A1 EP0036475A1 (en) | 1981-09-30 |
| EP0036475B1 true EP0036475B1 (en) | 1983-05-04 |
Family
ID=6094185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81100613A Expired EP0036475B1 (en) | 1980-02-09 | 1981-01-28 | Pile-stabilizing textile impregnant, process for preparing it and textile treated with this composition |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4351736A (en) |
| EP (1) | EP0036475B1 (en) |
| JP (1) | JPS56123480A (en) |
| AT (1) | ATE3217T1 (en) |
| CA (1) | CA1153511A (en) |
| DE (2) | DE3004824A1 (en) |
| DK (1) | DK52881A (en) |
| NO (1) | NO156094C (en) |
Families Citing this family (38)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3038984A1 (en) | 1980-10-15 | 1982-05-27 | Bayer Ag, 5090 Leverkusen | METHOD FOR CONTINUOUS COLORING AND SIMULTANEOUS EQUIPMENT OF TEXTILE MATERIALS |
| EP0075989B1 (en) * | 1981-09-25 | 1987-05-13 | THE PROCTER & GAMBLE COMPANY | Fabric softening compositions containing amino-silanes |
| DE3307420A1 (en) * | 1983-03-03 | 1984-09-13 | Bayer Ag, 5090 Leverkusen | TEXTILE EQUIPMENT |
| US4618522A (en) * | 1983-12-19 | 1986-10-21 | General Electric Company | Organosiloxane fabric coating compositions |
| JPH0663158B2 (en) * | 1984-03-27 | 1994-08-17 | 鐘淵化学工業株式会社 | Pile composition |
| JPS61159427A (en) * | 1984-12-29 | 1986-07-19 | Toshiba Silicone Co Ltd | Polyorganosiloxane composition for surface treatment |
| JPH0723585B2 (en) * | 1989-11-06 | 1995-03-15 | 信越化学工業株式会社 | Wool treating agent |
| DE4441982A1 (en) | 1994-11-25 | 1996-05-30 | Bayer Ag | Oil, water and dirt-repellent substrates and fluorine-containing agents |
| US6468587B2 (en) | 2000-06-30 | 2002-10-22 | 3M Innovative Properties Company | Treatment of fibrous substrates with acidic silsesquioxanes emulsions |
| MXPA03006716A (en) | 2001-01-31 | 2003-10-24 | 3M Innovative Properties Co | Soil resistant curable laminate coating. |
| US6736857B2 (en) | 2001-05-25 | 2004-05-18 | 3M Innovative Properties Company | Method for imparting soil and stain resistance to carpet |
| EP1264863A1 (en) * | 2001-06-08 | 2002-12-11 | Ciba Spezialitätenchemie Pfersee GmbH | Compositions of polysiloxanes and further polymers |
| CA2367812A1 (en) * | 2002-01-15 | 2003-07-15 | Robert F. Smith | Abrasive article with hydrophilic/lipophilic coating |
| US20060100359A1 (en) * | 2002-06-19 | 2006-05-11 | Blackwood William R | Fire and stain resistant compositions |
| US7313840B2 (en) * | 2002-07-25 | 2008-01-01 | Charles E. Watkins | Induction liquid pump and magnetic tank scrubber |
| US7335234B2 (en) * | 2002-10-16 | 2008-02-26 | Columbia Insurance Company | Method of treating fibers, carpet yarns and carpets to enhance repellency |
| US20040147188A1 (en) * | 2003-01-28 | 2004-07-29 | 3M Innovative Properties Company | Fluorochemical urethane composition for treatment of fibrous substrates |
| US20050015886A1 (en) | 2003-07-24 | 2005-01-27 | Shaw Industries Group, Inc. | Methods of treating and cleaning fibers, carpet yarns and carpets |
| US7135449B2 (en) * | 2004-02-20 | 2006-11-14 | Milliken & Company | Composition for removal of odors and contaminants from textiles and method |
| US7320956B2 (en) * | 2004-04-01 | 2008-01-22 | 3M Innovative Properties Company | Aqueous cleaning/treatment composition for fibrous substrates |
| US7785374B2 (en) | 2005-01-24 | 2010-08-31 | Columbia Insurance Co. | Methods and compositions for imparting stain resistance to nylon materials |
| JP5453103B2 (en) * | 2006-12-15 | 2014-03-26 | スリーエム イノベイティブ プロパティズ カンパニー | Fluorochemical urethane compound with side chain silyl group used for surface treatment |
| EP2121789A1 (en) * | 2006-12-20 | 2009-11-25 | 3M Innovative Properties Company | Fluorochemical urethane compounds having pendent silyl groups |
| US7745653B2 (en) | 2007-03-08 | 2010-06-29 | 3M Innovative Properties Company | Fluorochemical compounds having pendent silyl groups |
| US7335786B1 (en) | 2007-03-29 | 2008-02-26 | 3M Innovative Properties Company | Michael-adduct fluorochemical silanes |
| GB2447959A (en) * | 2007-03-30 | 2008-10-01 | 3M Innovative Properties Co | Fiber mat containing an organosilicon compound and pollution control device using it |
| US7652117B2 (en) * | 2007-06-20 | 2010-01-26 | 3M Innovative Properties Company | Fluorochemical urethane compounds and aqueous compositions thereof |
| US7652116B2 (en) * | 2007-06-20 | 2010-01-26 | 3M Innovative Properties Company | Fluorochemical urethane-silane compounds and aqueous compositions thereof |
| KR101539795B1 (en) * | 2007-10-09 | 2015-07-27 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Mat for mounting a pollution control element for the treatment of exhaust gas |
| US9834875B2 (en) * | 2007-10-09 | 2017-12-05 | 3M Innovative Properties Company | Method of making mounting mats for mounting a pollution control panel |
| JP5869220B2 (en) | 2007-10-09 | 2016-02-24 | スリーエム イノベイティブ プロパティズ カンパニー | Mounting mat containing inorganic nanoparticles and method for producing the same |
| US7754092B2 (en) * | 2007-10-31 | 2010-07-13 | E.I. Du Pont De Nemours And Company | Soil resist additive |
| DE102008000585A1 (en) | 2008-03-10 | 2009-09-17 | Wacker Chemie Ag | Binder-containing colloidal aqueous organopolysiloxane dispersions and their use |
| WO2010026039A1 (en) * | 2008-08-25 | 2010-03-11 | Basf Se | Method for treating textile substrates |
| EP2159319A1 (en) * | 2008-08-25 | 2010-03-03 | Basf Se | Method for treating textile substrates |
| GB0919014D0 (en) | 2009-10-30 | 2009-12-16 | 3M Innovative Properties Co | Soll and stain resistant coating composition for finished leather substrates |
| US8057693B1 (en) | 2010-07-26 | 2011-11-15 | Arrowstar, Llc | Compositions and methods for imparting liquid repellency and dry soil resistance to fibers and articles thereof |
| EP2734584B1 (en) | 2011-07-19 | 2018-11-21 | Continental Structural Plastics, Inc. | Enhanced thermoset resins containing pre-treated natural origin cellulosic fillers |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA794874A (en) * | 1968-09-17 | G. Neuroth Charles | Reaction product coatings of alkyltrimethoxysilane/tetraalkylorthosilicate | |
| BE635170A (en) * | 1955-08-17 | |||
| GB975302A (en) * | 1962-03-09 | 1964-11-11 | Stauffer Chemical Co | Novel silicon-containing compositions |
| FR1379313A (en) * | 1963-12-30 | 1964-11-20 | Monsanto Co | Process for treating polyamides, in particular in the form of threads, intended to prevent the slipping of the knots of threads of these polyamides |
| NL133796C (en) * | 1965-01-21 | 1900-01-01 | ||
| US3431142A (en) * | 1965-08-19 | 1969-03-04 | Petchen Corp | Method of improving wearing qualities of organic fibers and fabrics |
| US3642681A (en) * | 1969-01-14 | 1972-02-15 | Du Pont | Polysilicic acid coating composition |
| US3917893A (en) * | 1974-02-04 | 1975-11-04 | Allied Chem | Polyamide yarn |
| US3898090A (en) * | 1974-06-24 | 1975-08-05 | Dow Corning | Foundry mold and core compositions |
| US3944702A (en) * | 1974-06-24 | 1976-03-16 | Dow Corning Corporation | Fibrous structures bonded with a silsesquioxane-containing composition |
| US3959566A (en) * | 1974-10-21 | 1976-05-25 | E. I. Du Pont De Nemours And Company | Process for preparing polymeric surfaces to improve antistatic and soil resistant properties |
| US4177175A (en) * | 1977-12-23 | 1979-12-04 | Dow Corning Corporation | Organothiol-containing siloxane resins as adhesion promoters for siloxane resins |
| ZA795994B (en) * | 1978-11-30 | 1981-05-27 | Gen Electric | Silicone resin coating composition |
-
1980
- 1980-02-09 DE DE19803004824 patent/DE3004824A1/en not_active Withdrawn
-
1981
- 1981-01-22 US US06/227,444 patent/US4351736A/en not_active Expired - Lifetime
- 1981-01-28 DE DE8181100613T patent/DE3160212D1/en not_active Expired
- 1981-01-28 EP EP81100613A patent/EP0036475B1/en not_active Expired
- 1981-01-28 NO NO810295A patent/NO156094C/en unknown
- 1981-01-28 AT AT81100613T patent/ATE3217T1/en not_active IP Right Cessation
- 1981-02-06 DK DK52881A patent/DK52881A/en not_active Application Discontinuation
- 1981-02-06 CA CA000370255A patent/CA1153511A/en not_active Expired
- 1981-02-07 JP JP1632981A patent/JPS56123480A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3160212D1 (en) | 1983-06-09 |
| JPS56123480A (en) | 1981-09-28 |
| DE3004824A1 (en) | 1981-08-20 |
| CA1153511A (en) | 1983-09-13 |
| NO810295L (en) | 1981-08-10 |
| ATE3217T1 (en) | 1983-05-15 |
| US4351736A (en) | 1982-09-28 |
| DK52881A (en) | 1981-08-10 |
| NO156094B (en) | 1987-04-13 |
| JPS646313B2 (en) | 1989-02-02 |
| EP0036475A1 (en) | 1981-09-30 |
| NO156094C (en) | 1987-07-22 |
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