EP0190672B1 - Process for the impregnation of organic fibres - Google Patents
Process for the impregnation of organic fibres Download PDFInfo
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- EP0190672B1 EP0190672B1 EP86101240A EP86101240A EP0190672B1 EP 0190672 B1 EP0190672 B1 EP 0190672B1 EP 86101240 A EP86101240 A EP 86101240A EP 86101240 A EP86101240 A EP 86101240A EP 0190672 B1 EP0190672 B1 EP 0190672B1
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- Prior art keywords
- bonded
- radicals
- organopolysiloxane
- sic
- basic nitrogen
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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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
- D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
Definitions
- all organic fibers can be impregnated in the form of threads, yarns, nonwovens, mats, strands, woven, knitted or knitted textiles which have also been impregnated with organosilicon compounds.
- fibers which can be impregnated by the process according to the invention are thus those made of keratin, in particular wool, polyvinyl alcohol, copolymers of vinyl acetate, cotton, rayon, hemp, natural silk, polypropylene, polyethylene, polyester, polyurethane, polyamide, cellulose and mixtures from at least two such fibers.
- the fibers can be of natural or synthetic origin.
- the textiles can be in the form of fabric webs or items of clothing or parts of items of clothing.
- the diorganosiloxane units in the organopolysiloxane (1), in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals, are preferably those represented by the formula can be reproduced, where R is the same or different, monovalent hydrocarbon radicals, R1 is hydrogen or from carbon and hydrogen atom (s) and optionally an ether oxygen atom, radicals free of multiple bonds with 1 to 15 carbon atoms per radical and a is 0 or 1.
- radicals R preferably contain 1 to 18 carbon atoms per radical.
- radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl and isopropyl radical, and butyl, octyl, tetradecyl and octadecyl radicals; aliphatic hydrocarbon radicals with at least one double bond, those of the vinyl, allyl and butadienyl radical; cycloaliphatic hydrocarbon radicals, such as the cyclohexyl radical; aromatic hydrocarbon radicals such as the phenyl radical and naphthyl radicals; Alkaryl groups such as tolyl groups; and aralkyl radicals, such as the benzyl radical.
- at least 80% of the number of SiC-bonded hydrocarbon residues in the organopolysiloxane (1) are preferably methyl residues.
- hydrocarbon radicals R insofar as they represent free hydrocarbon radicals with a maximum of 15 carbon atoms per radical, also apply fully to the hydrocarbon radicals R 1, with the methyl, ethyl and isopropyl radicals being preferred.
- a preferred example of a radical R 1 composed of carbon and hydrogen atoms and an ether oxygen is the rest of the formula CH3O (CH2) 2-.
- the organopolysiloxanes (1) preferably contain at least 100 diorganosiloxane units, in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals, per molecule.
- the monoorganosiloxane units in which the SiC-bonded radicals with basic nitrogen are present in the organopolysiloxane (1) are preferably those represented by the formula can be reproduced while the diorganosiloxane units, in which SiC-bound radicals with basic nitrogen are present in the organopolysiloxane (1), preferably those which are represented by the formula can be reproduced, where R, R1 and a each have the meaning given above, R2 is hydrogen or identical or different alkyl or aminoalkyl or iminoalkyl radicals and R3 is identical or different, divalent hydrocarbon radicals and b is 0, 1 or 2.
- alkyl radicals R also apply fully to alkyl radicals R2.
- radical R 3 is that of the formula - (CH2) 3- particularly preferred. Further examples of R3 radicals are those of the formula
- the organopolysiloxane (1) or the organopolysiloxane (1) must have at least one monoorganosiloxane unit with a Sic-bonded radical contain with basic nitrogen and at least one diorganosiloxane unit with an SiC-bonded residue with basic nitrogen, one of these units per molecule of organopolysiloxane (1) being sufficient.
- the sum of the number of monoorganosiloxane units with an SiC-bonded radical with basic nitrogen and the number of diorganosiloxane units with an SiC-bonded radical with basic nitrogen is at most 20% of the number of diorganosiloxane units, in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals in order to avoid a risk of yellowing of the impregnated fibers and to avoid unnecessary effort.
- the ratio of the number of monoorganosiloxane units with basic nitrogen to the number of diorganosiloxane units with basic nitrogen is preferably 0.9: 3 to 3: 1, in particular 0.9: 1 to 1.1: 1.
- the organopolysiloxane (1) or a mixture of at least two different types of organopolysiloxane (1) preferably has an average viscosity of 100 to 100,000 mPa.s at 25 ° C.
- the organopolysiloxanes (1) can be prepared in a manner known per se for any of the organopolysiloxanes which contain monovalent SiC-bonded radicals containing basic nitrogen.
- organopolysiloxanes (2) with at least 3 Si-bonded hydrogen atoms per molecule the same organopolysiloxanes containing at least 3 Si-bonded hydrogen atoms can also be used in the process according to the invention, which could be used in all previously known processes for impregnating organic fibers.
- the silicon valences which are saturated by hydrogen and siloxane oxygen atoms, are preferably methyl, ethyl or Saturated phenyl radicals or a mixture of at least two such hydrocarbon radicals. It is further preferred that each silicon atom to which a hydrogen atom is bound also has one of the preferred hydrocarbon radicals mentioned above bound.
- Particularly preferred organopolysiloxanes (2) with at least 3 Si-bonded hydrogen atoms per molecule are those of the formula wherein R4 is hydrogen or the methyl, ethyl or phenyl radical and p is an integer from 10 to 500, with the proviso that at most one hydrogen atom is bonded to a silicon atom and that the ratio of R 4th 2nd SiO units in which both R4 are hydrocarbon radicals to the units with Si-bonded hydrogen is 0: 1 to 4: 1.
- R4 also preferably denotes a methyl radical if it is not hydrogen.
- organopolysiloxane can also be used as organopolysiloxanes (2) with at least 3 Si-bonded hydrogen atoms per molecule.
- Organopolysiloxane (2) with at least 3 Si-bonded hydrogen atoms per molecule can also be used in the process according to the invention in the same amounts as in the previously known processes for impregnating organic fibers in connection with directly on silicon bound organopolysiloxane containing condensable groups could be used.
- Such organopolysiloxane is preferably used in amounts of 0.01 to 0.50 part by weight of Si-bonded hydrogen per 100 parts by weight of organopolysiloxane (1).
- any catalysts for the condensation of condensable groups directly bonded to silicon can also be used in the process according to the invention which have hitherto been used to promote the condensation of directly bonded to silicon , condensable groups could be used.
- catalysts are, in particular, carboxylic acid salts of tin or zinc, it being possible for hydrocarbon radicals to be bonded directly to tin, such as di-n-butyltin dilaurate, tin octoates, di-2-ethyltin dilaurate, di-n-butyltin di-2-ethylhexoate, di-2- ethylhexyltin di-2-ethylhexoate, dibutyl or dioctyltin diacylates, the acylate groups each being derived from alkanoic acids having 3 to 16 carbon atoms per acid, in which at least two of the valences of the carbon atom bonded to the carboxyl group are saturated by at least two carbon atoms other than that of the carboxy group , and zinc octoates.
- catalysts (3) are alkyl titanates, such as butyl titanates and triethanolamine titanate, and zir
- catalysts (3) The same or different molecules of this type of catalyst can also be used as catalysts (3).
- the catalysts (3) can also be used in the process according to the invention in the same amounts in which they could previously be used to promote the condensation of condensable groups bonded directly to silicon.
- Catalyst (3) is preferably used in amounts of 1 to 10 parts by weight per 100 parts by weight of organopolysiloxane (1).
- further substances such as can conventionally be used for the impregnation of organic fibers, can optionally also be used in the process according to the invention.
- further substances in the terminal units are dimethylpolysiloxanes each having an Si-bonded hydroxyl group and having a viscosity of at most 10,000 mPa.s at 25 ° C, dimethylpolysiloxanes endblocked by trimethylsiloxy groups and having a viscosity of at most 10,000 mPa.s at 25 ° C and, especially if the fibers to be impregnated consist at least in part of cellulose or cotton, so-called "crease-free finishes", such as dimethyldihydroxyethylene urea (DMDHEU) in a mixture with zinc nitrate or magnesium chloride.
- DMDHEU dimethyldihydroxyethylene urea
- the substances used in the process according to the invention can be applied to the fibers to be impregnated in undiluted form or in the form of solutions in organic solvent or in the form of aqueous emulsions. If aqueous emulsions are used, these emulsions can contain, in addition to water, dispersant and the above-mentioned substances to be dispersed, thickeners, such as poly-N-vinylpyrrolidone.
- the substances used in the process according to the invention are preferably applied in the form of aqueous emulsions to the fibers to be impregnated. As dispersants in these dispersions are nonionic and cationogenic emulsifiers preferred. These emulsions can be prepared in a manner known for the emulsification of organopolysiloxanes.
- the substances used in the process according to the invention can be applied to the fibers to be impregnated in any suitable and well-known manner for the impregnation of fibers, e.g. B. by dipping, brushing, pouring, spraying, including spraying from aerosol packaging, rolling, padding or printing.
- the substances used in the process according to the invention are preferably applied in amounts such that the weight gain of the fiber by these substances, minus any diluents which may be used, is 1 to 20 percent by weight, based on the weight of the fiber.
- the organosilicon compounds used in the process according to the invention are crosslinked on the fiber at room temperature. B. accelerated 50 ° to 180 ° C.
- a fabric made of 50% cotton and 50% polyester with a weight of 210 g / m2 is immersed in an emulsion that 40 g / l of the emulsion, the preparation of which was described in Example 1 under b), 4 g / l of the emulsion, the preparation of which was described in Example 1 under c), 4 g / l of the emulsion, the preparation of which was described in Example 1 under d), 80 g / l DMDHEU 10 g / l magnesium chloride and contains the rest of water, and then squeezed to 80% fluid intake.
- the fabric so impregnated is then heated to 150 ° C. for 10 minutes.
- the impregnated fabric thus obtained has a soft, elastic handle, which is still present in a household washing machine even after 5 delicates at 60 ° C.
- the knitted fabrics impregnated according to Example 1 and the knitted fabrics impregnated according to the two comparative tests were evaluated for their grip by 9 people who had no knowledge of which knitted fabrics according to the comparative tests and which knitted fabric was impregnated according to Example 1. Before and after 5 delicates at 40 ° C. in a household washing machine, the knitted fabric impregnated according to Example 1 was rated 5 times and the knitted fabric impregnated according to the two comparative tests was rated twice.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Polymers (AREA)
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Abstract
Description
Aus US-A-4 098 701 (ausgegeben 4. Juli 1978, P. M. Burrill et al., Dow Corning Limited) und US-A-4 436 856 (ausgegeben 13. März 1984, K. Huhn et al ., Wacker-Chemie GmbH) ist es bereits bekannt, organische Fasern mit direkt an Silicium gebundene, kondensationsfähige Gruppen aufweisendem Organopolysiloxan, das zusätzlich zu Diorganosiloxaneinheiten, worin die beiden SiC-gebundenen, organischen Reste einwertige Kohlenwasserstoffreste sind, mindestens zwei einwertige SiC-gebundene Reste mit basischem Stickstoff enthält, Organopolysiloxan mit mindestens drei Si-gebundenen Wasserstoffatomen je Molekül und Katalysator für die Kondensation von direkt an Silicium gebundenen, kondensationsfähigen Gruppen zu imprägnieren. In der erstgenannten Druckschrift sind keine anderen Siloxaneinheiten mit basischem Stickstoff als Diorganosiloxaneinheiten erwähnt. Gemäß der anderen Druckschrift liegen alle SiC-gebundenen Reste mit basischem Stickstoff in Monoorganosiloxaneinheiten vor.From US-A-4 098 701 (issued July 4, 1978, PM Burrill et al., Dow Corning Limited) and US-A-4 436 856 (issued March 13, 1984, K. Huhn et al., Wacker-Chemie GmbH), it is already known to contain organic fibers with organopolysiloxane which has condensation groups bonded directly to silicon and which, in addition to diorganosiloxane units in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals, contain at least two monovalent SiC-bonded radicals with basic nitrogen, Impregnate organopolysiloxane with at least three Si-bonded hydrogen atoms per molecule and catalyst for the condensation of condensable groups bonded directly to silicon. No other siloxane units with basic nitrogen than diorganosiloxane units are mentioned in the first-mentioned publication. According to the other document, all SiC-bound residues with basic nitrogen are present in monoorganosiloxane units.
Es ist Aufgabe der Erfindung, ein Verfahren zur Imprägnierung von organischen Fasern bereitzustellen, das den Fasern in besonders hohem Ausmaß Glätte, angenehmen Griff, Beständigkeit gegenüber Pilling, Schrumpffestigkeit, Elastizität und Rückstellvermögen sowie besonders gute Vernähbarkeit verleiht, wobei diese den Fasern verliehenen vorteilhaften Eigenschaften auch beim Reinigen der Fasern mit Wasser oder organischem Lösungsmittel erhalten bleiben. Insbesondere ist es Aufgabe der Erfindung, ein verfahren zur Imprägnierung von organischen Fasern bereitzustellen, das den Fasern einen verbesserten Griff verleiht, wobei dieser verbesserte Griff auch beim Reinigen der Fasern mit Wasser oder organischem Lösungsmittel erhalten bleibt. Diese Aufgabe wird durch die Erfindung gelöst.It is an object of the invention to provide a process for the impregnation of organic fibers which gives the fibers a particularly high degree of smoothness, a pleasant grip, resistance to pilling, shrink resistance, elasticity and resilience, and particularly good sewability gives, these beneficial properties imparted to the fibers are retained even when cleaning the fibers with water or organic solvent. In particular, it is an object of the invention to provide a method for impregnating organic fibers which gives the fibers an improved grip, this improved grip being retained even when the fibers are cleaned with water or organic solvent. This object is achieved by the invention.
Gegenstand der Erfindung ist ein verfahren zur Imprägnierung von organischen Fasern mit
- (1) direkt an Silicium gebundene, kondensationsfähige Gruppen aufweisendem Organopolysiloxan, das zusätzlich zu Diorganosiloxaneinheiten, worin die beiden SiC-gebundenen, organischen Reste einwertige Kohlenwasserstoffreste sind, mindestens zwei einwertige SiC-gebundene Reste mit basischem Stickstoff enthält,
- (2) Organopolysiloxan mit mindestens 3 Si-gebundenen Wasserstoffatomen je Molekül und
- (3) Katalysator für die Kondensation von direkt an Silicium gebundenen, kondensationsfähigen Gruppen,
dadurch gekennzeichnet, daß die SiC-gebundenen Reste mit basischem Stickstoff im Organopolysiloxan (1) sowohl in Monoorganosiloxan- als auch in Diorganosiloxaneinheiten vorliegen.The invention relates to a method for impregnating organic fibers with
- (1) organopolysiloxane which has condensable groups and is bonded directly to silicon and which, in addition to diorganosiloxane units in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals, contains at least two monovalent SiC-bonded radicals with basic nitrogen,
- (2) Organopolysiloxane with at least 3 Si-bonded hydrogen atoms per molecule and
- (3) catalyst for the condensation of condensable groups bonded directly to silicon,
characterized in that the SiC-bonded residues with basic nitrogen in the organopolysiloxane (1) are present both in monoorganosiloxane and in diorganosiloxane units.
Nach dem erfindungsgemäßen verfahren können alle organischen Fasern in Form von Fäden, Garnen, Vliesen, Matten, Strängen, gewebten, gewirkten oder gestrickten Textilien imprägniert werden, die auch bisher mit Organosiliciumverbindungen imprägniert werden konnten. Beispiele für Fasern, die nach dem erfindungsgemäßen Verfahren imprägniert werden können, sind somit solche aus Keratin, insbesondere Wolle, Polyvinylalkohol, Mischpolymere von Vinylacetat, Baumwolle, Rayon, Hanf, natürliche Seide, Polypropylen, Polyethylen, Polyester, Polyurethan, Polyamid, Cellulose und Gemische aus mindestens zwei solcher Fasern. Wie aus der vorstehenden Aufzählung ersichtlich, können die Fasern natürlicher oder synthetischer Herkunft sein. Die Textilien können in Form von Stoffbahnen oder Kleidungsstücken bzw. Teilen von Kleidungsstücken vorliegen.According to the process according to the invention, all organic fibers can be impregnated in the form of threads, yarns, nonwovens, mats, strands, woven, knitted or knitted textiles which have also been impregnated with organosilicon compounds. Examples of fibers which can be impregnated by the process according to the invention are thus those made of keratin, in particular wool, polyvinyl alcohol, copolymers of vinyl acetate, cotton, rayon, hemp, natural silk, polypropylene, polyethylene, polyester, polyurethane, polyamide, cellulose and mixtures from at least two such fibers. As can be seen from the above list, the fibers can be of natural or synthetic origin. The textiles can be in the form of fabric webs or items of clothing or parts of items of clothing.
Bei Keratin, insbesondere Wolle, kann durch Imprägnierung nach dem erfindungsgemäßen Verfahren, vor allem, wenn das Keratin mit Chlor vorbehandelt, gespült und neutralisiert wurde, das Schrumpfen durch Verfilzen verhindert werden.In the case of keratin, in particular wool, the shrinkage due to matting can be prevented by impregnation by the process according to the invention, especially if the keratin has been pretreated, rinsed and neutralized.
Die Diorganosiloxaneinheiten im Organopolysiloxan (1), worin die beiden SiC-gebundenen, organischen Reste einwertige Kohlenwasserstoffreste sind, sind vorzugsweise solche, die durch die Formel
wiedergegeben werden können, wobei R gleiche oder verschiedene, einwertige Kohlenwasserstoffreste, R¹ Wasserstoff oder aus Kohlenstoff- und Wasserstoffatom(en) sowie gegebenenfalls einem Ethersauerstoffatom aufgebaute, von Mehrfachbindungen freie Reste mit 1 bis 15 Kohlenstoffatomen je Rest bedeutet und a 0 oder 1 ist.The diorganosiloxane units in the organopolysiloxane (1), in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals, are preferably those represented by the formula
can be reproduced, where R is the same or different, monovalent hydrocarbon radicals, R¹ is hydrogen or from carbon and hydrogen atom (s) and optionally an ether oxygen atom, radicals free of multiple bonds with 1 to 15 carbon atoms per radical and a is 0 or 1.
Vorzugsweise enthalten die Reste R 1 bis 18 Kohlenstoffatome je Rest. Beispiele für Reste R sind Alkylreste, wie der Methyl-, Ethyl-, n-Propyl- und Isopropylrest sowie Butyl-, Octyl-, Tetradecyl- und Octadecylreste; aliphatische Kohlenwasserstoffreste mit mindestens einer Doppelbindung, die der Vinyl-, Allyl- und Butadienylrest; cycloaliphatische Kohlenwasserstoffreste, wie der Cyclohexylrest; aromatische Kohlenwasserstoffreste, wie der Phenylrest und Naphthylreste; Alkarylreste, wie Tolylreste; und Aralkylreste, wie der Benzylrest. Insbesondere wegen der leichteren Zugänglichkeit sind vorzugsweise mindestens 80 % der Anzahl der SiC-gebundenen Kohlenwasserstoffreste im Organopolysiloxan (1) Methylreste.The radicals R preferably contain 1 to 18 carbon atoms per radical. Examples of radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl and isopropyl radical, and butyl, octyl, tetradecyl and octadecyl radicals; aliphatic hydrocarbon radicals with at least one double bond, those of the vinyl, allyl and butadienyl radical; cycloaliphatic hydrocarbon radicals, such as the cyclohexyl radical; aromatic hydrocarbon radicals such as the phenyl radical and naphthyl radicals; Alkaryl groups such as tolyl groups; and aralkyl radicals, such as the benzyl radical. In particular because of the easier accessibility, at least 80% of the number of SiC-bonded hydrocarbon residues in the organopolysiloxane (1) are preferably methyl residues.
Die Beispiele für Kohlenwasserstoffreste R, soweit sie von Mehrfachbindungen freie Kohlenwasserstoffreste mit höchstens 15 Kohlenstoffatomen je Rest darstellen, gelten im vollen Umfang auch für die Kohlenwasserstoffreste R¹, wobei der Methyl-, Ethyl- und Isopropylreste bevorzugt sind. Ein bevorzugtes Beispiel für einen aus Kohlenstoff- und Wasserstoffatomen sowie einem Ethersauerstoff aufgebauten Rest R¹ ist der Rest der Formel
CH₃O(CH₂)₂-.
The examples of hydrocarbon radicals R, insofar as they represent free hydrocarbon radicals with a maximum of 15 carbon atoms per radical, also apply fully to the hydrocarbon radicals R 1, with the methyl, ethyl and isopropyl radicals being preferred. A preferred example of a radical R 1 composed of carbon and hydrogen atoms and an ether oxygen is the rest of the formula
CH₃O (CH₂) ₂-.
Vorzugsweise enthalten die Organopolysiloxane (1) mindestens 100 Diorganosiloxaneinheiten, worin die beiden SiC-gebundenen, organischen Reste einwertige Kohlenwasserstoffreste sind, je Molekül.The organopolysiloxanes (1) preferably contain at least 100 diorganosiloxane units, in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals, per molecule.
Die Monoorganosiloxaneinheiten, in denen die SiC-gebundenen Reste mit basischem Stickstoff im Organopolysiloxan (1) vorliegen, sind vorzugsweise solche, die durch die Formel
wiedergegeben werden können, während die Diorganosiloxaneinheiten, in denen SiC-gebundene Reste mit basischem Stickstoff im Organopolysiloxan (1) vorliegen, vorzugsweise solche sind, die durch die Formel
wiedergegeben werden können, wobei R, R¹ und a jeweils die oben dafür angegebene Bedeutung haben, R² Wasserstoff oder gleiche oder verschiedene Alkyl- oder Aminoalkyl- bzw. Iminoalkylreste und R³ gleiche oder verschiedene, zweiwertige Kohlenwasserstoffreste bedeutet und b 0, 1 oder 2 ist.The monoorganosiloxane units in which the SiC-bonded radicals with basic nitrogen are present in the organopolysiloxane (1) are preferably those represented by the formula
can be reproduced while the diorganosiloxane units, in which SiC-bound radicals with basic nitrogen are present in the organopolysiloxane (1), preferably those which are represented by the formula
can be reproduced, where R, R¹ and a each have the meaning given above, R² is hydrogen or identical or different alkyl or aminoalkyl or iminoalkyl radicals and R³ is identical or different, divalent hydrocarbon radicals and b is 0, 1 or 2.
Die Beispiele für Alkylreste R gelten in vollem Umfang auch für Alkylreste R².The examples of alkyl radicals R also apply fully to alkyl radicals R².
Beispiele für Aminoalkylreste R² sind solche der Formel
H₂N(CH₂)₂-
H₂N(CH₂)₂NH(CH₂)₃-
H₂N(CH₂)₃-
(CH₃)₂N(CH₂)-
H₂N(CH₂)₅-
H(NHCH₂CH₂)₃- und
n-C₄H₉NHCH₂CH₂NHCH₂CH₂-.
Examples of aminoalkyl radicals R² are those of the formula
H₂N (CH₂) ₂-
H₂N (CH₂) ₂NH (CH₂) ₃-
H₂N (CH₂) ₃-
(CH₃) ₂N (CH₂) -
H₂N (CH₂) ₅-
H (NHCH₂CH₂) ₃- and
n-C₄H₉NHCH₂CH₂NHCH₂CH₂-.
Insbesondere wegen der leichten Zugänglichkeit ist als Rest R³ derjenige der Formel
-(CH₂)₃-
besonders bevorzugt. Weitere Beispiele für Reste R³ sind solche der Formel
- (CH₂) ₃-
particularly preferred. Further examples of R³ radicals are those of the formula
Damit die Forderung, daß die SiC-gebundenen Reste mit basischem Stickstoff im Organopolysiloxan (1) sowohl in Monoorganosiloxan-als auch in Diorganosiloxaneinheit vorliegen, muß das Organopolysiloxan (1) oder müssen die Organopolysiloxane (1 ) mindestens eine Monoorganosiloxaneinheit mit einem Sic-gebundenen Rest mit basischem Stickstoff und mindestens eine Diorganosiloxaneinheit mit einem SiC-gebundenen Rest mit basischem Stickstoff enthalten, wobei je eine dieser Einheiten je Molekül Organopolysiloxan (1) ausreicht.So that the requirement that the SiC-bonded radicals with basic nitrogen in the organopolysiloxane (1) exist in both the monoorganosiloxane unit and in the diorganosiloxane unit, the organopolysiloxane (1) or the organopolysiloxane (1) must have at least one monoorganosiloxane unit with a Sic-bonded radical contain with basic nitrogen and at least one diorganosiloxane unit with an SiC-bonded residue with basic nitrogen, one of these units per molecule of organopolysiloxane (1) being sufficient.
Vorzugsweise beträgt die Summe der Anzahl der Monoorganosiloxaneinheiten mit einem SiC-gebundenen Rest mit basischem Stickstoff und der Anzahl der Diorganosiloxaneinheiten mit einem SiC-gebundenen Rest mit basischem Stickstoff höchstens 20 % der Anzahl der Diorganosiloxaneinheiten, worin die beiden SiC-gebundenen, organischen Reste einwertige Kohlenwasserstoffreste sind, um eine Vergilbungsgefahr der imprägnierten Fasern zu vermeiden und um unnötigen Aufwand zu vermeiden.The sum of the number of monoorganosiloxane units with an SiC-bonded radical with basic nitrogen and the number of diorganosiloxane units with an SiC-bonded radical with basic nitrogen is at most 20% of the number of diorganosiloxane units, in which the two SiC-bonded organic radicals are monovalent hydrocarbon radicals in order to avoid a risk of yellowing of the impregnated fibers and to avoid unnecessary effort.
Vorzugsweise beträgt das Verhältnis der Anzahl der Monoorganosiloxaneinheiten mit basischem Stickstoff zu der Anzahl der Diorganosiloxaneinheiten mit basischem Stickstoff 0,9 : 3 bis 3 : 1, insbesondere 0,9 : 1 bis 1 ,1 : 1.The ratio of the number of monoorganosiloxane units with basic nitrogen to the number of diorganosiloxane units with basic nitrogen is preferably 0.9: 3 to 3: 1, in particular 0.9: 1 to 1.1: 1.
Vorzugsweise hat das Organopolysiloxan (1) oder ein Gemisch aus mindestens zwei verschiedenen Arten von Organopolysiloxan (1) eine durchschnittliche Viskosität von 100 bis 100 000 mPa.s bei 25°C.The organopolysiloxane (1) or a mixture of at least two different types of organopolysiloxane (1) preferably has an average viscosity of 100 to 100,000 mPa.s at 25 ° C.
Die Herstellung der Organopolysiloxane (1) kann in beliebiger für die Herstellung von Organopolysiloxanen, die einwertige SiC-gebundene Reste mit basischem Stickstoff enthalten, an sich bekannter Weise erfolgen.The organopolysiloxanes (1) can be prepared in a manner known per se for any of the organopolysiloxanes which contain monovalent SiC-bonded radicals containing basic nitrogen.
Als Organopolysiloxane (2) mit mindestens 3 Si-gebundenen Wasserstoffatomen je Molekül können auch bei dem erfindungsgemäßen Verfahren die gleichen mindestens 3 Si-gebundene Wasserstoffatome aufweisenden Organopolysiloxane verwendet werden, die bei allen bisher bekannten Verfahren zur Imprägnierung von organischen Fasern eingesetzt werden konnten.As organopolysiloxanes (2) with at least 3 Si-bonded hydrogen atoms per molecule, the same organopolysiloxanes containing at least 3 Si-bonded hydrogen atoms can also be used in the process according to the invention, which could be used in all previously known processes for impregnating organic fibers.
Im Organopolysiloxan (2) mit mindestens 3 Si-gebundenen Wasserstoffatomen je Molekül sind die anders als durch Wasserstoff- und Siloxansauerstoffatome abgesättigten Siliciumvalenzen vorzugsweise durch Methyl-, Ethyl- oder Phenylreste oder ein Gemisch aus mindestens zwei solcher Kohlenwasserstoffreste abgesättigt. Weiterhin ist bevorzugt, daß an jedes Siliciumatom, an das ein Wasserstoffatom gebunden ist, auch einer der vorstehend genannten bevorzugten Kohlenwasserstoffreste gebunden ist.In organopolysiloxane (2) with at least 3 Si-bonded hydrogen atoms per molecule, the silicon valences, which are saturated by hydrogen and siloxane oxygen atoms, are preferably methyl, ethyl or Saturated phenyl radicals or a mixture of at least two such hydrocarbon radicals. It is further preferred that each silicon atom to which a hydrogen atom is bound also has one of the preferred hydrocarbon radicals mentioned above bound.
Besonders bevorzugt als Organopolysiloxane (2) mit mindestens 3 Si-gebundenen Wasserstoffatomen je Molekül sind solche der Formel
worin R⁴ Wasserstoff oder den Methyl-, Ethyl- oder Phenylrest und p eine ganze Zahl im Wert von 10 bis 500 bedeutet, mit der Maßgabe, daß an ein Siliciumatom höchstens ein Wasserstoffatom gebunden ist und daß das Verhältnis von R
wherein R⁴ is hydrogen or the methyl, ethyl or phenyl radical and p is an integer from 10 to 500, with the proviso that at most one hydrogen atom is bonded to a silicon atom and that the ratio of R
Auch als Organopolysiloxane (2) mit mindestens 3 Si-gebundenen Wasserstoffatomen je Molekül können gleiche oder verschiedene Moleküle dieser Organopolysiloxanart eingesetzt werden.The same or different molecules of this type of organopolysiloxane can also be used as organopolysiloxanes (2) with at least 3 Si-bonded hydrogen atoms per molecule.
Organopolysiloxan (2) mit mindestens 3 Si-gebundenen Wasserstoffatomen je Molekül kann auch bei dem erfindungsgemäßen Verfahren in den gleichen Mengen eingesetzt werden, in denen es bei den bisher bekannten Verfahren zum Imprägnieren von organischen Fasern in Verbindung mit direkt an Silicium gebundene kondensationsfähige Gruppen aufweisendem Organopolysiloxan eingesetzt werden konnte. Vorzugsweise wird derartiges Organopolysiloxan in Mengen von 0,01 bis 0,50 Gewichtsteilen Si-gebundenen Wasserstoffs je 100 Gewichtsteile Organopolysiloxan (1) eingesetzt.Organopolysiloxane (2) with at least 3 Si-bonded hydrogen atoms per molecule can also be used in the process according to the invention in the same amounts as in the previously known processes for impregnating organic fibers in connection with directly on silicon bound organopolysiloxane containing condensable groups could be used. Such organopolysiloxane is preferably used in amounts of 0.01 to 0.50 part by weight of Si-bonded hydrogen per 100 parts by weight of organopolysiloxane (1).
Als Katalysatoren (3) für die Kondensation von direkt an Silicium gebundenen, kondensationsfähigen Gruppen können ebenfalls auch bei dem erfindungsgemäßen Verfahren beliebige Katalysatoren für die Kondensation von direkt an Silicium gebundenen, kondensationsfähigen Gruppen eingesetzt werden, die bisher zur Förderung der Kondensation von direkt an Silicium gebundenen, kondensationsfähigen Gruppen eingesetzt werden konnten. Beispiele für solche Katalysatoren sind insbesondere Carbonsäuresalze von Zinn oder Zink, wobei an Zinn Kohlenwasserstoffreste direkt gebunden sein können, wie Di-n-butylzinndilaurat, Zinnoctoate, Di-2-ethylzinndilaurat, Di-n-butylzinndi-2-ethylhexoat, Di-2-ethylhexylzinndi-2-ethylhexoat, Dibutyl- oder Dioctylzinndiacylate, wobei sich die Acylatgruppen jeweils von Alkansäuren mit 3 bis 16 Kohlenstoffatomen je Säure ableiten, bei denen mindestens zwei der Valenzen des an die Carboxylgruppe gebundenen Kohlenstoffatoms durch mindestens zwei andere Kohlenstoffatome als dasjenige der Carboxygruppe abgesättigt sind, und Zinkoctoate.Weitere Beispiele für Katalysatoren (3) sind Alkyltitanate, wie Butyltitanate und Triethanolamintitanat, sowie Zirkoniumverbindungen.As catalysts (3) for the condensation of condensable groups directly bonded to silicon, any catalysts for the condensation of condensable groups directly bonded to silicon can also be used in the process according to the invention which have hitherto been used to promote the condensation of directly bonded to silicon , condensable groups could be used. Examples of such catalysts are, in particular, carboxylic acid salts of tin or zinc, it being possible for hydrocarbon radicals to be bonded directly to tin, such as di-n-butyltin dilaurate, tin octoates, di-2-ethyltin dilaurate, di-n-butyltin di-2-ethylhexoate, di-2- ethylhexyltin di-2-ethylhexoate, dibutyl or dioctyltin diacylates, the acylate groups each being derived from alkanoic acids having 3 to 16 carbon atoms per acid, in which at least two of the valences of the carbon atom bonded to the carboxyl group are saturated by at least two carbon atoms other than that of the carboxy group , and zinc octoates. Further examples of catalysts (3) are alkyl titanates, such as butyl titanates and triethanolamine titanate, and zirconium compounds.
Auch als Katalysatoren (3) können gleiche oder verschiedene Moleküle dieser Katalysatorart eingesetzt werden.The same or different molecules of this type of catalyst can also be used as catalysts (3).
Die Katalysatoren (3) können auch bei dem erfindungsgemäßen Verfahren in den gleichen Mengen eingesetzt werden, in denen sie bisher zur Förderung der Kondensation von direkt an Silicium gebundenen kondensationsfähigen Gruppen eingesetzt werden konnten. Vorzugsweise wird Katalysator (3) in Mengen von 1 bis 10 Gewichtsteilen je 100 Gewichtsteile Organopolysiloxan (1) eingesetzt.The catalysts (3) can also be used in the process according to the invention in the same amounts in which they could previously be used to promote the condensation of condensable groups bonded directly to silicon. Catalyst (3) is preferably used in amounts of 1 to 10 parts by weight per 100 parts by weight of organopolysiloxane (1).
Zusätzlich zu den bisher genannten Stoffen (1), (2) und (3) können bei dem erfindungsgemäßen Verfahren gegebenenfalls weitere Stoffe, wie sie zur Imprägnierung von organischen Fasern herkömmlicherweise mitverwendet werden können, mitverwendet werden. Beispiele für derartige weitere Stoffe sind in den endständigen Einheiten je eine Si-gebundene Hydroxylgruppe aufweisende Dimethylpolysiloxane mit einer Viskosität von höchstens 10 000 mPa.s bei 25°C, durch Trimethylsiloxygruppen endblockierte Dimethylpolysiloxane mit einer Viskosität von hochstens 10 000 mPa.s bei 25°C und, vor allem, wenn die zu imprägnierenden Fasern mindestens zum Teil aus Cellulose oder Baumwolle bestehen, sogenannte "Knitterfrei-Ausrüstungen", wie Dimethyldihydroxyethylenharnstoff (DMDHEU) im Gemisch mit Zinknitrat oder Magnesiumchlorid.In addition to the previously mentioned substances (1), (2) and (3), further substances, such as can conventionally be used for the impregnation of organic fibers, can optionally also be used in the process according to the invention. Examples of such further substances in the terminal units are dimethylpolysiloxanes each having an Si-bonded hydroxyl group and having a viscosity of at most 10,000 mPa.s at 25 ° C, dimethylpolysiloxanes endblocked by trimethylsiloxy groups and having a viscosity of at most 10,000 mPa.s at 25 ° C and, especially if the fibers to be impregnated consist at least in part of cellulose or cotton, so-called "crease-free finishes", such as dimethyldihydroxyethylene urea (DMDHEU) in a mixture with zinc nitrate or magnesium chloride.
Die bei dem erfindungsgemäßen Verfahren eingesetzten Stoffe können in unverdünnter Form oder in Form von Lösungen in organischem Lösungsmittel oder in Form wäßriger Emulsionen auf die zu imprägnierenden Fasern aufgetragen werden. Werden dabei wäßrige Emulsionen eingesetzt, so können diese Emulsionen zusätzlich zu Wasser, Dispergiermittel und den oben genannten, zu dispergierenden Stoffen Verdickungsmittel, wie Poly-N-vinylpyrrolidon, enthalten. Vorzugsweise werden die bei dem erfindungsgemäßen Verfahren eingesetzten Stoffe in Form wäßriger Emulsionen auf die zu imprägnierenden Fasern aufgetragen. Als Dispergiermittel in diesen Dispersionen sind nichtionogene und kationogene Emulgatoren bevorzugt. Die Herstellung dieser Emulsionen kann in für die Emulgierung von Organopolysiloxanen bekannter Weise erfolgen.The substances used in the process according to the invention can be applied to the fibers to be impregnated in undiluted form or in the form of solutions in organic solvent or in the form of aqueous emulsions. If aqueous emulsions are used, these emulsions can contain, in addition to water, dispersant and the above-mentioned substances to be dispersed, thickeners, such as poly-N-vinylpyrrolidone. The substances used in the process according to the invention are preferably applied in the form of aqueous emulsions to the fibers to be impregnated. As dispersants in these dispersions are nonionic and cationogenic emulsifiers preferred. These emulsions can be prepared in a manner known for the emulsification of organopolysiloxanes.
Das Auftragen der bei dem erfindungsgemäßen Verfahren verwendeten Stoffe auf die zu imprägnierenden Fasern kann in beliebiger für die Imprägnierung von Fasern geeigneter und vielfach bekannter Weise erfolgen, z. B. durch Tauchen, Streichen, Gießen, Sprühen, einschließlich Sprühen aus Aerosolverpackung, Aufwalzen, Klotzen oder Drucken.The substances used in the process according to the invention can be applied to the fibers to be impregnated in any suitable and well-known manner for the impregnation of fibers, e.g. B. by dipping, brushing, pouring, spraying, including spraying from aerosol packaging, rolling, padding or printing.
Vorzugsweise werden die bei dem erfindungsgemäßen Verfahren verwendeten Stoffe in solchen Mengen aufgetragen, daß die Gewichtszunahme der Faser durch diese Stoffe, abzüglich der dabei gegebenenfalls mitverwendeten Verdünnungsmittel, 1 bis 20 Gewichtsprozent, bezogen auf das Gewicht der Faser, beträgt.The substances used in the process according to the invention are preferably applied in amounts such that the weight gain of the fiber by these substances, minus any diluents which may be used, is 1 to 20 percent by weight, based on the weight of the fiber.
Die Vernetzung der bei dem erfindungsgemäßen Verfahren eingesetzten Organosiliciumverbindungen auf der Faser erfolgt bei Raumtemperatur: Sie kann durch Erwärmen auf z. B. 50° bis 180°C beschleunigt werden.The organosilicon compounds used in the process according to the invention are crosslinked on the fiber at room temperature. B. accelerated 50 ° to 180 ° C.
In den folgenden Teilen der Beschreibung beziehen sich alle Angaben von Teilen und Prozentsätzen auf das Gewicht, soweit nichts anderes angegeben ist.In the following parts of the description, all parts and percentages are by weight unless otherwise stated.
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a) Ein Gemisch aus 1 Teil des Silans der Formel
H₂N(CH₂)₂NH(CH₂)₃CH₃Si(OCH₃)₂,
1 Teil des Silans der Formel
H₂N(CH₂)₂NH(CH₂)₃Si(OCH₃)₃
und 160 Teilen einer Mischung von cyclischen Dimethylpolysiloxanen mit 3 bis 10 Siloxaneinheiten je Molekül und 0,03 Teilen einer 40 %-igen Lösung von Benzyltrimethylammoniumhydroxyd in Methanol wird unter Stickstoff und Rühren 4 Stunden auf 80°C erwärmt. Dann wird das quaternäre Ammoniumhydroxyd durch 60 Minuten Erwärmen auf 150°C bei 13 hPa (abs.) unwirksam gemacht und gleichzeitig das Organopolysiloxan von unter diesen Bedingungen siedenden Bestandteilen befreit. Das so erhaltene Organopolysiloxan enthält als direkt an Silicium gebundene, kondensationsfähige Gruppen Methoxygruppen und zusätzlich zu Dimethylsiloxaneinheiten sowohl Monoorganosiloxaneinheiten mit basischem Stickstoff als auch Diorganosiloxaneinheiten mit basischem Stickstoff. Es hat eine Viskosität von 7 400 mm² . s-¹ bei 25°C.a) A mixture of 1 part of the silane of the formula
H₂N (CH₂) ₂NH (CH₂) ₃CH₃Si (OCH₃) ₂,
1 part of the silane of the formula
H₂N (CH₂) ₂NH (CH₂) ₃Si (OCH₃) ₃
and 160 parts of a mixture of cyclic dimethylpolysiloxanes with 3 to 10 siloxane units per molecule and 0.03 part of a 40% solution of benzyltrimethylammonium hydroxide in methanol is heated to 80 ° C. for 4 hours under nitrogen and with stirring. Then the quaternary ammonium hydroxide is rendered ineffective by heating for 60 minutes at 150 ° C. at 13 hPa (abs.) And at the same time the organopolysiloxane is freed from constituents boiling under these conditions. The organopolysiloxane thus obtained contains methoxy groups as condensable groups bonded directly to silicon and, in addition to dimethylsiloxane units, both monoorganosiloxane units with basic nitrogen and diorganosiloxane units with basic nitrogen. It has a viscosity of 7,400 mm². s - ¹ at 25 ° C. - b) 35 Teile des Organopolysiloxans, dessen Herstellung vorstehend unter a) beschrieben wurde, werden unter Verwendung von 2 Teilen Polyglykolether, der durch Umsetzung von Isotridecanol (1 Mol) mit Ethylenoxyd (etwa 10 Mol) hergestellt wurde, und 2 Teilen Stearydimethylbenzylammoniumchlorid als Dispergiermitteln in 61 Teilen Wasser emulgiert.b) 35 parts of the organopolysiloxane, the preparation of which was described above under a), using 2 parts of polyglycol ether, which was prepared by reacting isotridecanol (1 mol) with ethylene oxide (about 10 mol), and 2 parts of stearydimethylbenzylammonium chloride as dispersants in 61 parts of water emulsified.
- c) 35 Teile Methylwasserstoffpolysiloxan mit 1,6 % Si-gebundenem Wasserstoff und einer Viskosität von 21 mm² . s-¹ bei 25°C werden unter Verwendung von 3 Teilen Polyglykolether, der durch Umsetzung von Nonylphenol (1 Mol) mit Ethylenoxyd (etwa 10 Mol) hergestellt wurde, als Dispergiermittel in 61,9 Teilen Wasser und 0,1 Teilen Eisessig emulgiert.c) 35 parts of methyl hydrogen polysiloxane with 1.6% Si-bonded hydrogen and a viscosity of 21 mm². s - 1 at 25 ° C using 3 parts of polyglycol ether, which is prepared by reacting nonylphenol (1 mole) with ethylene oxide (about 10 moles) was emulsified as a dispersant in 61.9 parts of water and 0.1 part of glacial acetic acid.
- d) 25 Teile Di-n-butylzinndilaurat werden unter Verwendung von 3 Teilen Polyglykolether, der durch Um-Setzung von Nonylphenol (1 Mol) mit Ethylenoxyd (etwa 10 Mol) hergestellt wurde, als Dispergiermittel in 72 Teilen Wasser emulgiert.d) 25 parts of di-n-butyltin dilaurate are emulsified in 72 parts of water using 72 parts of polyglycol ether, which was prepared by reacting nonylphenol (1 mole) with ethylene oxide (about 10 moles) as a dispersant.
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e) Ein Polyamid-Gewirke mit einem Gewicht von 180 g/m² wird in eine Emulsion getaucht, die
50 g/l der Emulsion, deren Herstellung oben unter b) beschrieben wurde,
2,5 g/l der Emulsion, deren Herstellung oben unter c) beschrieben wurde,
2,5 g/l der Emulsion, deren Herstellung oben unter d) beschrieben wurde, und als Rest Wasser enthält,
und dann auf 90 % Flüssigkeitsaufnahme abgequetscht. Danach wird das so imprägnierte Gewirke 5 Minuten auf 150°C erwärmt.
Das so erhaltene imprägnierte Gewirke besitzt einen weichen elastischen Griff und ausgezeichnetes Rückstellvermögen. Diese vorteilhaften Eigenschaften sind auch noch nach 5 Feinwäschen bei 40°C in einer Haushaltswaschmaschine vorhanden.e) A knitted polyamide fabric weighing 180 g / m² is immersed in an emulsion which
50 g / l of the emulsion, the preparation of which was described above under b),
2.5 g / l of the emulsion, the preparation of which was described above under c),
2.5 g / l of the emulsion, the preparation of which was described under d) above, and contains water as the balance,
and then squeezed to 90% fluid intake. The knitted fabric impregnated in this way is then heated to 150 ° C. for 5 minutes.
The impregnated knitted fabric thus obtained has a soft, elastic feel and excellent resilience. These advantageous properties are still present after 5 delicates at 40 ° C in a household washing machine.
Ein Gewebe aus 50 % Baumwolle und 50 % Polyester mit einem Gewicht von 210 g/m² wird in eine Emulsion getaucht, die
40 g/l der Emulsion, deren Herstellung in Beispiel 1 unter b) beschrieben wurde,
4 g/l der Emulsion, deren Herstellung in Beispiel 1 unter c) beschrieben wurde,
4 g/l der Emulsion, deren Herstellung in Beispiel 1 unter d) beschrieben wurde,
80 g/l DMDHEU
10 g/l Magnesiumchlorid
und als Rest Wasser enthält, und dann auf 80 % Flüssigkeitsaufnahme abgequetscht. Danach wird das so imprägnierte Gewebe 10 Minuten auf 150°C erwärmt.A fabric made of 50% cotton and 50% polyester with a weight of 210 g / m² is immersed in an emulsion that
40 g / l of the emulsion, the preparation of which was described in Example 1 under b),
4 g / l of the emulsion, the preparation of which was described in Example 1 under c),
4 g / l of the emulsion, the preparation of which was described in Example 1 under d),
80 g / l DMDHEU
10 g / l magnesium chloride
and contains the rest of water, and then squeezed to 80% fluid intake. The fabric so impregnated is then heated to 150 ° C. for 10 minutes.
Das so erhaltene imprägnierte Gewebe besitzt einen weichen elastischen Griff, der auch nach 5 Feinwäschen bei 60°C in einer Haushaltswaschmaschine noch vorhanden ist.The impregnated fabric thus obtained has a soft, elastic handle, which is still present in a household washing machine even after 5 delicates at 60 ° C.
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f) Die in Beispiel 1 unter a) beschriebene Arbeitsweise wird wiederholt mit den Abänderungen, daß anstelle von 1 Teil des Silans der Formel
H₂N(CH₂)₂NH(CH₂)₃CH₃Si(OCH₃)₂
3 Teile dieses Silans und
anstelle von 160 Teilen der Mischung von cyclischen Dimethylpolysiloxanen mit 3 bis 10 Siloxaneinheiten je Molekül 100 Teile dieser Mischung von cyclischen Dimethylpolysiloxanen verwendet werden.f) The procedure described in Example 1 under a) is repeated with the modifications that instead of 1 part of the silane of the formula
H₂N (CH₂) ₂NH (CH₂) ₃CH₃Si (OCH₃) ₂
3 parts of this silane and
instead of 160 parts of the mixture of cyclic dimethylpolysiloxanes with 3 to 10 siloxane units per molecule, 100 parts of this mixture of cyclic dimethylpolysiloxanes are used. - g) Die in Beispiel 1 unter b) beschriebene Arbeitsweise wird wiederholt mit der Abänderung, daß 35 Teile des Organopolysiloxans, dessen Herstellung vorstehend unter f) beschrieben wurde, anstelle des Organopolysiloxans, dessen Herstellung in Beispiel 1 unter a) beschrieben wurde, verwendet werden.g) The procedure described in Example 1 under b) is repeated with the modification that 35 parts of the organopolysiloxane, the preparation of which was described under f) above, are used instead of the organopolysiloxane, the preparation of which was described in Example 1 under a).
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h) Ein Wollstoff mit einem Gewicht von 400 g/m² wird in eine Emulsion getaucht, die
50 g/l der Emulsion, deren Herstellung oben unter g) beschrieben wurde,
1 g/l der Emulsion, deren Herstellung in Beispiel 1 unter c) beschrieben wurde,
1 g/l der Emulsion, deren Herstellung in Beispiel 1 unter d) beschrieben wurde,
und als Rest Wasser enthält, und dann auf 100 % Flussigkeitsaufnahme abgequetscht. Danach wird das so imprägnierte Gewebe 10 Minuten auf 150°C erwärmt. Das so imprägnierte Gewebe besitzt einen weichen elastischen Griff und ist beim Waschen bei 30°C in einer Haushaltswaschmaschine dimensionsbeständig.h) A wool fabric with a weight of 400 g / m² is immersed in an emulsion which
50 g / l of the emulsion, the preparation of which was described above under g),
1 g / l of the emulsion, the preparation of which was described in Example 1 under c),
1 g / l of the emulsion, the preparation of which was described in Example 1 under d),
and the rest contains water, and then squeezed to 100% liquid absorption. The fabric so impregnated is then heated to 150 ° C. for 10 minutes. The fabric impregnated in this way has a soft, elastic handle and is dimensionally stable when washed at 30 ° C in a household washing machine.
- (1) Die in Beispiel 1 unter b) beschriebenen Arbeitsweise wird wiederholt mit der Abänderung, daß anstelle der 35 Teile des dort verwendeten Organopolysiloxans 35 Teile des gemäß US-A-4 098 701, Beispiel 1, zur Emulsionsherstellung eingesetzten Organopolysiloxans eingesetzt werden.(1) The procedure described in Example 1 under b) is repeated with the modification that instead of the 35 parts of the organopolysiloxane used there, 35 parts of the organopolysiloxane used in emulsion preparation according to US Pat. No. 4,098,701, Example 1, are used.
- (2) Die in Beispiel 1 unter e) beschriebene Arbeitsweise wird wiederholt mit der Abänderung, daß 50g/l der Emulsion, deren Herstellung vorstehend unter (1) beschrieben wurde, anstelle der 50g/l der Emulsion, deren Herstellung in Beispiel 1 unter b) beschrieben wurde, eingesetzt werden.(2) The procedure described in Example 1 under e) is repeated with the modification that 50 g / l of the emulsion, the preparation of which was described in (1) above, instead of the 50 g / l of the emulsion, the preparation of which in Example 1 under b ) was used.
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(3) Die in Beispiel 1 unter b) beschriebene Arbeitsweise wird wiederholt mit der Abänderung, daß anstelle der 35 Teile des dort verwendeten Organopolysiloxans
- 30 Teile
- eines in den endständigen Einheiten je eine Si-gebundene Hydroxylgruppe aufweisenden Dimethylpolysiloxans mit einer Viskosität von 6000 mPa.s bei 25°C und
- 5 Teile
- eines Umsetzungsprodukts aus in den endständigen Einheiten je eine Si-gebundene Hydroxylgruppe aufweisendem Dimethylpolysiloxan mit einer Viskosität von 100 mPa.s bei 25°C und dem Silan der Formel
H₂N(CH₂)₂NH(CH₂)₃Si(OCH₃)₃
wobei dieses Umsetzungsprodukt eine Aminzahl von 0,5 und eine Viskosität von 160 mPa.s bei 25°C hat,
- 30 parts
- a dimethylpolysiloxane each having an Si-bonded hydroxyl group in the terminal units and having a viscosity of 6000 mPa.s at 25 ° C. and
- 5 parts
- a reaction product of dimethylpolysiloxane each having an Si-bonded hydroxyl group in the terminal units and having a viscosity of 100 mPa.s at 25 ° C. and the silane of the formula
H₂N (CH₂) ₂NH (CH₂) ₃Si (OCH₃) ₃
wherein this reaction product has an amine number of 0.5 and a viscosity of 160 mPa.s at 25 ° C,
- (4) Die in Beispiel 1 unter e) beschriebene Arbeitsweise wird wiederholt mit der Abänderung, daß 50g/l der Emulsion, deren Herstellung vorstehend unter (3) beschrieben wurde, anstelle 50g/l der Emulsion, deren Herstellung in Beispiel 1 unter b) beschrieben wurde, verwendet werden.(4) The procedure described in Example 1 under e) is repeated with the modification that 50 g / l of the emulsion whose preparation was described above under (3) instead of 50 g / l of the emulsion whose preparation in Example 1 under b) has been used.
Die gemäß Beispiel 1 imprägnierten Gewirke und die gemäß den beiden Vergleichsversuchen imprägnierten Gewirke wurden von 9 Personen, die keine Kenntnis davon besaßen, welche Gewirke gemäß den Vergleichsversuchen und welches Gewirk gemäß Beispiel 1 imprägniert wurde, hinsichtlich ihres Griffs bewertet. Dabei wurde vor und nach 5 Feinwäschen bei 40°C in einer Haushaltswaschmaschine jeweils das gemäß Beispiel 1 imprägnierte Gewirke 5 mal und die gemäß den beiden Vergleichsversuchen imprägnierten Gewirke jeweils 2 mal am besten bewertet.The knitted fabrics impregnated according to Example 1 and the knitted fabrics impregnated according to the two comparative tests were evaluated for their grip by 9 people who had no knowledge of which knitted fabrics according to the comparative tests and which knitted fabric was impregnated according to Example 1. Before and after 5 delicates at 40 ° C. in a household washing machine, the knitted fabric impregnated according to Example 1 was rated 5 times and the knitted fabric impregnated according to the two comparative tests was rated twice.
Claims (3)
- Process for the impregnation of organic fibres with (1) an organopolysiloxane which has condensable groups bonded directly to the silicon and, in addition to diorganosiloxane units wherein the two SiC-bonded organic radicals are monovalent hydrocarbon radicals, contains at least two monovalent SiC-bonded radicals containing basic nitrogen, (2) an organopolysiloxane having at least 3 Si-bonded hydrogen atoms per molecule and (3) a catalyst for the condensation of condensable groups bonded directly to the silicon, characterized in that the SiC-bonded radicals containing basic nitrogen are present in the organopolysiloxane (1) both in monoorganosiloxane and in diorganosiloxane units.
- Process according to Claim 1, characterized in that the ratio of the number of monoorganosiloxane units containing basic nitrogen to the number of diorganosiloxane units containing basic nitrogen is 0.1 : 3 to 3 : 1.
- Process according to Claim 1 or 2, characterized in that the ratio of the number of monoorganosiloxane units containing basic nitrogen to the number of diorganosiloxane units containing basic nitrogen is 0.9 : 1 to 1.1 : 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86101240T ATE63583T1 (en) | 1985-02-01 | 1986-01-30 | PROCESS FOR IMPREGNATION OF ORGANIC FIBERS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853503457 DE3503457A1 (en) | 1985-02-01 | 1985-02-01 | METHOD FOR IMPREGNATING ORGANIC FIBERS |
| DE3503457 | 1985-02-01 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0190672A2 EP0190672A2 (en) | 1986-08-13 |
| EP0190672A3 EP0190672A3 (en) | 1988-09-28 |
| EP0190672B1 true EP0190672B1 (en) | 1991-05-15 |
Family
ID=6261426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86101240A Expired - Lifetime EP0190672B1 (en) | 1985-02-01 | 1986-01-30 | Process for the impregnation of organic fibres |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4720520A (en) |
| EP (1) | EP0190672B1 (en) |
| JP (1) | JPS61179376A (en) |
| KR (1) | KR890001790B1 (en) |
| AT (1) | ATE63583T1 (en) |
| BR (1) | BR8600117A (en) |
| CA (1) | CA1274731A (en) |
| DE (2) | DE3503457A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4800026A (en) * | 1987-06-22 | 1989-01-24 | The Procter & Gamble Company | Curable amine functional silicone for fabric wrinkle reduction |
| DE3727181A1 (en) * | 1987-08-14 | 1989-02-23 | Wacker Chemie Gmbh | USE OF SELF-CROSS-LINKED VINYLESTER DISPERSIONS WITH REDUCED RELATIONSHIPS WITHOUT FORMALDEHYDE CONTENT FOR STRENGTHENING TEXTILE FIBER FABRICS |
| JPS6461576A (en) * | 1987-08-27 | 1989-03-08 | Lion Corp | Gloss preventing composition |
| DE3730413A1 (en) * | 1987-09-10 | 1989-03-30 | Wacker Chemie Gmbh | METHOD FOR IMPREGNATING ORGANIC FIBERS |
| GB8725921D0 (en) * | 1987-11-05 | 1987-12-09 | Precision Proc Textiles Ltd | Treatment of wool |
| EP0360383A3 (en) * | 1988-09-21 | 1991-12-11 | International Paper Company | Resilient cotton fiber and related method |
| GB8828414D0 (en) * | 1988-12-06 | 1989-01-05 | Precision Proc Textiles Ltd | Method for treatment of cellulosic fibres |
| GB9303815D0 (en) * | 1993-02-25 | 1993-04-14 | Unilever Plc | Use of fabric treatment compositions |
| DE102006052730A1 (en) | 2006-11-08 | 2008-05-15 | Wacker Chemie Ag | Process for the treatment of filler fibers with aqueous dispersions of organopolysiloxanes |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1419968A (en) * | 1963-12-07 | 1965-12-03 | Shinetsu Chem Ind Co | Improvements to the compositions and processes for waterproofing fabrics |
| GB1434017A (en) * | 1972-07-15 | 1976-04-28 | Dow Corning Ltd | Treatment of fibres |
| GB1570983A (en) * | 1976-06-26 | 1980-07-09 | Dow Corning Ltd | Process for treating fibres |
| JPS5328468A (en) * | 1976-08-27 | 1978-03-16 | Citizen Watch Co Ltd | Electronic wristwatch with electronic calculator |
| JPS57111354A (en) * | 1980-12-29 | 1982-07-10 | Toray Silicone Co Ltd | Organopolysiloxane composition |
| DE3104582A1 (en) * | 1981-02-10 | 1982-09-02 | Wacker-Chemie GmbH, 8000 München | "METHOD FOR IMPREGNATING TEXTILE AREAS" |
| JPS5825789A (en) * | 1981-08-07 | 1983-02-16 | Matsushita Electric Ind Co Ltd | Color television receiver for multisystem receiving |
| JPS61296184A (en) * | 1985-06-20 | 1986-12-26 | 信越化学工業株式会社 | Fiber treatment agent |
-
1985
- 1985-02-01 DE DE19853503457 patent/DE3503457A1/en not_active Withdrawn
- 1985-12-10 CA CA000497249A patent/CA1274731A/en not_active Expired - Lifetime
-
1986
- 1986-01-14 BR BR8600117A patent/BR8600117A/en not_active IP Right Cessation
- 1986-01-14 KR KR1019860000183A patent/KR890001790B1/en not_active IP Right Cessation
- 1986-01-30 DE DE8686101240T patent/DE3679206D1/en not_active Expired - Lifetime
- 1986-01-30 EP EP86101240A patent/EP0190672B1/en not_active Expired - Lifetime
- 1986-01-30 AT AT86101240T patent/ATE63583T1/en active
- 1986-01-31 JP JP61018265A patent/JPS61179376A/en active Granted
-
1987
- 1987-04-09 US US07/039,811 patent/US4720520A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0190672A2 (en) | 1986-08-13 |
| DE3679206D1 (en) | 1991-06-20 |
| CA1274731A (en) | 1990-10-02 |
| JPS61179376A (en) | 1986-08-12 |
| ATE63583T1 (en) | 1991-06-15 |
| DE3503457A1 (en) | 1986-08-07 |
| US4720520A (en) | 1988-01-19 |
| EP0190672A3 (en) | 1988-09-28 |
| KR890001790B1 (en) | 1989-05-22 |
| JPS641591B2 (en) | 1989-01-12 |
| BR8600117A (en) | 1986-09-23 |
| KR860006597A (en) | 1986-09-13 |
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