EP0051138A1 - Process for rendering waterrepellent fibrous material - Google Patents
Process for rendering waterrepellent fibrous material Download PDFInfo
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- EP0051138A1 EP0051138A1 EP81107352A EP81107352A EP0051138A1 EP 0051138 A1 EP0051138 A1 EP 0051138A1 EP 81107352 A EP81107352 A EP 81107352A EP 81107352 A EP81107352 A EP 81107352A EP 0051138 A1 EP0051138 A1 EP 0051138A1
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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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
- D06M13/507—Organic silicon compounds without carbon-silicon bond
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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
Definitions
- the present invention relates to a process for hydrophobicizing fiber material, the fiber materials being treated with aqueous liquors which contain an emulsified organopolysiloxane with at least two, optionally modified hydroxyl groups, a polysilicic acid ester emulsion and a reaction product which is produced by the action of at least one halohydrin and / or epoxy group organic compound containing a nitrogen-bonded hydrogen atom-containing organic compound is obtained, which is water-soluble in the form of its salt or at least water-dispersible, contained and then be finished in a conventional manner.
- DE-AS 1 282 597 discloses a process for rendering textiles water repellent, the same using aqueous emulsions of organopolysiloxanes containing hydroxyl groups, silicic acid esters and a catalyst combination of esters of zirconic or titanium acid with aliphatic tertiary amines which contain at least 2-ß-hydroxyalkyl groups wear, and water-soluble salts of zinc or cadmium treated with organic or inorganic acids and on are then briefly heated.
- This known method only provides inadequate water repellency effects which no longer meet today's requirements (see comparative experiments in Example 1).
- alkyl hydrogen polysiloxanes As organopolysiloxanes or at least to use them as crosslinking agents for organopolysiloxanes which contain groups capable of crosslinking.
- these emulsified alkyl hydrogen polysiloxanes tend to release hydrogen, which leads to a loss of their effectiveness. Warehousing is also difficult.
- the present invention was therefore based on the object of obtaining good hydrophobizing effects on fiber materials in the absence of organohydrogenpolysiloxanes. This object was achieved by the method according to the invention.
- organopolysiloxanes used are known (see, for example, "Ullmann's Encyclopedia of Industrial Chemistry", Verlag Urban & Schwarzenberg, Kunststoff-Berlin, Volume 15, (1964), pages 784 ff, section "Silicone Rubber”). Those organopolysiloxanes which carry terminal hydroxyl groups are preferably used. These hydroxyl groups can, however, also be modified, but the ability of these groups to crosslink must be ensured. Otherwise, the organopolysiloxanes are customary dialkyl, in particular dimethylpolysiloxanes, which may have been modified by special substituents.
- the alkyl, in particular methyl groups in the reactive end groups-containing polysiloxanes can be substituted by phenyl, benzyl, ethylphenyl or ethyl groups.
- organopolysiloxanes also play a role in which some of the alkyl groups are replaced by unsaturated organic groups, e.g. Vinyl groups, is replaced.
- the organopolysiloxanes described are emulsified with the aid of nonionic or cationic emulsifiers.
- Polyvinyl alcohols are particularly suitable as nonionic emulsifiers.
- ethylene oxide conversion products of higher fatty acids, fatty alcohols, fatty acid amides and higher amines are also suitable.
- the ethoxylation products of the higher amines can also be used in the form of their salts with low carboxylic acids, such as acetic, formic or propionic acids, or mineral acids, such as hydrochloric acid, hydrobromic acid or sulfuric acid.
- emulsifiers examples are e.g. in GB-PS 1 404 356 and US-PS 3 748 275.
- Quaternary ammonium salts may be mentioned as cationic emulsifiers.
- examples of such compounds are lauryl- and cetylbenzyldi methylammonium chloride or octadecyloxymethylpyridinium chloride.
- reaction products C) are particularly preferably used as emulsifiers for the organopolysiloxanes (see explanations below). This eliminates the need for these reaction products to be added separately to the equipment fleet, which considerably simplifies their manufacture.
- the emulsifiers mentioned are used in an amount of at least 4% by weight, in particular 10-40% by weight, calculated as a 100% emulsifier, based on the organopolysiloxane with at least two, preferably terminal, optionally etherified or crosslinkable esterified hydroxyl groups.
- the polysilicic acid esters used according to the invention which are derived from silicic acid esters of monohydric alcohols having 1 to 4 carbon atoms, are those with a molecular weight of approximately 300 to 750. Examples include methyl, n-propyl, n -Butyl polysilicate and especially called ethyl polysilicate. As comparative experiments have shown, monomeric silicic acid esters are less suitable for the process according to the invention, and it is surprising that the polysilicic acid esters described have an outstandingly favorable effect on the hydrophobizing effect.
- the polysilicic acid esters mentioned are emulsified with the aid of nonionic emulsifiers.
- the compounds already mentioned above can be used as nonionic emulsifiers, these compounds being used in an amount of about 4 to 40% by weight, based on the polysilicic acid ester.
- the polysilicic acid ester emulsions can be prepared in a known manner. For this purpose, a pre-emulsion is first prepared, which is then e.g. is converted into a stable, storable emulsion by high-pressure homogenization. If nonionic emulsifiers are used to prepare emulsions B), it is readily possible to emulsify the organopolysiloxane together with the emulsification of the polysilicic acid ester.
- reaction products C) further used according to the invention are known as such. They are described in the literature as emulsifiers for water-insoluble substances, but also as curing agents for silicones (see US Pat. Nos. 3,320,197, 3,848,022, 3,729,437 and 3,211,580 and GB Pat. No. 1,056,808). These reaction products are generally obtained by reacting organic compounds which contain at least one halohydrin and / or epoxy group with a compound which has nitrogen-bonded hydrogen atoms, reaction products being formed which are water-soluble or at least in the form of the salts are water dispersible.
- organic compounds with at least one halohydrin and / or epoxy group are glycidyl or halogen, in particular chlorohydrin ethers of polyvalent phenols, such as 4,4'-dihydroxydiphenylpropane and methane, resorcinol or of polyvalent aliphatic alcohols, such as ethylene and propylene glycol , Glycerin, polyalkylene glycols and sorbitol or the glycidyl or halohydrin esters of dicarboxylic acids, such as adipic acid or terephthalic acid, and mixtures of the compounds mentioned.
- Organopolysiloxanes containing epoxy groups are also quite suitable. The compounds containing epoxy groups are generally preferred for practical considerations.
- di- or polyamines such as ethylene and propylene diamine, diethylene triamine, triethylene tetramine, dipropylene triamine, cycloaliphatic diamines, such as 1,4-diaminocyclohexane and heterocyclic compounds with at least 2 secondary amine groups, such as piperazine.
- Such compounds are also urea or imino urea or their derivatives (eg dicyandiamide, cyanamide, aryl or alkyl guanamines, melamine) or the heating products thereof. If these compounds are used to prepare the reaction products C), it is additionally necessary to use compounds of the formula to be used in which R 1 is an alkyl group with 2 to 4 carbon atoms or an alkanol group with 2 to 5 carbon atoms, R 2 and R 3 are independently hydrogen, an alkyl group with 1 to 4 carbon atoms or an alkanol group with 2 to 5 carbon atoms and in the molecule at least 2 reactive hydrogen atoms are contained. If R 2 and R 3 are hydrogen, these compounds can also be used in the absence of urea or the urea derivatives to prepare the reaction products C). Examples of these compounds are described in U.S. Patent No. 3,725,502.
- Both the organic compounds with at least one halohydrin and / or epoxy group and those with nitrogen-bonded hydrogen atoms can be wholly or partly by lipophilic residues, such as higher molecular weight alkyl, alkylcycloalkyl and / or alkylaryl residues with at least 8, preferably 12 to 18 C- Atoms are substituted.
- lipophilic residues such as higher molecular weight alkyl, alkylcycloalkyl and / or alkylaryl residues with at least 8, preferably 12 to 18 C- Atoms are substituted.
- halophine and / or epoxy compounds containing lipophilic groups are the reaction product of 1 mol of coconut fatty amine with 2 mol of epichlorohydrin and the bischlorohydrin ether of glycerol mono lauric acid ester listed.
- N-stearylethylenediamine N-acylamidoamines and reaction products of fatty alcohol monochlorohydrin ethers or fatty acid chlorohydrin esters with di- or polyamines.
- the starting compounds containing the lipophilic residues it is also sufficient if only one of the reaction components for the preparation of the reaction products C) has all or some of the lipophilic residues.
- the amounts of the substances mentioned for the preparation of the reaction products C) are described in detail in the listed patents (see also patent claims).
- the manufacture is also specified in detail.
- the starting substances are reacted with one another in aqueous, aqueous / alcoholic or alcoholic solution at elevated temperature for up to 1 hour and then - if necessary - by adding volatile acids, e.g. Acetic acid or hydrochloric acid, the reaction is stopped and adjusted to the desired concentration with water.
- volatile acids e.g. Acetic acid or hydrochloric acid
- reaction products C) as emulsifiers for the organopolysiloxanes already described in more detail above, since this makes simplified storage and liquor production possible. In this case, too, better hydrophobic effects are obtained.
- reaction products C particular preference is given to those whose preparation is described in US Pat. No. 3,320,197 and US Pat. No. 3,211,580, since this results in particularly favorable hydrophobicity values.
- the treatment liquors can be prepared in a simple manner by combining the constituents A), B) and C) and diluting with water and adjusting the pH to 5.5 to 7.5, in particular 6 to 7, in a known manner with preferably volatile acids . So much of the usually 20 to 40% by weight polysiloxane emulsion A) is used that the liquor is at least 6, in particular 8 to 50 g Contains organopolysiloxane per liter. Of the polysilicic acid ester dispersion B), which generally contains 35 to 65% by weight of polysilicic acid ester, 2 to 30 g, in particular 2 to 20 g, per liter of finishing liquor are used.
- the reaction product C which is generally an 8 to 25% solution, is used in amounts such that at least 6% by weight, in particular 10 to 40% by weight, of 100% reaction product C), based on organopolysiloxane, are present in the fleet. If the reaction product C) is used as an emulsifier for the organopolysiloxane emulsion A), which is preferred, the same amounts are used and, of course, subsequent addition of the same is unnecessary.
- the treatment liquors obtained are extremely stable, so that the good hydrophobic effects are obtained even after a standing time of 12 to 24 hours.
- the finishing liquor is applied to the material in customary amounts by padding, slapping, spraying or other known methods (liquor absorption, depending on the fiber material, 40 to 120% by weight) and is then completed by simple heating. In general, it is dried at up to 100 ° C. and condensed at 130 to 170 ° C. for about 2 to 5 minutes. However, it is also possible to carry out the aftertreatment at 110 ° C. for 10 to 20 minutes. It is a particular advantage of the process according to the invention that even low temperatures are sufficient to obtain the good hydrophobic effects.
- the present process for the hydrophobization of fiber materials, in particular textiles, can be combined with conventional crease-free finishing.
- the known synthetic resins can be used.
- Conventional compounds such as magnesium chloride, zinc salts and amine hydrochlorides are suitable as catalysts.
- Fiber materials include leather, synthetic leather, paper, nonwovens and in particular textiles.
- the fiber material preferably consists of natural or regenerated cellulose or mixtures of cellulose with animal or synthetic fibers.
- fiber materials which contain animal, in particular wool, or synthetic fibers, in particular polyester, polyamide and polyacrylonitrile fibers, alone or in mixtures with one another, can also be finished according to the invention.
- Textiles containing cellulose or cellulose are particularly preferably hydrophobized.
- a cotton poplin fabric (approx. 230 g / m 2 ) is impregnated with an aqueous liquor which contains 125 g / 1 of the emulsion specified below and 40 g / 1 of the epoxyamine reaction product used in Example 1 of US Pat. No. 3,320,197 (pH value 7.2), squeezed to a liquor pick-up of 72% and then dried for 10 minutes at 100 ° C. and condensed for 5 minutes at 150 ° C.
- the fabric treated in this way has a water absorption of 17% and a very good water repellent effect (4/4/4).
- the same cotton poplin is equipped in accordance with the prior art (DE-AS 1 282 597), 125 g / 1 of the emulsion also being used, but instead of the ethyl polysilicate the same amount of silica tetraisopropyl ester and instead of the epoxyamine reaction product being the same as that of the DE AS specified catalyst solution contains.
- the pH of the equipment fleet is 7.2.
- the fabric treated in this way has a water absorption of 72% and an insufficient beading effect (1). So that's the superiority of the inventive method clearly recognizable.
- 240 g of a 10% polyvinyl alcohol solution (for data see Example 1) and 310 g of water are placed in this solution and 450 g of ethyl polysilicate (average molecular weight 610; density at 20 ° C. 1.05 to 1.06) are stirred in using a high-speed stirrer and the Pre-emulsion obtained at 200 bar and homogenized at 20 to 25 ° C.
- ethyl polysilicate average molecular weight 610; density at 20 ° C. 1.05 to 1.06
- the pH of the liquor is 7.3.
- Example 1 The cotton poplin mentioned in Example 1 is equipped with these liquors immediately after production, after 2 hours and 12 hours of standing under the conditions mentioned in Example 1.
- the cotton popeline described above is padded with these liquors (liquor absorption about 65%) and then at 110 ° C. for 15 minutes dried.
- a cotton poplin (150 g / m 2 ) is mixed with an aqueous liquor containing 40 g of the ⁇ , ⁇ -dihydroxydimethylpolysiloxane emulsion prepared according to Example 4 of GB-PS 1 404 356, 15 g of that according to Example 1 a of GB-PS 1 056 808 produced epoxyamine reaction product and 10 g of the ethyl polysilicate emulsion prepared in Example 2, padded (liquor absorption approx. 68%) and finally dried and condensed at 110 ° C. for 20 minutes.
- the fabric treated in this way has very good water repellency and a good beading effect.
- an emulsion is prepared using 5 g of nonylphenol polyglycol ether (10 moles of ethylene oxide per mole of nonylphenol) as an emulsifier (emulsion B).
- the pH of the liquors A) to D) is 7.1 to 7.3.
Abstract
Die vorliegende Erfindung betrifft ein Verfahren zum Hydrophobieren von Fasermaterial, wobei die Fasermaterialien mit wäßrigen Flotten behandelt werden, die ein emulgiertes Organopolysiloxan mit mindestens 2, gegebenenfalls vernetzungsfähig modifizierten Hydroxylgruppen, eine nichtionogene Polykieselsäureesteremulsion und ein Umsetzungsprodukt, das durch Einwirkung einer mindestens eine Halogenhydrin- und oder Epoxygruppe enthaltenden organischen Verbindung auf eine Stickstoff-gebundene Wasserstoffatome enthaltende organische Verbindung erhalten worden ist, das in Form seines Salzes wasserlöslich oder zumindest wasserdispergierbar ist, enthalten und dann in üblicher Weise fertiggestellt werden. Es werden nach diesem Verfahren sehr gute wasserabweisende Effekte in Abwesenheit von Alkylwasserstoffpolysiloxanen erhalten.The present invention relates to a process for the hydrophobization of fiber material, the fiber materials being treated with aqueous liquors which contain an emulsified organopolysiloxane with at least 2, optionally crosslinkably modified hydroxyl groups, a nonionic polysilicic acid ester emulsion and a reaction product which is produced by the action of at least one halohydrin and or Organic compound containing epoxy group has been obtained on an organic compound containing nitrogen-bonded hydrogen atoms, which is water-soluble or at least water-dispersible in the form of its salt, and then be finished in a customary manner. Very good water-repellent effects are obtained in the absence of alkyl hydrogen polysiloxanes by this process.
Description
Die vorliegende Erfindung betrifft ein Verfahren zum Hydrophobieren von Fasermaterial, wobei die Fasermaterialien mit wäßrigen Flotten behandelt werden, die ein emulgiertes Organopolysiloxan mit mindestens zwei, gegebenenfalls modifizierten Hydroxylgruppen, eine Polykieselsäureesteremulsion und ein Umsetzungsprodukt, das durch Einwirkung einer mindestens eine Halogenhydrin- und/oder Epoxygruppe enthaltenden organischen Verbindung auf eine Stickstoff-gebundene Wasserstoffatome enthaltende organische Verbindung erhalten worden ist, das in Form seines Salzes wasserlöslich oder zumindestens wasserdispergierbar ist, enthalten und dann in üblicher Weise fertiggestellt werden.The present invention relates to a process for hydrophobicizing fiber material, the fiber materials being treated with aqueous liquors which contain an emulsified organopolysiloxane with at least two, optionally modified hydroxyl groups, a polysilicic acid ester emulsion and a reaction product which is produced by the action of at least one halohydrin and / or epoxy group organic compound containing a nitrogen-bonded hydrogen atom-containing organic compound is obtained, which is water-soluble in the form of its salt or at least water-dispersible, contained and then be finished in a conventional manner.
Aus der DE-AS 1 282 597 ist ein Verfahren zum Wasserabstoßendmachen von Textilien bekannt, wobei dieselben mit wäßrigen Emulsionen von Hydroxylgruppen enthaltenden Organopolysiloxanen, Kieselsäureestern und einer Katalysatorkombination aus Estern der Zirkon- oder Titansäure mit aliphatischen tertiären Aminen, die mindestens 2-ß-Hydroxyalkylgruppen tragen, und wasserlöslichen Salzen des Zinks oder Cadmiums mit organischen oder anorganischen Säuren behandelt und anschließend kurzzeitig erhitzt werden. Dieses bekannte Verfahren liefert nur ungenügende Hydrophobiereffekte, die den heutigen Anforderungen nicht mehr gerecht werden (siehe Vergleichsversuche im Beispiel 1).DE-AS 1 282 597 discloses a process for rendering textiles water repellent, the same using aqueous emulsions of organopolysiloxanes containing hydroxyl groups, silicic acid esters and a catalyst combination of esters of zirconic or titanium acid with aliphatic tertiary amines which contain at least 2-ß-hydroxyalkyl groups wear, and water-soluble salts of zinc or cadmium treated with organic or inorganic acids and on are then briefly heated. This known method only provides inadequate water repellency effects which no longer meet today's requirements (see comparative experiments in Example 1).
Um gute Hydrophobiereffekte auf Fasermaterialien zu erzielen, ist man deshalb darauf angewiesen, als Organopolysiloxane stets Alkylwasserstoffpolysiloxane einzusetzen oder sie zumindest als Vernetzungsmittel für Organopolysiloxane einzusetzen, die zur Vernetzung befähigte Gruppen enthalten. Diese Alkylwasserstoffpolysiloxane neigen jedoch in emulgierter Form zur Abspaltung von Wasserstoff, was zu einer Einbuße ihrer Wirksamkeit führt. Außerdem ist die Lagerhaltung erschwert.In order to achieve good hydrophobizing effects on fiber materials, it is therefore necessary to always use alkyl hydrogen polysiloxanes as organopolysiloxanes or at least to use them as crosslinking agents for organopolysiloxanes which contain groups capable of crosslinking. However, these emulsified alkyl hydrogen polysiloxanes tend to release hydrogen, which leads to a loss of their effectiveness. Warehousing is also difficult.
Der vorliegenden Erfindung lag also die Aufgabe zugrunde, in Abwesenheit von Organowasserstoffpolysiloxanen gute Hydrophobiereffekte auf Fasermaterialien zu erhalten. Diese Aufgabe wurde durch das erfindungsgemäße Verfahren gelöst.The present invention was therefore based on the object of obtaining good hydrophobizing effects on fiber materials in the absence of organohydrogenpolysiloxanes. This object was achieved by the method according to the invention.
Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Hydrophobieren von Fasermaterial, insbesondere von Textilien durch Behandeln des Fasermaterials mit einer wäßrigen Flotte, die
- A) ein emulgiertes Organopolysiloxan mit mindestens 2, vorzugsweise endständigen, gegebenenfalls vernetzungsfähig modifizierten Hydroxylgruppen, und
- B) eine Emulsion eines Kieselsäureesters von einwertigen Alkoholen mit 1 bis 4 C-Atomen, der mit Hilfe eines nichtionogenen Emulgators emulgiert worden ist, enthält und einen pH-Wert von 5 bis 7,5 aufweist, und übliche Fertigstellung, das dadurch gekennzeichnet ist, daß die Flotte als Kieselsäureester (B) Polykieselsäureester und zusätzlich
- C) ein Umsetzungsprodukt enthält, das durch Einwirkung einer mindestens eine Halogenhydrin- und/oder Epoxygruppe enthaltenden organischen Verbindung auf eine Stickstoff-gebundene Wasserstoffatome enthaltende organische Verbindung erhalten worden ist, das in Form seines Salzes wasserlöslich oder zumindest wasserdispergierbar ist.
- A) an emulsified organopolysiloxane with at least 2, preferably terminal, optionally crosslinkable modified hydroxyl groups, and
- B) contains an emulsion of a silicic acid ester of monohydric alcohols with 1 to 4 carbon atoms, which has been emulsified with the aid of a nonionic emulsifier and has a pH of 5 to 7.5, and customary completion, which is characterized in that that the liquor as silicic acid ester (B) polysilicic acid ester and additionally
- C) contains a reaction product which ent by the action of an organic compound containing at least one halohydrin and / or epoxy group on a nitrogen-bonded hydrogen atom Holding organic compound has been obtained, which is water-soluble or at least water-dispersible in the form of its salt.
Die verwendeten Organopolysiloxane sind bekannt (siehe z.B. "Ullmanns Encyklopädie der technischen Chemie", Verlag Urban & Schwarzenberg, München-Berlin, Band 15, (1964), Seiten 784 ff, Abschnitt "Silikonkautschuk"). Vorzugsweise werden solche Organopolysiloxane verwendet, die endständige Hydroxylgruppen tragen. Diese Hydroxylgruppen können aber durchaus auch modifiziert sein, wobei aber die Vernetzungsfähigkeit dieser Gruppen gewährleistet sein muß. Im übrigen handelt es sich bei den Organopolysiloxanen um übliche, gegebenenfalls durch spezielle Substituenten abgewandelte Dialkyl-, insbesondere Dimethylpolysiloxane. Die Alkyl-, insbesondere Methylgruppen in den reaktionsfähige Endgruppen enthaltenden Polysiloxanen können dabei durch Phenyl-, Benzyl-, Äthylphenyl- oder Äthylgruppen substituiert sein. Daneben spielen auch Organopolysiloxane eine Rolle, bei denen ein Teil der Alkylgruppen durch ungesättigte organische Gruppen, z.B. Vinylgruppen, ersetzt ist.The organopolysiloxanes used are known (see, for example, "Ullmann's Encyclopedia of Industrial Chemistry", Verlag Urban & Schwarzenberg, Munich-Berlin, Volume 15, (1964), pages 784 ff, section "Silicone Rubber"). Those organopolysiloxanes which carry terminal hydroxyl groups are preferably used. These hydroxyl groups can, however, also be modified, but the ability of these groups to crosslink must be ensured. Otherwise, the organopolysiloxanes are customary dialkyl, in particular dimethylpolysiloxanes, which may have been modified by special substituents. The alkyl, in particular methyl groups in the reactive end groups-containing polysiloxanes can be substituted by phenyl, benzyl, ethylphenyl or ethyl groups. In addition, organopolysiloxanes also play a role in which some of the alkyl groups are replaced by unsaturated organic groups, e.g. Vinyl groups, is replaced.
Die beschriebenen Organopolysiloxane werden mit Hilfe von nichtionogenen oder kationaktiven Emulgatoren emulgiert. Dabei kommen als nichtionogene Emulgatoren insbesondere Polyvinylalkohole in Betracht. Aber auch Äthylenoxydumsetzungsprodukte von höheren Fettsäuren, Fettalkoholen, Fettsäureamiden und höheren Aminen sind geeignet. Die Äthoxylierungsprodukte der höheren Amine können dabei auch in Form ihrer Salze mit niedrigen Carbonsäuren, wie Essig-, Ameisen- oder Propionsäuren oder Mineralsäuren, wie Salzsäure, Bromwasserstoffsäure oder Schwefelsäure verwendet werden.The organopolysiloxanes described are emulsified with the aid of nonionic or cationic emulsifiers. Polyvinyl alcohols are particularly suitable as nonionic emulsifiers. But ethylene oxide conversion products of higher fatty acids, fatty alcohols, fatty acid amides and higher amines are also suitable. The ethoxylation products of the higher amines can also be used in the form of their salts with low carboxylic acids, such as acetic, formic or propionic acids, or mineral acids, such as hydrochloric acid, hydrobromic acid or sulfuric acid.
Beispiele für derartige Emulgatoren sind z.B. in der GB-PS 1 404 356 und der US-PS 3 748 275 beschrieben.Examples of such emulsifiers are e.g. in GB-PS 1 404 356 and US-PS 3 748 275.
Als kationische Emulgatoren seien quaternäre Ammoniumsalze genannt. Beispiele für derartige Verbindungen sind Lauryl- bzw. Cetylbenzyldimethylammoniumchlorid oder Octadecyloxymethylpyridiniumchlorid.Quaternary ammonium salts may be mentioned as cationic emulsifiers. Examples of such compounds are lauryl- and cetylbenzyldi methylammonium chloride or octadecyloxymethylpyridinium chloride.
Besonders bevorzugt werden als Emulgatoren für die Organopolysiloxane die Umsetzungsprodukte C) eingesetzt (siehe nachfolgende Ausführungen). Dadurch erübrigt sich der gesonderte Zusatz dieser Umsetzungsprodukte zur Ausrüstungsflotte, wodurch deren Herstellung noch wesentlich vereinfacht wird.The reaction products C) are particularly preferably used as emulsifiers for the organopolysiloxanes (see explanations below). This eliminates the need for these reaction products to be added separately to the equipment fleet, which considerably simplifies their manufacture.
Die genannten Emulgatoren werden in einer Menge von mindestens 4 Gew.%, insbesondere 10 - 40 Gew.% - gerechnet als 100%iger Emulgator - bezogen auf das Organopolysiloxan mit mindestens zwei, vorzugsweise endständigen, gegebenenfalls verätherten bzw. vernetzungsfähig veresterten Hydroxylgruppen, eingesetzt.The emulsifiers mentioned are used in an amount of at least 4% by weight, in particular 10-40% by weight, calculated as a 100% emulsifier, based on the organopolysiloxane with at least two, preferably terminal, optionally etherified or crosslinkable esterified hydroxyl groups.
Die Herstellung der Organopolysiloxanemulsionen A) gelingt nach bekannten Verfahren, so daß sich hierzu weitere Ausführungen erübrigen. Ein gängiges Verfahren ist z.B. in der bereits genannten GB-PS 1 404 356 beschrieben.The organopolysiloxane emulsions A) can be prepared by known processes, so that further explanations are unnecessary. A common procedure is e.g. in the aforementioned GB-PS 1 404 356.
Bei den erfindungsgemäß eingesetzten Polykieselsäureestern, die sich von Kieselsäureestern von 1-wertigen Alkoholen mit 1 bis 4 C-Atomen ableiten, handelt es sich um solche mit einem Molekulargewicht von etwa 300 bis 750. Als Beispiele seien Methyl-, n-Propyl-, n-Butylpolysilikat und insbesondere Äthylpolysilikat genannt. Wie Vergleichsversuche gezeigt haben, sind monomere Kieselsäureester für das erfindungsgemäße Verfahren weniger geeignet und es ist überraschend, daß die beschriebenen Polykieselsäureester den Hydrophobiereffekt in so hervorragender Weise günstig beeinflussen.The polysilicic acid esters used according to the invention, which are derived from silicic acid esters of monohydric alcohols having 1 to 4 carbon atoms, are those with a molecular weight of approximately 300 to 750. Examples include methyl, n-propyl, n -Butyl polysilicate and especially called ethyl polysilicate. As comparative experiments have shown, monomeric silicic acid esters are less suitable for the process according to the invention, and it is surprising that the polysilicic acid esters described have an outstandingly favorable effect on the hydrophobizing effect.
Die genannten Polykieselsäureester werden mit Hilfe von nichtionogenen Emulgatoren emulgiert. Als nichtionogene Emulgatoren können dabei die oben bereits genannten Verbindungen eingesetzt werden, wobei diese Verbindungen in einer Menge von etwa 4 bis 40 Gew.%, bezogen auf den Polykieselsäureester, zur Anwendung gelangen.The polysilicic acid esters mentioned are emulsified with the aid of nonionic emulsifiers. The compounds already mentioned above can be used as nonionic emulsifiers, these compounds being used in an amount of about 4 to 40% by weight, based on the polysilicic acid ester.
Die Herstellung der Emulsionen der Polykieselsäureester kann in bekannter Weise vorgenommen werden. Dazu wird zuerst eine Voremulsion hergestellt, die dann z.B. durch Hochdruckhomogenisierung in eine beständige, lagerfähige Emulsion übergeführt wird. Werden nichtionogene Emulgatoren zur Herstellung der Emulsionen B) verwendet, so ist es ohne weiteres möglich, die Emulgierung des Organopolysiloxans zusammen mit der Emulgierung des Polykieselsäureesters vorzunehmen.The polysilicic acid ester emulsions can be prepared in a known manner. For this purpose, a pre-emulsion is first prepared, which is then e.g. is converted into a stable, storable emulsion by high-pressure homogenization. If nonionic emulsifiers are used to prepare emulsions B), it is readily possible to emulsify the organopolysiloxane together with the emulsification of the polysilicic acid ester.
Die erfindungsgemäß weiterhin eingesetzten Umsetzungsprodukte C) sind als solche bekannt. Sie werden in der Literatur als Emulgatoren für wasserunlösliche Substanzen, aber auch als Härtungsmittel für Silikone beschrieben (siehe US-PSS 3 320 197, 3 848 022, 3 729 437 und 3 211 580 sowie GB-PS 1 056 808). Diese Umsetzungsprodukte werden generell dadurch erhalten, daß organische Verbindungen, die mindestens eine Halogenhydrin- und/oder Epoxygruppe enthalten, mit einer Verbindung, die Stickstoff-gebundene Wasserstoffatome aufweist, zur Reaktion gebracht werden, wobei Umsetzungsprodukte entstehen, die in Form der Salze wasserlöslich oder wenigstens wasserdispergierbar sind.The reaction products C) further used according to the invention are known as such. They are described in the literature as emulsifiers for water-insoluble substances, but also as curing agents for silicones (see US Pat. Nos. 3,320,197, 3,848,022, 3,729,437 and 3,211,580 and GB Pat. No. 1,056,808). These reaction products are generally obtained by reacting organic compounds which contain at least one halohydrin and / or epoxy group with a compound which has nitrogen-bonded hydrogen atoms, reaction products being formed which are water-soluble or at least in the form of the salts are water dispersible.
Als organische Verbindungen mit mindestens einer Halogenhydrin- und/oder Epoxygruppe seien beispielsweise Glycidyl- bzw. Halogen-, insbesondere Chlorhydrinäther von polyvalenten Phenolen, wie 4,4'-Dihydroxydiphenylpropan und -methan, Resorcinol oder von polyvalenten aliphatischen Alkoholen, wie Äthylen- und Propylenglykol, Glycerin, Polyalkylenglykolen und Sorbit oder die Glycidyl- bzw. Halogenhydrinester von Dicarbonsäuren, wie Adipinsäure oder Terephthalsäure sowie Mischungen der genannten Verbindungen genannt. Auch Epoxygruppen enthaltende Organopolysiloxane sind durchaus geeignet. Die Epoxygruppen enthaltenden Verbindungen werden aus praktischen Überlegungen im allgemeinen bevorzugt.Examples of organic compounds with at least one halohydrin and / or epoxy group are glycidyl or halogen, in particular chlorohydrin ethers of polyvalent phenols, such as 4,4'-dihydroxydiphenylpropane and methane, resorcinol or of polyvalent aliphatic alcohols, such as ethylene and propylene glycol , Glycerin, polyalkylene glycols and sorbitol or the glycidyl or halohydrin esters of dicarboxylic acids, such as adipic acid or terephthalic acid, and mixtures of the compounds mentioned. Organopolysiloxanes containing epoxy groups are also quite suitable. The compounds containing epoxy groups are generally preferred for practical considerations.
Als organische Verbindungen mit Stickstoff-gebundenen Wasserstoffatomen seien folgende aufgeführt: Di- oder Polyamine, wie Äthylen-und Propylendiamin, Diäthylentriamin, Triäthylentetramin, Dipropylentriamin, cycloaliphatische Diamine, wie 1,4-Diaminocyclohexan und heterocyclische Verbindungen mit mindestens 2 sekundären Amingruppen, wie Piperazin.The following are listed as organic compounds with nitrogen-bonded hydrogen atoms: di- or polyamines, such as ethylene and propylene diamine, diethylene triamine, triethylene tetramine, dipropylene triamine, cycloaliphatic diamines, such as 1,4-diaminocyclohexane and heterocyclic compounds with at least 2 secondary amine groups, such as piperazine.
Als derartige Verbindungen kommen auch Harnstoff oder Iminoharnstoff bzw. deren Derivate (z.B. Dicyandiamid, Cyanamid, Aryl- oder Alkylguanamine, Melamin) oder die Erhitzungsprodukte derselben in Betracht. Werden diese Verbindungen zur Herstellung der Umsetzungsprodukte C) eingesetzt, so ist es notwendig, zusätzlich noch Verbindungen der Formel
Sowohl die organischen Verbindungen mit mindestens einer Halogenhydrin-und/oder Epoxygruppe als auch diejenigen mit Stickstoff-gebundenen Wasserstoffatomen können ganz oder teilweise durch lipophile Reste, wie höhermolekulare Alkyl-, Alkylcycloalkyl- und/oder Alkylarylreste mit wenigstens 8, vorzugsweise 12 bis 18 C-Atomen substituiert sein. Als Beispiele für lipophile Gruppen enthaltende Halogenhydrin- und/oder Epoxyverbindungen seien das Umsetzungsprodukt von 1 Mol Kokosfettamin mit 2 Mol Epichlorhydrin und der Bischlorhydrinäther des Glycerinmonolaurinsäureesters aufgeführt. Beispiele für die weiterhin genannten Verbindungen sind: N-Stearyläthylendiamin, N-Acylamidoamine und Umsetzungsprodukte von Fettalkoholmonochlorhydrinäthern bzw. Fettsäurechlorhydrinestern mit Di- oder Polyaminen. Bei Verwendung der die lipophilen Reste enthaltenden Ausgangsverbindungen genügt es auch, wenn nur eine der Reaktionskomponenten zur Herstellung der Umsetzungsprodukte C) ganz oder zum Teil lipophile Reste aufweist.Both the organic compounds with at least one halohydrin and / or epoxy group and those with nitrogen-bonded hydrogen atoms can be wholly or partly by lipophilic residues, such as higher molecular weight alkyl, alkylcycloalkyl and / or alkylaryl residues with at least 8, preferably 12 to 18 C- Atoms are substituted. Examples of halophine and / or epoxy compounds containing lipophilic groups are the reaction product of 1 mol of coconut fatty amine with 2 mol of epichlorohydrin and the bischlorohydrin ether of glycerol mono lauric acid ester listed. Examples of the compounds also mentioned are: N-stearylethylenediamine, N-acylamidoamines and reaction products of fatty alcohol monochlorohydrin ethers or fatty acid chlorohydrin esters with di- or polyamines. When using the starting compounds containing the lipophilic residues, it is also sufficient if only one of the reaction components for the preparation of the reaction products C) has all or some of the lipophilic residues.
Die verwendeten Mengen an den genannten Substanzen zur Herstellung der Umsetzungsprodukte C) sind in den aufgeführten Patentschriften im Detail beschrieben (siehe auch Patentansprüche). Auch die Herstellung ist im einzelnen angegeben. Im allgemeinen werden die Ausgangssubstanzen in wäßriger, wäßrig/alkoholischer oder alkoholischer Lösung bei erhöhter Temperatur bis zu 1 Stunde miteinander umgesetzt und dann - sofern notwendig - durch Zugabe von flüchtigen Säuren, z.B. Essigsäure oder Salzsäure, die Reaktion abgestoppt und mit Wasser auf die gewünschte Konzentration eingestellt.The amounts of the substances mentioned for the preparation of the reaction products C) are described in detail in the listed patents (see also patent claims). The manufacture is also specified in detail. In general, the starting substances are reacted with one another in aqueous, aqueous / alcoholic or alcoholic solution at elevated temperature for up to 1 hour and then - if necessary - by adding volatile acids, e.g. Acetic acid or hydrochloric acid, the reaction is stopped and adjusted to the desired concentration with water.
Wie bereits oben erwähnt, ist es besonders vorteilhaft, die Umsetzungsprodukte C) als Emulgatoren für die oben bereits näher beschriebenen Organopolysiloxane einzusetzen, da dadurch eine vereinfachte Lagerhaltung und Flottenherstellung möglich ist. Auch werden in diesem Fall bessere Hydrophobiereffekte erhalten. Von den Umsetzungsprodukten C) werden besonders diejenigen bevorzugt, deren Herstellung in der US-PS 3 320 197 und US-PS 3 211 580 beschrieben ist, da hiermit besonders günstige Hydrophobierwerte erhalten werden.As already mentioned above, it is particularly advantageous to use the reaction products C) as emulsifiers for the organopolysiloxanes already described in more detail above, since this makes simplified storage and liquor production possible. In this case, too, better hydrophobic effects are obtained. Of the reaction products C), particular preference is given to those whose preparation is described in US Pat. No. 3,320,197 and US Pat. No. 3,211,580, since this results in particularly favorable hydrophobicity values.
Die Herstellung der Behandlungsflotten gelingt in einfacher Weise durch Zusammengeben der Bestandteile A), B) und C) und Verdünnen mit Wasser sowie Einstellen des pH-Wertes auf 5,5 bis 7,5, insbesondere 6 bis 7 in bekannter Weise mit vorzugsweise flüchtigen Säuren. Dabei wird von der üblicherweise 20 bis 40-gew.%igen Polysiloxanemulsion A) soviel eingesetzt, daß die Flotte mindestens 6, insbesondere 8 bis 50 g Organopolysiloxan je Liter enthält. Von der Polykieselsäureesterdispersion B), die allgemein 35 bis 65 Gew.% Polykieselsäureester enthält, werden 2 bis 30 g, insbesondere 2 bis 20 g je Liter Ausrüstungsflotte verwendet. Das Umsetzungsprodukt C), das im allgemeinen eine 8 bis 25%ige Lösung ist, kommt in solchen Mengen zum Einsatz, daß mindestens 6 Gew.%, insbesondere 10 bis 40 Gew.% an 100%igem Umsetzungsprodukt C), bezogen auf Organopolysiloxan, in der Flotte zugegen sind. Wird das Umsetzungsprodukt C) als Emulgator für die Organopolysiloxanemulsion A) herangezogen, was bevorzugt ist, so kommen die gleichen Mengen zum Einsatz und es erübrigt sich selbstverständlich eine nachträgliche Zugabe derselben.The treatment liquors can be prepared in a simple manner by combining the constituents A), B) and C) and diluting with water and adjusting the pH to 5.5 to 7.5, in particular 6 to 7, in a known manner with preferably volatile acids . So much of the usually 20 to 40% by weight polysiloxane emulsion A) is used that the liquor is at least 6, in particular 8 to 50 g Contains organopolysiloxane per liter. Of the polysilicic acid ester dispersion B), which generally contains 35 to 65% by weight of polysilicic acid ester, 2 to 30 g, in particular 2 to 20 g, per liter of finishing liquor are used. The reaction product C), which is generally an 8 to 25% solution, is used in amounts such that at least 6% by weight, in particular 10 to 40% by weight, of 100% reaction product C), based on organopolysiloxane, are present in the fleet. If the reaction product C) is used as an emulsifier for the organopolysiloxane emulsion A), which is preferred, the same amounts are used and, of course, subsequent addition of the same is unnecessary.
Die erhaltenen Behandlungsflotten sind äußerst beständig, so daß die guten Hydrophobiereffekte auch noch nach einer Standzeit von 12 bis 24 Stunden erhalten werden.The treatment liquors obtained are extremely stable, so that the good hydrophobic effects are obtained even after a standing time of 12 to 24 hours.
Die Ausrüstungsflotte wird durch Foulardieren, Pflatschen, Sprühen oder andere bekannte Methoden auf das Material in üblichen Mengen (Flottenaufnahme in Abhängigkeit vom Fasermaterial 40 bis 120 Gew.%) aufgebracht und abschließend durch einfaches Erhitzen fertiggestellt. Im allgemeinen wird bei bis zu 100°C getrocknet und etwa 2 bis 5 Minuten bei 130 bis 170°C kondensiert. Es ist aber auch möglich, die Nachbehandlung während 10 bis 20 Minuten bei 1100C vorzunehmen. Es ist ein besonderer Vorteil des erfindungsgemäßen Verfahrens, daß schon niedrige Temperaturen ausreichen, um die guten Hydrophobiereffekte zu erhalten.The finishing liquor is applied to the material in customary amounts by padding, slapping, spraying or other known methods (liquor absorption, depending on the fiber material, 40 to 120% by weight) and is then completed by simple heating. In general, it is dried at up to 100 ° C. and condensed at 130 to 170 ° C. for about 2 to 5 minutes. However, it is also possible to carry out the aftertreatment at 110 ° C. for 10 to 20 minutes. It is a particular advantage of the process according to the invention that even low temperatures are sufficient to obtain the good hydrophobic effects.
Das vorliegende Verfahren zur Hydrophobierung von Fasermaterialien, insbesondere Textilien, kann mit einer üblichen Knitterfreiausrüstung kombiniert werden. Dabei sind die bekannten Kunstharze einsetzbar. Als Katalysatoren sind übliche Verbindungen, wie Magnesiumchlorid, Znsalze und Aminhydrochloride geeignet.The present process for the hydrophobization of fiber materials, in particular textiles, can be combined with conventional crease-free finishing. The known synthetic resins can be used. Conventional compounds such as magnesium chloride, zinc salts and amine hydrochlorides are suitable as catalysts.
In der beschriebenen Weise werden Fasermaterialien aller Art behandelt. Unter Fasermaterialien sind dabei Leder, Kunstleder, Papier, Vliese und insbesondere Textilien zu verstehen. Das Fasermaterial besteht vorzugsweise aus natürlicher oder regenerierter Cellulose oder Mischungen von Cellulose mit tierischen oder synthetischen Fasern. Selbstverständlich können auch Fasermaterialien, die tierische, insbesondere Wolle, oder synthetische Fasern, insbesondere Polyester-, Polyamid- und Polyacrylnitrilfasern allein oder in Mischungen untereinander enthalten, erfindungsgemäß ausgerüstet werden. Besonders bevorzugt werden Cellulose- bzw. Cellulose enthaltende Textilien hydrophobiert.All types of fiber materials are treated in the manner described. Fiber materials include leather, synthetic leather, paper, nonwovens and in particular textiles. The fiber material preferably consists of natural or regenerated cellulose or mixtures of cellulose with animal or synthetic fibers. Of course, fiber materials which contain animal, in particular wool, or synthetic fibers, in particular polyester, polyamide and polyacrylonitrile fibers, alone or in mixtures with one another, can also be finished according to the invention. Textiles containing cellulose or cellulose are particularly preferably hydrophobized.
Die Vorteile des erfindungsgemäßen Verfahrens gegenüber dem angegebenen Stand der Technik liegen vor allem in der wesentlich verbesserten Hydrophobierwirkung. Es konnte nicht erwartet werden, daß durch die Verwendung der Polykieselsäureester anstelle der einfachen Kieselsäureester zusammen mit den Umsetzungsprodukten C) die wasserabweisenden Effekte in so gravierender Weise verbessert werden. Während nämlich nach dem Stand der Technik die Hydrophobiereffekteohne Alkylwasserstoffpolysiloxane völlig unzureichend sind, wird nach dem erfindungsgemäßen Verfahren nunmehr in Abwesenheit von Organowasserstoffpolysiloxanen eine Hydrophobierung erhalten, wie sie bisher nur unter Mitverwendung von Alkylwasserstoffpolysiloxanen erreicht werden konnte. Besonders günstig sind die Effekte dabei, wenn die Umsetzungsprodukte C) von vorneherein als Emulgatoren für die Organopolysiloxanemulsionen A) verwendet werden.The advantages of the method according to the invention compared to the stated prior art lie above all in the substantially improved hydrophobic effect. It could not be expected that the use of the polysilicic acid esters instead of the simple silicic acid esters together with the reaction products C) would improve the water-repellent effects in such a serious way. In fact, while the hydrophobing effects without alkylhydrogenpolysiloxanes are completely inadequate in the prior art, the process according to the invention in the absence of organohydrogenpolysiloxanes now gives a hydrophobization which has hitherto been achieved only with the use of alkylhydrogenpolysiloxanes. The effects are particularly favorable when the reaction products C) are used from the outset as emulsifiers for the organopolysiloxane emulsions A).
Die in den nachfolgenden Beispielen angegebenen Werte für die Wasserabweisung und den Abperleffekt wurden nach DIN 53 888 bestimmt..The water repellency and water repellency values given in the following examples were determined in accordance with DIN 53 888.
Ein Baumwollpopelinegewebe (ca. 230 g/m2) wird mit einer wäßrigen Flotte imprägniert, die 125 g/1 der nachfolgend angegebenen Emulsion und 40 g/1 des im Beispiel 1 der US-PS 3 320 197 verwendeten Epoxyaminumsetzungsproduktes enthält (pH-Wert 7,2), auf eine Flottenaufnahme von 72 % abgequetscht und dann 10 Minuten bei 100°C getrocknet sowie 5 Minuten bei 150°C kondensiert.A cotton poplin fabric (approx. 230 g / m 2 ) is impregnated with an aqueous liquor which contains 125 g / 1 of the emulsion specified below and 40 g / 1 of the epoxyamine reaction product used in Example 1 of US Pat. No. 3,320,197 (pH value 7.2), squeezed to a liquor pick-up of 72% and then dried for 10 minutes at 100 ° C. and condensed for 5 minutes at 150 ° C.
Das so ausgerüstete Gewebe weist eine Wasseraufnahme von 17 % und einen sehr guten Abperleffekt (4/4/4) auf.The fabric treated in this way has a water absorption of 17% and a very good water repellent effect (4/4/4).
Die verwendete Emulsion wurde wie folgt hergestellt:
- 1830 g Wasser und 600 g einer 10%igen Polyvinylalkohollösung (Polyvinylalkohol mit einer Verseifungszahl von 140 und einer Viskosität von 25 mPa·s bei 200C in 4%iger Lösung) werden vorgelegt und eine Lösung von 360 g OH-Gruppen endblockiertem Dimethylpolysiloxan (5000 mPa·s bei 20°C) und 60 g Äthylpolysilikat (Daten siehe Beispiel 2) in 750 g Methylenchlorid unter dem Schnellrührer einemulgiert und das Ganze anschließend auf der Hochdruckhomogenisiermaschine bei 200 bar homogenisiert, wobei die Temperatur unter 25°C gehalten wird.
- 1830 g water and 600 g of a 10% polyvinyl alcohol solution (polyvinyl alcohol having a saponification value of 140 and a viscosity of 25 mPa.s at 20 0 C in a 4% solution) and a solution of 360 g of OH-groups endblocked dimethylpolysiloxane ( 5000 mPa · s at 20 ° C) and 60 g of ethyl polysilicate (for data see Example 2) in 750 g of methylene chloride under the high-speed stirrer and then homogenized on a high-pressure homogenizer at 200 bar, the temperature being kept below 25 ° C.
Zum Vergleich wird entsprechend dem Stand der Technik (DE-AS 1 282 597) der gleiche Baumwollpopeline ausgerüstet, wobei ebenfalls 125 g/1 der Emulsion, die aber anstelle des Äthylpolysilikats die gleiche Menge Kieselsäuretetraisopropylester und anstelle des Epoxyaminumsetzungsproduktes die im Beispiel der genannten DE-AS angegebene Katalysatorlösung enthält. Der pH-Wert der Ausrüstungsflotte liegt ebenso wie im obigen Fall bei 7,2.For comparison, the same cotton poplin is equipped in accordance with the prior art (DE-AS 1 282 597), 125 g / 1 of the emulsion also being used, but instead of the ethyl polysilicate the same amount of silica tetraisopropyl ester and instead of the epoxyamine reaction product being the same as that of the DE AS specified catalyst solution contains. As in the case above, the pH of the equipment fleet is 7.2.
Das so ausgerüstete Gewebe weist eine Wasseraufnahme von 72 % und einen ungenügenden Abperleffekt (1) auf. Damit ist die Überlegenheit des erfindungsgemäßen Verfahrens deutlich erkennbar.The fabric treated in this way has a water absorption of 72% and an insufficient beading effect (1). So that's the superiority of the inventive method clearly recognizable.
Zur Herstellung von Behandlungsflotten werden folgende Emulsionen bereitet:
- 650 g des im Beispiel 7 der US-PS 3 320 197 verwendeten Epoxyaminumsetzungsproduktes und 20 g Wasser werden vorgelegt und in diese Lösung eine Lösung von 250 g OH-Gruppen endblockiertem Dimethylpolysiloxan (Viskosität siehe Beispiel 1) in 80 g Tetrachloräthylen unter dem Schnellrührer einemulgiert und die erhaltene Voremulsion auf einer Hochdruckhomogenisiermaschine bei 300 bar und maximal 30°C homogenisiert.
- 650 g of the epoxyamine reaction product used in Example 7 of US Pat. No. 3,320,197 and 20 g of water are initially introduced and a solution of 250 g of OH-endblocked dimethylpolysiloxane (for viscosity, see Example 1) in 80 g of tetrachlorethylene is emulsified under the high-speed stirrer in this solution and the pre-emulsion obtained is homogenized on a high-pressure homogenizing machine at 300 bar and a maximum of 30 ° C.
240 g einer 10%igen Polyvinylalkohollösung (Daten siehe Beispiel 1) und 310 g Wasser werden vorgelegt und in diese Lösung 450 g Äthylpolysilikat (durchschnittliches Mokekulargewicht 610; Dichte bei 20°C 1,05 bis 1,06) mittels eines Schnellrührers eingerührt und die erhaltene Voremulsion bei 200 bar und 20 bis 25°C homogenisiert.240 g of a 10% polyvinyl alcohol solution (for data see Example 1) and 310 g of water are placed in this solution and 450 g of ethyl polysilicate (average molecular weight 610; density at 20 ° C. 1.05 to 1.06) are stirred in using a high-speed stirrer and the Pre-emulsion obtained at 200 bar and homogenized at 20 to 25 ° C.
40 g/1 der Organopolysiloxanemulsion und 8 g/1 der Äthylpolysilikatemulsion.40 g / 1 of the organopolysiloxane emulsion and 8 g / 1 of the ethyl polysilicate emulsion.
Der pH-Wert der Flotte beträgt 7,3.The pH of the liquor is 7.3.
Wie Flotte A, wobei zusätzlich 20 g/1 des nach Beispiel 1 der US-PS 4 102 840 hergestellten Kondensationsproduktes und 6 ml/1 einer 30%igen wäßrigen Zinknitratlösung (pH-Wert ca. 1) zugesetzt werden. Der pH-Wert der Flotte beträgt 6,5.Like fleet A, with an additional 20 g / 1 of that according to Example 1 of the US PS 4 102 840 produced condensation product and 6 ml / 1 of a 30% aqueous zinc nitrate solution (pH approx. 1) are added. The pH of the liquor is 6.5.
Wie Flotte B, wobei aber 6 g/1 Magnesiumchloridhexahydrat als Katalysator eingesetzt werden. Der pH-Wert der Flotte beträgt 6,9.Like fleet B, but using 6 g / 1 magnesium chloride hexahydrate as catalyst. The pH of the liquor is 6.9.
Wie Flotte B, aber mit 8 ml/1 einer wäßrigen 40%igen 2-Amino-2-methyl- propanolhydrochloridlösung (pH-wert ca. 7) als Katalysator. Der pH-Wert dieser Flotte liegt ebenfalls bei 6,9.Like fleet B, but with 8 ml / l of an aqueous 40% 2-amino-2-methylpropanol hydrochloride solution (pH approx. 7) as a catalyst. The pH of this liquor is also 6.9.
Mit diesen Flotten wird der im Beispiel 1 genannte Baumwollpopeline sofort nach der Herstellung, nach 2 Stunden und 12 Stunden Standzeit unter den im Beispiel 1 genannten Bedingungen ausgerüstet. Die erhaltenen Hydrophobiereffekte sind in der nachfolgend aufgeführten Tabelle zusammengestellt ( a = Wasseraufnahme; b = Abperleffekt):
Wird bei den Flotten A bis D der pH-Wert mit 60%iger Essigsäure auf 5,0 (Flotte A), 5,6 (Flette B), 5,6 (Flotte C) und 5,8 (Flotte D) eingestellt, so sind insgesamt gesehen die Anfangseffekte etwas niedriger, doch erhöht sich dadurch die Haltbarkeit der Flotten und es findet keine Abnahme der Effekte auch bei Ausrüstung nach 12 Stunden statt.If the pH of liquors A to D is adjusted to 5.0 (liquor A), 5.6 (liquor B), 5.6 (liquor C) and 5.8 (liquor D) with 60% acetic acid, Overall, the initial effects are somewhat lower, but this increases the durability of the fleets and there is no decrease in the effects even after 12 hours.
Eine Flotte zur Ausrüstung von Baumwollpopeline mit etwa 200 g/m2 wird wie folgt bereitet:
- 40 g einer Organopolysiloxanemulsion (Herstellung siehe Beispiel 2, wobei aber ein α, ω -Dipropoxydimethylpolysiloxan mit einer Viskosität von 20.000 mPa·s verwendet wird) und 18 g/1 einer Butylpolysilikatemulsion (Herstellung analog den Angaben im Beispiel 2; durchschnittliches Molekulargewicht des Butylpolysilikats 700) werden in einem Liter Wasser dispergiert. Der pH-Wert der Flotte stellt sich auf 7,2 ein (Flotte A). Mit Essigsäure wird der pH-Wert außerdem auf 6,5 (Flotte B) eingestellt.
- 40 g of an organopolysiloxane emulsion (preparation see Example 2, but using an α, ω-dipropoxydimethylpolysiloxane with a viscosity of 20,000 mPa · s) and 18 g / 1 of a butyl polysilicate emulsion (preparation analogous to the information in Example 2; average molecular weight of the butyl polysilicate 700 ) are dispersed in one liter of water. The pH of the liquor adjusts to 7.2 (liquor A). The pH is also adjusted to 6.5 (liquor B) with acetic acid.
Mit diesen Flotten wird der oben beschriebene Baumwollpopeline foulardiert (Flottenaufnahme etwa 65 %) und dann 15 Minuten bei 110°C getrocknet.The cotton popeline described above is padded with these liquors (liquor absorption about 65%) and then at 110 ° C. for 15 minutes dried.
Die erhaltenen Effekte sind in der nachfolgenden Tabelle zusammengestellt:
Es ist also nach dem erfindungsgemäßen Verfahren möglich, schon durch einfaches Trocknen sehr gute wasserabweisende Effekte zu erhalten.It is therefore possible by the process according to the invention to obtain very good water-repellent effects simply by drying.
Ein Baumwollpopeline (150 g/m2) wird mit einer wäßrigen Flotte, die im Liter 40 g der nach Beispiel 4 der GB-PS 1 404 356 hergestellten α,ω -Dihydroxydimethylpolysiloxanemulsion, 15 g des nach Beispiel 1 a der GB-PS 1 056 808 hergestellten Epoxyaminumsetzungsproduktes und 10 g der im Beispiel 2 hergestellten Äthylpolysilikatemulsion enthält, foulardiert (Flottenaufhahme ca. 68 %) und abschließend 20 Minuten bei 110°C getrocknet und kondensiert.A cotton poplin (150 g / m 2 ) is mixed with an aqueous liquor containing 40 g of the α, ω-dihydroxydimethylpolysiloxane emulsion prepared according to Example 4 of GB-PS 1 404 356, 15 g of that according to Example 1 a of GB-PS 1 056 808 produced epoxyamine reaction product and 10 g of the ethyl polysilicate emulsion prepared in Example 2, padded (liquor absorption approx. 68%) and finally dried and condensed at 110 ° C. for 20 minutes.
Das so ausgerüstete Gewebe weist eine sehr gute Wasserabweisung und einen guten Abperleffekt auf.The fabric treated in this way has very good water repellency and a good beading effect.
Zur Ausrüstung von Polyester/Baumwollmischgewebe 65 : 35 (220 g/m2) und Polyester/Viskosezellwollmischgewebe 67 : 33 (300 g/m2) werden folgende wäßrigen Flotten bereitet:
- Flotte A
- Fleet A
40 g/1 der im Beispiel 2 beschriebenen Organopolysiloxanemulsion, 8 g/1 einer Methylpolysilikatemulsion (durchschnittliches Molekulargewicht 360 bis 470; Dichte bei 20°C 1,14 bis 1,16; Herstellung analog den Angaben im Beispiel 2). Der pH-Wert der Lösung stellt sich auf 7,5 ein.40 g / 1 of the organopolysiloxane emulsion described in Example 2, 8 g / 1 of a methylpolysilicate emulsion (average molecular weight 360 to 470; density at 20 ° C. 1.14 to 1.16; preparation analogous to the information in Example 2). The pH of the solution adjusts to 7.5.
Wie Flotte A, wobei zusätzlich 20 g/1 einer 75%igen Aminoplastharzlösung (mit Methanol verätherter Dimethyloldihydroxyäthylenharnstoff) und 8 g/1 einer 40%igen wäßrigen 2-Amino-2-methylpropanolhydrochlorid- lösung enthalten sind (pH-Wert 7,2).Like fleet A, but additionally containing 20 g / 1 of a 75% aminoplast resin solution (dimethyloldihydroxyethylene urea etherified with methanol) and 8 g / 1 of a 40% aqueous 2-amino-2-methylpropanol hydrochloride solution (pH 7.2) .
Wie Flotte B, wobei aber als Aminoplastharzlösung 30 g/1 eines 60%igen mit Methanol verätherten Pentamethylolmelamins eingesetzt wird (pH-Wert 6,8).Like liquor B, but 30 g / 1 of a 60% strength pentamethylolmelamine etherified with methanol is used as the aminoplast resin solution (pH 6.8).
Wie Flotte B, wobei aber als Aminoplastharz 30 g/1 einer 68%igen Mischung aus mit Methanol veräthertem Hexamethylolmelamin und mit Methanol veräthertem Dimethylolharnstoff im Verhältnis 6 : 4 eingesetzt wird (pH-Wert 6,7).Like liquor B, but 30 g / 1 of a 68% mixture of hexamethylolmelamine etherified with methanol and dimethylolurea etherified with methanol in a ratio of 6: 4 is used as the aminoplast resin (pH 6.7).
Die oben beschriebenen Gewebe werden mit den angegebenen Flotten foulardiert (Flottenaufnahme 55 bis 60 %), dann 10 Minuten bei 100°C getrocknet und 3 Minuten bei 160°C kondensiert. Die erhaltenen Effekte sind in der nachfolgenden Tabelle zusammengefaßt:
Die durchwegs guten Ergebnisse lassen die Überlegenheit des erfindungsgemäßen Verfahrens besonders deutlich werden.The consistently good results make the superiority of the method according to the invention particularly clear.
Zur Herstellung von Behandlungsflotten werden folgende Organopolysiloxanemulsionen bereitet:
- 25 g einer wäßrig/alkoholischen Lösung von Cetyldimethylbenzylammoniumchlorid (50%ig) und 650 g Wasser werden vorgelegt und in diese Lösung eine Lösung von 250 g α,ω -Dihydroxydimethylpolysiloxan (Viskosität 750 mPa.s bei 20°C) in 80 g Tetrachloräthylen unter dem Schnellrührer einemulgiert und die erhaltene Voremulsion auf einer Hochdruckhomogenisiermaschine bei 300 bar und maximal 30°C homogenisiert (Emulsion A).
- 25 g of an aqueous / alcoholic solution of cetyldimethylbenzylammonium chloride (50%) and 650 g of water are introduced and a solution of 250 g of α, ω-dihydroxydimethylpolysiloxane (viscosity 750 mPa.s at 20 ° C.) in 80 g of tetrachlorethylene in this solution emulsified in the high-speed stirrer and the pre-emulsion obtained was homogenized on a high-pressure homogenizing machine at 300 bar and a maximum of 30 ° C. (emulsion A).
In gleicher Weise wird eine Emulsion hergestellt unter Verwendung von 5 g Nonylphenolpolyglykoläther (10 Mol Äthylenoxyd je Mol Nonylphenol) als Emulgator (Emulsion B).In the same way, an emulsion is prepared using 5 g of nonylphenol polyglycol ether (10 moles of ethylene oxide per mole of nonylphenol) as an emulsifier (emulsion B).
40 g/1 der Organopolysiloxanemulsion (A), 20 g/1 einer Lösung eines Epoxyaminumsetzungsproduktes (Herstellung siehe Beispiel 7 der US-PS 3 320 197) und 22 g/1 der im Beispiel 2 beschriebenen Äthylpolysilikatemulsion.40 g / 1 of the organopolysiloxane emulsion (A), 20 g / 1 of a solution of an epoxyamine reaction product (for preparation see Example 7 of US Pat. No. 3,320,197) and 22 g / 1 of the ethyl polysilicate emulsion described in Example 2.
Wie Flotte A, aber mit 30 g/1 des Epoxyaminumsetzungsproduktes.Like fleet A, but with 30 g / 1 of the epoxyamine reaction product.
Wie Flotte A, aber mit 40 g/1 der Organopolysiloxanemulsion (B).Like fleet A, but with 40 g / 1 of the organopolysiloxane emulsion (B).
Wie Flotte C, aber mit 30 g/1 des Epoxyaminumsetzungsproduktes.Like liquor C, but with 30 g / 1 of the epoxyamine reaction product.
Der pH-Wert der Flotten A) bis D) liegt bei 7,1 bis 7,3.The pH of the liquors A) to D) is 7.1 to 7.3.
Mit diesen Flotten wird der im Beispiel 1 genannte Baumwollpopeline unter den dort genannten Bedingungen ausgerüstet. Die erhaltenen Hydrophobiereffekte sind in der nachfolgend aufgeführten Tabelle zusammengestellt:
Claims (6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AT81107352T ATE6530T1 (en) | 1980-09-23 | 1981-09-17 | PROCESS FOR HYDROPHOBIZING FIBER MATERIAL. |
Applications Claiming Priority (2)
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DE19803035824 DE3035824A1 (en) | 1980-09-23 | 1980-09-23 | METHOD FOR HYDROPHOBIZING FIBER MATERIAL |
DE3035824 | 1980-09-23 |
Publications (2)
Publication Number | Publication Date |
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EP0051138A1 true EP0051138A1 (en) | 1982-05-12 |
EP0051138B1 EP0051138B1 (en) | 1984-03-07 |
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ID=6112637
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EP81107352A Expired EP0051138B1 (en) | 1980-09-23 | 1981-09-17 | Process for rendering waterrepellent fibrous material |
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US (1) | US4390650A (en) |
EP (1) | EP0051138B1 (en) |
AT (1) | ATE6530T1 (en) |
DE (1) | DE3035824A1 (en) |
ES (1) | ES505681A0 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0195139A1 (en) * | 1983-07-05 | 1986-09-24 | Texaco Development Corporation | Synthesis gas generation with control of ratio of steam to dry gas |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
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US5191734A (en) * | 1990-04-24 | 1993-03-09 | Kimberly-Clark Corporation | Biodegradable latex web material |
DE4117864A1 (en) * | 1991-05-31 | 1992-12-03 | Pfersee Chem Fab | WAITER DISPERSIONS OF POLYSILOXANES |
US5227200A (en) * | 1992-03-09 | 1993-07-13 | Dow Corning Corporation | Silicone containing automotive vinyl and rubber protectant |
DE4330967A1 (en) * | 1993-09-13 | 1995-03-16 | Pfersee Chem Fab | Compositions containing organic silicon compounds for the treatment of fiber materials |
DE19857106C2 (en) * | 1998-12-10 | 2000-10-26 | Heinz Neubaur | Swimwear made from a water-repellent fabric and process for its manufacture |
US6756076B2 (en) * | 2000-10-13 | 2004-06-29 | Michael Brier | Process for producing fabric articles having water-resistant and/or antimicrobial characteristics |
WO2008127519A1 (en) | 2007-04-11 | 2008-10-23 | Dow Corning Corporation | Silcone polyether block copolymers having organofunctional endblocking groups |
US8268975B2 (en) | 2009-04-03 | 2012-09-18 | Dow Agrosciences Llc | Demulsification compositions, systems and methods for demulsifying and separating aqueous emulsions |
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GB949959A (en) * | 1959-07-23 | 1964-02-19 | Gen Electric | Siloxane compositions and methods of rendering cellulosic materials non-adherent |
GB1056808A (en) * | 1964-12-01 | 1967-02-01 | Boehme Fettchemie Gmbh | Aqueous emulsions of silicones |
US3320197A (en) * | 1963-03-26 | 1967-05-16 | Pfersee Chem Fab | Process of producing concentrated aqueous emulsions of water-insoluble substances and emulsions produced by such process |
GB1123447A (en) * | 1965-05-26 | 1968-08-14 | Dow Corning | A method of imparting durable creases to garments |
DE1282597B (en) * | 1964-02-19 | 1968-11-14 | Hoechst Ag | Process for making textiles water repellent with organopolysiloxane emulsions |
FR1575695A (en) * | 1968-04-10 | 1969-07-25 | ||
DE1519072A1 (en) * | 1961-01-30 | 1970-05-21 | Dow Corning | Process for making objects of all kinds, especially textiles, repellent |
US3848022A (en) * | 1969-07-19 | 1974-11-12 | Pfersee Chem Fab | Water-soluble or inherently water-dispersible condensation products which cross link with heating and the use of these condensation products as curing agents for organopolysiloxanes |
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DE1769666U (en) | 1955-01-17 | 1958-07-03 | Conrad Mollenhauer Holzblasins | MOUTH HOLE FOR CROSS FLOETS, BOEHMFLOETS OD. DGL. |
US3418162A (en) * | 1963-12-07 | 1968-12-24 | Shinetsu Chem Ind Co | Composition of waterproof agent and process for manufacture of waterproof cloth using the same |
GB1181347A (en) * | 1967-06-26 | 1970-02-11 | Dow Corning | Polydimethylsiloxane Coatings |
CH492071A (en) * | 1968-06-13 | 1970-02-13 | Ciba Geigy | Use of aqueous preparations made from organopolysiloxanes and curing catalysts for finishing textile materials |
BE756758A (en) * | 1969-09-29 | 1971-03-29 | Rhone Poulenc Sa | CONCENTRATED AQUEOUS EMULSIONS FOR HYDROFUGATION OF TEXTILES |
US3772351A (en) * | 1970-10-12 | 1973-11-13 | Dow Corning | Urea-functional organosilicon compounds |
BE791827A (en) | 1971-11-25 | 1973-03-16 | Pfersee Chem Fab | PROCESS FOR THE MANUFACTURING OF STABLE EMULSIONS OF HIGHLY VISCOUS CROSS-LINKABLE ORGANOPOLYSILOXANES |
JPS4947436A (en) | 1972-09-08 | 1974-05-08 | ||
GB1478126A (en) * | 1973-08-28 | 1977-06-29 | Nat Res Dev | Water-repellent treatment |
-
1980
- 1980-09-23 DE DE19803035824 patent/DE3035824A1/en active Granted
-
1981
- 1981-09-14 US US06/301,569 patent/US4390650A/en not_active Expired - Fee Related
- 1981-09-17 AT AT81107352T patent/ATE6530T1/en not_active IP Right Cessation
- 1981-09-17 EP EP81107352A patent/EP0051138B1/en not_active Expired
- 1981-09-22 ES ES505681A patent/ES505681A0/en active Granted
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GB949959A (en) * | 1959-07-23 | 1964-02-19 | Gen Electric | Siloxane compositions and methods of rendering cellulosic materials non-adherent |
DE1519072A1 (en) * | 1961-01-30 | 1970-05-21 | Dow Corning | Process for making objects of all kinds, especially textiles, repellent |
US3320197A (en) * | 1963-03-26 | 1967-05-16 | Pfersee Chem Fab | Process of producing concentrated aqueous emulsions of water-insoluble substances and emulsions produced by such process |
DE1282597B (en) * | 1964-02-19 | 1968-11-14 | Hoechst Ag | Process for making textiles water repellent with organopolysiloxane emulsions |
GB1056808A (en) * | 1964-12-01 | 1967-02-01 | Boehme Fettchemie Gmbh | Aqueous emulsions of silicones |
GB1123447A (en) * | 1965-05-26 | 1968-08-14 | Dow Corning | A method of imparting durable creases to garments |
FR1575695A (en) * | 1968-04-10 | 1969-07-25 | ||
DE1918284A1 (en) * | 1968-04-10 | 1970-02-19 | Rhodiaceta | Coating filaments with organopolysiloxane elastomers |
US3848022A (en) * | 1969-07-19 | 1974-11-12 | Pfersee Chem Fab | Water-soluble or inherently water-dispersible condensation products which cross link with heating and the use of these condensation products as curing agents for organopolysiloxanes |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0195139A1 (en) * | 1983-07-05 | 1986-09-24 | Texaco Development Corporation | Synthesis gas generation with control of ratio of steam to dry gas |
Also Published As
Publication number | Publication date |
---|---|
DE3035824C2 (en) | 1988-09-15 |
ES8206701A1 (en) | 1982-08-16 |
US4390650A (en) | 1983-06-28 |
EP0051138B1 (en) | 1984-03-07 |
DE3035824A1 (en) | 1982-05-06 |
ES505681A0 (en) | 1982-08-16 |
ATE6530T1 (en) | 1984-03-15 |
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