EP0196309B1 - Method for obtaining wash- and cleaning-resistant textile finishes using reactive perfluoroalkyl rest-containing (co)polymers and/or precondensates - Google Patents

Method for obtaining wash- and cleaning-resistant textile finishes using reactive perfluoroalkyl rest-containing (co)polymers and/or precondensates Download PDF

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Publication number
EP0196309B1
EP0196309B1 EP85904458A EP85904458A EP0196309B1 EP 0196309 B1 EP0196309 B1 EP 0196309B1 EP 85904458 A EP85904458 A EP 85904458A EP 85904458 A EP85904458 A EP 85904458A EP 0196309 B1 EP0196309 B1 EP 0196309B1
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EP
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Prior art keywords
groups
blocked
process according
compounds containing
nco
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EP85904458A
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German (de)
French (fr)
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EP0196309A1 (en
Inventor
Hans Deiner
Bernhard Sandner
Franz Mosch
Willy Bernheim
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Chemische Fabrik Pfersee GmbH
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Chemische Fabrik Pfersee GmbH
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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
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D06M15/437—Amino-aldehyde resins containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/295—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine

Definitions

  • the present invention describes a process for achieving washable and cleaning-resistant textile finishes by impregnation with conventional reactive (co) polymers containing perfluoroalkyl radicals and / or precondensates which contain OH or OR groups as reactive groups, where R is an alkyl radical with 1 to 3 carbon atoms, in aqueous dispersion and final heating, the dispersions containing NCO groups (low molecular weight polyurethanes with isocyanate groups and / or polyisocyanates) which have a molecular weight of at least 450 and / or a polyisocyanate mixture based on diphenylmethane in blocked Form included.
  • NCO groups low molecular weight polyurethanes with isocyanate groups and / or polyisocyanates
  • R f perfluoroalkyl radical with at least 4, in particular 6 to 14, C. Atoms.
  • These finishes can be used in combination with known finishing agents, methylolated compounds in particular, but also diisocyanates, being mentioned.
  • the disadvantage here is that the diisocyanates have to be prepared from solvents (aqueous emulsions are not stable) and the improvement in cleaning resistance achieved is insufficient.
  • washing and cleaning-resistant textile finishes with reactive, perfluoroalkyl group-containing (co) polymers and / or precondensates are obtained from aqueous dispersion when selected compounds containing NCO groups are used in blocked form.
  • the present invention thus relates to the method described in claim 1 and embodiments of this method specified in the subclaims.
  • the reactive, perfluoroalkyl groups contain the (co) polymers which contain OH or OR groups as reactive groups, in which R denotes an alkyl radical having 1 to 3 C atoms, are sufficiently known to the person skilled in the art (see, for example, DE -AS 1 419 505).
  • copolymers based on vinyl esters, in particular vinyl acetate and acrylic acid esters, in particular butyl acrylate.
  • Comonomers come from a wide variety of compounds, such as other acrylates, e.g. As ethyl, methyl or 2-ethylhexyl acrylate, ethylene, styrene, acrylamide and acrylonitrile into consideration, which also contain small amounts of carboxyl-containing monomers, for. B. itaconic acid and (meth) acrylic acid, or monomers with several double bonds, e.g. B. butanediol diacrylate, copolymerized.
  • These (co) polymers contain customary monomers containing perfluoroalkyl groups, which may also be the main component.
  • the perfluoroalkyl group-containing (co) polymers containing N-methylol or N-methylol (C 1 to C 3 alkyl) ether groups used as reactive groups are those which are obtained by using methylolated and optionally etherified (meth) acrylamides or allyl carbamates be built into the copolymer.
  • OH group-containing comonomers e.g. B. hydroxyalkyl (meth) acrylates, such as 2-hydroxyethyl or 2-hydroxypropyl acrylate, very suitable.
  • the monomers with the reactive groups are generally polymerized in amounts of 2 to 20, in particular 2.5 to 12,% by weight, based on the total polymer. These copolymers are prepared in a known manner by emulsion copolymerization in an aqueous medium.
  • Pre-condensates containing reactive perfluoroalkyl groups are used as reactive compounds instead of or together with the (co) polymeric.
  • these are the customary methylolmelamines or methylolureas, which are optionally etherified with C 1 to C 3 alcohols and are present in a form modified with perfluoroalkyl groups.
  • a typical representative of this group of compounds is described in EP-OS 073 364.
  • R f polyurethanes containing free OH groups may be mentioned as examples.
  • reactive (co) polymers containing R f groups should therefore be interpreted broadly.
  • Low molecular weight polyurethanes are suitable as compounds containing NCO groups. These polyurethanes are - and this is well known to the person skilled in the art - by reacting polyvalent, aliphatic, cycloaliphatic, araliphatic and aromatic polyisocyanates, such as, for example, hexamethylene-1,6-diisocyanate, the various isomers of tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and the like with low molecular weight compounds with at least 2, preferably at least 3 OH groups.
  • low molecular weight polyols are trimethylolpropane, 1,3,5-hexanetriol, glycerin, pentaerythritol, but also propylene glycol, hexylene glycol or diethylene glycol.
  • Other low molecular weight polyhydroxy compounds such as triethanolamine, are also suitable.
  • the molecular weight of the polyhydroxy compounds which can be used is in the range from 62 to about 400, in particular up to about 250.
  • the production of the low molecular weight polyurethanes which have a molecular weight of at least 450, in particular at least 600, is known per se.
  • the polyhydroxy compounds mentioned are reacted with an excess of polyisocyanates.
  • the equivalent ratio of OH to NCO groups is at least 1: 1.3, in particular 1: 1.5 to 2.5.
  • the upper limit is variable, but connections with a ratio of 1: over 6.0 are no longer particularly important.
  • polyisocyanates with a molecular weight of at least 450, in particular at least 600, are also included as compounds containing NCO groups
  • the method according to the invention can be used after the blocking described below.
  • Such polyisocyanates are known. Examples include: trimeric isophorone diisocyanate or trimeric hexamethylene-1, 6-diisocyanate or DESMODUR RF (Bayer AG, Leverkusen).
  • a polyisocyanate mixture based on diphenylmethane is also suitable.
  • the selected compounds containing NCO groups described are not used as such, but rather in blocked form.
  • the blocking takes place by reacting these compounds with approximately stoichiometric amounts of blocking agent. After the reaction, the free NCO groups have practically completely disappeared.
  • Suitable blocking agents are phenols, malonic esters, acetoacetic esters and other known substances, but preferably C 2 -C 8 -alkanone oximes, in particular butanone oxime (see, for example, EP-OS 107 838).
  • the compounds containing blocked NCO groups can be broken down in the heat, so that again ready-to-react compounds are present.
  • the compounds blocked with C 2- to C 8-alkanone oximes, in particular butanone oxime, can be broken down again at relatively low temperatures, which is why these blocking agents are preferred.
  • the cleavage by adding catalysts, for. B. Sn alkyl compounds are accelerated.
  • the blocked low molecular weight polyurethane or the blocked polyisocyanate are used to achieve the washing and (chemical) cleaning-resistant textile equipment as so-called extenders, i.e. substances that improve oil and water repellency and thereby reduce the amount of compounds containing fluoroalkyl residues.
  • extenders i.e. substances that improve oil and water repellency and thereby reduce the amount of compounds containing fluoroalkyl residues.
  • Amounts of 3 to 25% by weight, in particular 7 to 17% by weight, based on 100% reactive perfluoroalkyl group-containing (co) polymer and / or precondensate, are completely sufficient, so that higher amounts are sufficient Cost reasons are out of the question.
  • the compounds containing blocked NCO groups are added to the finishing liquor in emulsified form.
  • These emulsions are prepared in a known manner using known emulsifiers and are ultimately in solvent-free form. These production processes are known to the person skilled in the art and it is not necessary to go into them in more detail.
  • the blocked NCO group-containing compounds must not be dissolved in the solvent alone, but only together with another known water-insoluble textile auxiliary, if appropriate at a slightly elevated temperature, in order to achieve fleets which are stable for several hours, only then, as is known, this solution stirred into an emulsifier / water mixture (commercially available products can be used as emulsifiers) and then subjected to high-pressure homogenization, and the mixture obtained is then subjected to high-pressure homogenization. Finally, as usual, the solvent is distilled off under reduced pressure at a slightly elevated temperature and the emulsion is adjusted to the desired dry substance content with water.
  • Such additives include customary crease and softening agents, flame retardants, oleophobicizing agents, water repellents, finishing agents and others. Of course, it is also appropriate, if necessary, to use known hardening agents.
  • the method according to the invention is used to impregnate all types of textiles from an aqueous medium.
  • the water is of course used in different quantities, depending on whether impregnation, i.e. impregnation of the material, is carried out by padding, spraying, splashing or the like.
  • impregnation is a very common finishing method, which the skilled worker is familiar with. These methods therefore require no special explanation and reference can be made to the known literature. Further details can be found in the examples. It should be noted, however, that the use of organic solvents is not necessary in the process according to the invention, but is carried out without solvents.
  • the method according to the invention is suitable for impregnating textiles of all kinds, be it in the form of woven, knitted or non-woven fabrics. These can be made both from natural fibers, such as cellulose or keratin fibers, and from synthetic fibers, such as polyacrylonitrile, polyamide, polyvinyl alcohol or polyester. Of course, textile materials that consist of mixtures of natural and synthetic fibers are also suitable. It should be emphasized that even slightly adjusted fabrics, such as taffeta or slightly adjusted poplin fabrics, can be finished using the method according to the invention. This is important, for example, for rain protective clothing such as anoraks and the like.
  • the oil repellency is tested using the method as specified in AATCC 118-1972.
  • the dry cleaning is carried out in a liquor ratio of 1:10 (sample weight to liquor volume) for 15 minutes, the tetrachlorethylene used being renewed for each cleaning. The samples are washed in the manner specified in each case.
  • the fleet intake is 78%.
  • the fabric treated in this way is then dried at 110 ° C. for 10 minutes and then condensed at 150 ° C. for 5 minutes (equipment A).
  • equipment B is carried out in the same way, but the emulsion is produced in the absence of the blocked low-molecular-weight polyurethane, but with the liquor batch 20 g / 1 of a commercially available extender based on fat-modified synthetic resin (see, for example, DE-PS 12 33 874, Examples 1 and 4) can also be used.
  • a commercially available extender based on fat-modified synthetic resin see, for example, DE-PS 12 33 874, Examples 1 and 4
  • Example 1 is repeated using the perfluoroalkyl-modified methylol melamine ether according to Example 2 B of EP-OS 073 364, with comparable results.
  • polyisocyanates are blocked in succession with butanone oxime in the manner described in Example 1: trimeric isophorone diisocyanate (A), DESMODUR RF from Bayer (B), trimeric hexamethylene-1,6-diisocyanate (C), hexamethylene-1,6-diisocyanate (D) and naphthylene-1,5-diisocyanate (E).
  • A trimeric isophorone diisocyanate
  • DESMODUR RF from Bayer
  • C trimeric hexamethylene-1,6-diisocyanate
  • D hexamethylene-1,6-diisocyanate
  • E naphthylene-1,5-diisocyanate
  • methyl ethyl ketone 100 g of the blocked polyurethane prepared as described below are added at about 60 ° C. and heated to 60 ° C.
  • the liquid consists of two immiscible layers. It is turbinated in a solution of 10 g of the emulsifier described in Example 1 in 290 g of water at a temperature of 60 ° C. and then homogenized on a high-pressure homogenizing machine, likewise at a temperature of 60 ° C.
  • the solvent is then distilled off in vacuo at 30 to 40 ° C. with stirring and the emulsion is adjusted to 25% by weight dry matter content with water.

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

A method for obtaining a coating for washing- and cleaning-resistant textiles comprises the impregnation of the textile material with conventional reactive perfluoroalkyl rest-containing (co)polymers and/or precondensates in an aqueous dispersion followed by heating. The despersion comprises bonds containing NCO groups having a molecular weight of at least 450, and a mixture of polyisocyanates of diphenylmethane in blocked form. The method enables to protect textiles with a water- and oil-impervious coating having a very good resistance to washing and cleaning.

Description

Die vorliegende Erfindung beschreibt ein Verfahren zur Erzielung wasch- und reinigungsbeständiger Textilausrüstungen durch Imprägnieren mit üblichen reaktiven, Perfluoralkylreste enthaltenden (Co)polymeren und bzw. oder Vorkondensaten, die als reaktive Gruppen OH- bzw. OR-Gruppen enthalten, wobei R einen Alkylrest mit 1 bis 3 C-Atomen bedeutet, in wäßriger Dispersion und abschließendes Erhitzen, wobei die Dispersionen NCO-Gruppen enthaltende Verbindungen (niedermolekulare Polyurethane mit Isocyanatgruppen und/oder Polyisocyanate), die ein Molekulargewicht von mindestens 450 aufweisen, und/oder ein Polyisocyanatgemisch auf Diphenylmethanbasis in blockierter Form enthalten.The present invention describes a process for achieving washable and cleaning-resistant textile finishes by impregnation with conventional reactive (co) polymers containing perfluoroalkyl radicals and / or precondensates which contain OH or OR groups as reactive groups, where R is an alkyl radical with 1 to 3 carbon atoms, in aqueous dispersion and final heating, the dispersions containing NCO groups (low molecular weight polyurethanes with isocyanate groups and / or polyisocyanates) which have a molecular weight of at least 450 and / or a polyisocyanate mixture based on diphenylmethane in blocked Form included.

Die öl- und wasserabweisende Ausrüstung mit den unterschiedlichsten reaktiven Rf-Polymeren bzw. Rf-Vorkondensaten ist bekannt (EP-OS 073 364; US-PS 3 356 628; Rf = Perfluoralkylrest mit mindestens 4, insbesondere 6 bis 14 C-Atomen). Diese Ausrüstungen können in Kombination mit bekannten Ausrüstungsmitteln erfolgen, wobei vor allem methylolierte Verbindungen, aber auch Diisocyanate genannt sind. Nachteilig ist dabei, daß die Ausrüstung mit den Diisocyanaten aus Lösungsmitteln erfolgen muß (wäßrige Emulsionen sind unbeständig) und die erzielte Verbesserung der Reinigungsbeständigkeit ungenügend bleibt.The oil- and water-repellent finish with a wide variety of reactive R f polymers or R f precondensates is known (EP-OS 073 364; US Pat. No. 3,356,628; R f = perfluoroalkyl radical with at least 4, in particular 6 to 14, C. Atoms). These finishes can be used in combination with known finishing agents, methylolated compounds in particular, but also diisocyanates, being mentioned. The disadvantage here is that the diisocyanates have to be prepared from solvents (aqueous emulsions are not stable) and the improvement in cleaning resistance achieved is insufficient.

Es wurde nun gefunden, daß wasch- und reinigungsbeständige Textilausrüstungen mit reaktiven, Perfluoralkylgruppen enthaltenden (Co)polymeren und bzw. oder Vorkondensaten aus wäßriger Dispersion dann erhalten werden, wenn ausgewählte NCO-Gruppen enthaltende Verbindungen in blockierter Form zum Einsatz kommen.It has now been found that washing and cleaning-resistant textile finishes with reactive, perfluoroalkyl group-containing (co) polymers and / or precondensates are obtained from aqueous dispersion when selected compounds containing NCO groups are used in blocked form.

Die vorliegende Erfindung betrifft somit das im Anspruch 1 beschriebene Verfahren und in den Unteransprüchen angegebene Ausgestaltungen dieses Verfahrens.The present invention thus relates to the method described in claim 1 and embodiments of this method specified in the subclaims.

Die reaktiven, Perflouralkylgruppen enthalten den (Co)polymeren, die als reaktive Gruppen OH- bzw. OR-Gruppen enthalten, in denen R einen Alkylrest mit 1 bis 3 C-Atomen bedeutet, sind dem Fachmann hinreichend bekannt (siehe z. B. DE-AS 1 419 505).The reactive, perfluoroalkyl groups contain the (co) polymers which contain OH or OR groups as reactive groups, in which R denotes an alkyl radical having 1 to 3 C atoms, are sufficiently known to the person skilled in the art (see, for example, DE -AS 1 419 505).

Im allgemeinen handelt es sich um Copolymerisate auf Basis von Vinylestern, insbesondere Vinylacetat und Acrylsäureestern, insbesondere Butylacrylat. Als Comonomere kommen dabei die unterschiedlichsten Verbindungen, wie andere Acrylate, z. B. Ethyl-, Methyl- oder 2-Ethylhexylacrylat, Ethylen, Styrol, Acrylamid und Acrylnitril in Betracht, die auch geringe Mengen an carboxylgruppenhaltigen Monomeren, z. B. Itaconsäure und (Meth)Acrylsäure, oder Monomere mit mehreren Doppel-bindungen, z. B. Butandioldiacrylat, einpolymerisiert enthalten können. Diese (Co)polymeren enthalten übliche Perfluoralkylgruppen enthaltende Monomere einpolymerisiert, wobei diese Monomeren durchaus auch die Hauptkomponente sein können. Als reaktive Gruppen enthalten die verwendeten Perfluoralkylgruppen enthaltenden (Co)polymeren N-Methylol- bzw. N-Methylol-(C 1- bis C 3-Alkyl)ether-gruppen, die durch Verwendung von methylolierten und gegebenenfalls veretherten (Meth)acrylamiden oder Allylcarbamaten in das Copolymere eingebaut werden. Daneben sind aber auch OH-gruppenhaltige Comonomere, z. B. Hydroxyalkyl(meth)acrylate, wie 2-Hydroxyethyl- oder 2-Hydroxypropyl-acrylat, sehr gut geeignet. Die Monomeren mit den reaktiven Gruppen sind im allgemeinen in Mengen von 2 bis 20, insbesondere 2,5 bis 12 Gew.-%, bezogen auf das gesamte Polymerisat, einpolymerisiert. Diese Copolymerisate werden in bekannter Weise durch Emulsionscopolymerisation in wäßrigem Medium hergestellt.In general, they are copolymers based on vinyl esters, in particular vinyl acetate and acrylic acid esters, in particular butyl acrylate. Comonomers come from a wide variety of compounds, such as other acrylates, e.g. As ethyl, methyl or 2-ethylhexyl acrylate, ethylene, styrene, acrylamide and acrylonitrile into consideration, which also contain small amounts of carboxyl-containing monomers, for. B. itaconic acid and (meth) acrylic acid, or monomers with several double bonds, e.g. B. butanediol diacrylate, copolymerized. These (co) polymers contain customary monomers containing perfluoroalkyl groups, which may also be the main component. The perfluoroalkyl group-containing (co) polymers containing N-methylol or N-methylol (C 1 to C 3 alkyl) ether groups used as reactive groups are those which are obtained by using methylolated and optionally etherified (meth) acrylamides or allyl carbamates be built into the copolymer. In addition, there are also OH group-containing comonomers, e.g. B. hydroxyalkyl (meth) acrylates, such as 2-hydroxyethyl or 2-hydroxypropyl acrylate, very suitable. The monomers with the reactive groups are generally polymerized in amounts of 2 to 20, in particular 2.5 to 12,% by weight, based on the total polymer. These copolymers are prepared in a known manner by emulsion copolymerization in an aqueous medium.

Als reaktive Verbindungen werden anstelle oder auch zusammen mit den (Co)polymeren reaktive Perfluoralkylgruppen enthaltende Vorkondensate verwendet. Vor allem handelt es sich dabei um die üblichen gegebenenfalls mit C 1- bis C 3-Alkoholen veretherten Methylolmelamine bzw. Methylolharnstoffe, die in mit Perfluoralkylgruppen modifizierter Form vorliegen. Ein typischer Vertreter dieser Gruppe von Verbindungen wird in der EP-OS 073 364 beschrieben.Pre-condensates containing reactive perfluoroalkyl groups are used as reactive compounds instead of or together with the (co) polymeric. Above all, these are the customary methylolmelamines or methylolureas, which are optionally etherified with C 1 to C 3 alcohols and are present in a form modified with perfluoroalkyl groups. A typical representative of this group of compounds is described in EP-OS 073 364.

Weitere, weniger gut geeignete reaktive Verbindungen für das erfindungsgemäße Verfahren sind dem Fachmann ebenfalls bekannt. Als Beispiele seien freie OH-Gruppen enthaltende Rf-Polyurethane genannt. Der Begriff reaktive, Rf-Gruppen enthaltende (Co)polymere ist also weit auszulegen.Other, less suitable reactive compounds for the process according to the invention are also known to the person skilled in the art. R f polyurethanes containing free OH groups may be mentioned as examples. The term reactive (co) polymers containing R f groups should therefore be interpreted broadly.

Als NCO-Gruppen enthaltende Verbindungen sind niedermolekulare Polyurethane geeignet. Diese Polyurethane werden - und das ist dem Fachmann durchaus bekannt - durch Umsetzung von mehrwertigen, aliphatischen, cycloaliphatischen, araliphatischen und aromatischen Polyisocyanaten, wie beispielsweise Hexamethylen-1,6-diisocyanat, den verschiedenen Isomeren des Toluylendiisocyanats, Diphenylmethandiisocyanat, Isophorondiisocyanat und dergleichen mit niedermolekularen Verbindungen mit mindestens 2, vorzugsweise mindestens 3 OH-Gruppen, hergestellt. Als niedermolekulare Polyole kommen dabei insbesondere Trimethylolpropan, 1,3,5-Hexantriol, Glycerin, Pentaaerythrit, aber auch Propylenglykol, Hexylenglykol oder Diethylenglykol in Betracht. Daneben sind auch andere niedermolekulare Polyhydroxyverbindungen, wie Triethanolamin, geeignet. Das Molekulargewicht der verwendbaren Polyhydroxyverbindungen liegt im Bereich von 62 bis etwa 400, insbesondere bis etwa 250.Low molecular weight polyurethanes are suitable as compounds containing NCO groups. These polyurethanes are - and this is well known to the person skilled in the art - by reacting polyvalent, aliphatic, cycloaliphatic, araliphatic and aromatic polyisocyanates, such as, for example, hexamethylene-1,6-diisocyanate, the various isomers of tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and the like with low molecular weight compounds with at least 2, preferably at least 3 OH groups. Particularly suitable low molecular weight polyols are trimethylolpropane, 1,3,5-hexanetriol, glycerin, pentaerythritol, but also propylene glycol, hexylene glycol or diethylene glycol. Other low molecular weight polyhydroxy compounds, such as triethanolamine, are also suitable. The molecular weight of the polyhydroxy compounds which can be used is in the range from 62 to about 400, in particular up to about 250.

Die Herstellung der niedermolekularen Polyurethane, die ein Molekulargewicht von mindestens 450, insbesondere mindestens 600 aufweisen, ist an und für sich bekannt. Es werden dazu die genannten Polyhydroxyverbindungen mit einem Überschuß an Polyisocyanaten umgesetzt. Das Äquivalentverhältnis von OH- zu NCO-Gruppen liegt dabei bei mindestens 1 : 1,3, insbesondere 1 : 1,5 bis 2,5. Die obere Grenze ist variabel, doch kommt Verbindungen mit einem Verhältnis von 1 : über 6,0 keine besondere Bedeutung mehr zu.The production of the low molecular weight polyurethanes, which have a molecular weight of at least 450, in particular at least 600, is known per se. For this purpose, the polyhydroxy compounds mentioned are reacted with an excess of polyisocyanates. The equivalent ratio of OH to NCO groups is at least 1: 1.3, in particular 1: 1.5 to 2.5. The upper limit is variable, but connections with a ratio of 1: over 6.0 are no longer particularly important.

Neben den niedermolekularen Polyurethanen sind als NCO-Gruppen enthaltende Verbindungen auch Polyisocyanate mit einem Molekulargewicht von mindestens 450, insbesondere mindestens 600 im Rahmen des erfindungsgemäßen Verfahrens nach der unten beschriebenen Blockierung einsetzbar. Derartige Polyisocyanate sind bekannt. Als Beispiele seien genannt: trimeres isophorondiisocyanat bzw. trimeres Hexamethylen-1 ,6-diisocyanat oder DESMODUR RF (Firma Bayer AG, Leverkusen).In addition to the low molecular weight polyurethanes, polyisocyanates with a molecular weight of at least 450, in particular at least 600, are also included as compounds containing NCO groups The method according to the invention can be used after the blocking described below. Such polyisocyanates are known. Examples include: trimeric isophorone diisocyanate or trimeric hexamethylene-1, 6-diisocyanate or DESMODUR RF (Bayer AG, Leverkusen).

Als einzige Ausnahme ist neben den höhermolekularen NCO-Gruppen enthaltenden Verbindungen auch ein Polyisocyanatgemisch auf Diphenylmethanbasis geeignet. Diese lassen sich ebenso wie die vorher schon genannten NCO-Gruppen enthaltenden Verbindungen überraschenderweise gut emulgieren, was verständlicherweise die Voraussetzung für ihre Anwendung ist.As the only exception, in addition to the compounds containing higher molecular weight NCO groups, a polyisocyanate mixture based on diphenylmethane is also suitable. These, like the previously mentioned compounds containing NCO groups, can surprisingly be emulsified well, which is understandably the prerequisite for their use.

Die beschriebenen ausgewählten NCO-Gruppen enthaltenden Verbindungen kommen erfindungsgemäß nicht als solche, sondern in blockierter Form zum Einsatz. Die Blockierung erfolgt dabei durch Umsetzung dieser Verbindungen mit etwa stöchiometrischen Mengen an Blockierungsmittel. Nach der Umsetzung sind die freien NCO-Gruppen praktisch vollständig verschwunden. Als Blockierungsmittel sind Phenole, Malonester, Acetessigester und andere bekannte Substanzen, bevorzugt jedoch C 2- bis C 8-Alkanonoxime, insbesondere das Butanonoxim, geeignet (siehe z. B. EP-OS 107 838). Die blockierten NCO-Gruppen enthaltenden Verbindungen können in der Hitze aufgespalten werden, so daß wiederum reaktionsbereite Verbindungen vorliegen. Die mit C 2- bis C 8-Alkanonoximen, insbesondere Butanonoxim, blockierten Verbindungen lassen sich bei relativ niedrigen Temperaturen wieder aufspalten, weshalb diese Blockierungsmittel bevorzugt sind. Gegebenenfalls kann die Rückspaltung durch Zusatz von Katalysatoren, z. B. Sn-Alkylverbindungen, beschleunigt werden.According to the invention, the selected compounds containing NCO groups described are not used as such, but rather in blocked form. The blocking takes place by reacting these compounds with approximately stoichiometric amounts of blocking agent. After the reaction, the free NCO groups have practically completely disappeared. Suitable blocking agents are phenols, malonic esters, acetoacetic esters and other known substances, but preferably C 2 -C 8 -alkanone oximes, in particular butanone oxime (see, for example, EP-OS 107 838). The compounds containing blocked NCO groups can be broken down in the heat, so that again ready-to-react compounds are present. The compounds blocked with C 2- to C 8-alkanone oximes, in particular butanone oxime, can be broken down again at relatively low temperatures, which is why these blocking agents are preferred. Optionally, the cleavage by adding catalysts, for. B. Sn alkyl compounds are accelerated.

Das blockierte niedermolekulare Polyurethan bzw. das blockierte Polyisocyanat werden zur Erzielung der wasch- und (chemisch)-reinigungsbeständigen Textilausrüstung als sogenannte Extender, also Stoffe, die die Öl- und Wasserabweisung verbessern und dabei eine Verringerung der Menge der Fluoralkylreste enthaltenden Verbindungen ermöglichen, eingesetzt. Dafür sind Mengen von 3 bis 25 Gew.-%, insbesondere 7 bis 17 Gew.-%, bezogen auf 100%-iges reaktives, Perfluoralkylgruppen enthaltendes (Co)polymer und bzw. oder Vorkondensat, vollkommen ausreichend, so daß höhere Mengen schon aus Kostengründen nicht in Betracht kommen.The blocked low molecular weight polyurethane or the blocked polyisocyanate are used to achieve the washing and (chemical) cleaning-resistant textile equipment as so-called extenders, i.e. substances that improve oil and water repellency and thereby reduce the amount of compounds containing fluoroalkyl residues. Amounts of 3 to 25% by weight, in particular 7 to 17% by weight, based on 100% reactive perfluoroalkyl group-containing (co) polymer and / or precondensate, are completely sufficient, so that higher amounts are sufficient Cost reasons are out of the question.

Bei dem erfindungsgemäßen Verfahren zum Behandeln von Textilien werden die blockierten NCO-Gruppen enthaltenden Verbindungen der Ausrüstungsflotte in emulgierter Form zugesetzt. Diese Emulsionen werden in bekannter Weise unter Verwendung bekannter Emulgatoren hergestellt und liegen schlußendlich in lösungsmittelfreier Form vor. Diese Herstellungsverfahren sind dem Fachmann bekannt und es ist nicht notwendig, darauf näher einzugehen.In the process according to the invention for treating textiles, the compounds containing blocked NCO groups are added to the finishing liquor in emulsified form. These emulsions are prepared in a known manner using known emulsifiers and are ultimately in solvent-free form. These production processes are known to the person skilled in the art and it is not necessary to go into them in more detail.

Eine besondere Ausgestaltung der Emulsionsherstellung ist allerdings bei der Verwendung von Melaminvorkondensaten als reaktives Rf-Vorkondensat erforderlich. Werden solche verwendet, so dürfen zur Erzielung von über mehrere Stunden beständigen Flotten die blockierten NCO-Gruppen enthaltenden Verbindungen nicht allein, sondern nur zusammen mit einem weiteren bekannten wasserunlöslichen Textilhilfsmittel im Lösungsmittel, gegebenenfalls bei leicht erhöhter Temperatur, gelöst, dann erst wie bekannt diese Lösung in ein Emulgator-Wasser-Gemisch (als Emulgatoren sind die handelsüblichen Produkte verwendbar) eingerührt bzw. einturbiniert und anschließend das erhaltene Gemisch einer Hochdruckhomogenisierung unterworfen werden. Abschließend wird wie üblich das Lösungsmittel unter vermindertem Druck bei leicht erhöhter Temperatur abdestilliert und die Emulsion auf den gewünschten Trockensubstanzgehalt mit Wasser eingestellt.However, a special embodiment of the emulsion preparation is required when using melamine precondensates as reactive R f precondensates. If such are used, the blocked NCO group-containing compounds must not be dissolved in the solvent alone, but only together with another known water-insoluble textile auxiliary, if appropriate at a slightly elevated temperature, in order to achieve fleets which are stable for several hours, only then, as is known, this solution stirred into an emulsifier / water mixture (commercially available products can be used as emulsifiers) and then subjected to high-pressure homogenization, and the mixture obtained is then subjected to high-pressure homogenization. Finally, as usual, the solvent is distilled off under reduced pressure at a slightly elevated temperature and the emulsion is adjusted to the desired dry substance content with water.

Neben den verschiedenen reaktiven, Perfluoralkylgruppen enthaltenden (Co)polymeren bzw. Vorkondensaten können im Rahmen des erfindungsgemäßen Verfahrens auch andere übliche Textilhilfsmittel, deren Zusatz schon bei der Herstellung von Compounds (siehe oben), aber selbstverständlich auch erst nachträglich erfolgen kann, mitverwendet werden.In addition to the various reactive (co) polymers containing perfluoroalkyl groups or precondensates, other customary textile auxiliaries, the addition of which can be added during the manufacture of compounds (see above), but of course can also be added subsequently, can also be used in the process according to the invention.

Als solche Zusätze sind übliche Knitterfrei- und Weichgriffmittel, Flammfestmittel, Oleophobierungsmittel, Hydrophobiermittel, Appreturmittel und andere zu nennen. Selbstverständlich ist es auch angebracht, soweit erforderlich, bekannte Härtungsmittel mitzuverwenden.Such additives include customary crease and softening agents, flame retardants, oleophobicizing agents, water repellents, finishing agents and others. Of course, it is also appropriate, if necessary, to use known hardening agents.

Das erfindungsgemäße Verfahren dient zum Imprägnieren von Textilien aller Art aus wäßrigem Medium. Das Wasser kommt dabei natürlich in unterschiedlichen Mengen zum Einsatz, je nachdem, ob durch Foulardieren, Sprühen, Pflatschen oder ähnliches eine Imprägnierung, also Durchtränkung des Materials, vorgenommen wird. Bei der Imprägnierung handelt es sich um durchaus gängige Ausrüstungsmethoden, die dem Fachmann geläufig sind. Diese Verfahren bedürfen daher keiner besonderen Erläuterung und es kann auf die bekannte Literatur verwiesen werden. Einzelheiten sind überdies den Beispielen zu entnehmen. Festzuhalten bleibt allerdings, daß die Verwendung von organischen Lösungsmitteln bei dem erfindungsgemäßen Verfahren nicht erforderlich ist, sondern lösungsmittelfrei gearbeitet wird.The method according to the invention is used to impregnate all types of textiles from an aqueous medium. The water is of course used in different quantities, depending on whether impregnation, i.e. impregnation of the material, is carried out by padding, spraying, splashing or the like. The impregnation is a very common finishing method, which the skilled worker is familiar with. These methods therefore require no special explanation and reference can be made to the known literature. Further details can be found in the examples. It should be noted, however, that the use of organic solvents is not necessary in the process according to the invention, but is carried out without solvents.

Das erfindungsgemäße Verfahren ist zum Imprägnieren von Textilien aller Art, sei es in Form von Geweben, Gewirken oder Vliesen geeignet. Diese können sowohl aus natürlichen Fasern, wie Cellulose- oder Keratinfasern, als auch aus synthetischen Fasern, wie Polyacrylnitril, Polyamid, Polyvinylalkohol oder Polyester, hergestellt sein. Selbstverständlich kommen auch Textilmaterialien in Betracht, die aus Mischungen von natürlichen mit synthetischen Fasern bestehen. Hervorzuheben ist, daß nach dem erfindungsgemäßen Verfahren auch leicht eingestellte Gewebe, wie Taft oder leicht eingestellte Popelinestoffe, ausgerüstet werden können. Dies ist beispielsweise für Regenschutzbekleidung, wie Anoraks und dergleichen, von Bedeutung.The method according to the invention is suitable for impregnating textiles of all kinds, be it in the form of woven, knitted or non-woven fabrics. These can be made both from natural fibers, such as cellulose or keratin fibers, and from synthetic fibers, such as polyacrylonitrile, polyamide, polyvinyl alcohol or polyester. Of course, textile materials that consist of mixtures of natural and synthetic fibers are also suitable. It should be emphasized that even slightly adjusted fabrics, such as taffeta or slightly adjusted poplin fabrics, can be finished using the method according to the invention. This is important, for example, for rain protective clothing such as anoraks and the like.

Erst durch das erfindungsgemäße Verfahren ist es möglich geworden, Textilien derart wasser- und ölabweisend auszurüsten, daß diese Ausrüstungen sehr gut wasch- und/oder (chemisch)reinigungsbeständig sind.Only through the method according to the invention has it become possible to make textiles so water and oil repellent that these finishes are very washable and / or (chemically) resistant to cleaning are.

Die bekannten Verfahren haben zwar auch schon in dieser Richtung einige Fortschritte gebracht, aber durch den Zusatz der ausgewählten blockierten niedermolekularen Polyurethane bzw. der blockierten Polyisocyanate wird diese Reinigungsbeständigkeit nochmals deutlich verbessert (siehe auch Vergleichsbeispiele), so daß die erhaltenen Effekte nunmehr allen Anforderungen in dieser Hinsicht genügen.The known methods have already made some progress in this direction, but the addition of the selected blocked low molecular weight polyurethanes or the blocked polyisocyanates further improves this cleaning resistance (see also comparative examples), so that the effects obtained now meet all requirements in this Respects are enough.

In den folgenden Beispielen erfolgt die Prüfung der Ölabweisung nach der Methode, wie sie in AATCC 118-1972 angegeben ist. Die Prüfung der Wasserabweisung erfolgt nach DIN 53 888 (a = Wasseraufnahme in %, b = Abperleffekt) bzw. dem Spraytest entsprechend AATCC 22-1974. Die Trockenreinigung wird - wenn nicht anders angegeben - im Flottenverhältnis 1 : 10 (Mustergewicht zu Flottenvolumen) während 15 Minuten durchgeführt, wobei für jede Reinigung das verwendete Tetrachlorethylen erneuert wird. Die Wäsche der Muster wird in der jeweils angegebenen Weise vorgenommen.In the following examples, the oil repellency is tested using the method as specified in AATCC 118-1972. The water repellency is tested according to DIN 53 888 (a = water absorption in%, b = water repellent effect) or the spray test according to AATCC 22-1974. Unless otherwise stated, the dry cleaning is carried out in a liquor ratio of 1:10 (sample weight to liquor volume) for 15 minutes, the tetrachlorethylene used being renewed for each cleaning. The samples are washed in the manner specified in each case.

Beispiel 1example 1 a) Herstellung eines blockierten niedermolekularen Polyurethansa) Production of a blocked low molecular weight polyurethane

30 g einer 75gew.-%-igen Lösung des Umsetzungsproduktes aus 3 Mol Toluylendiisocyanat und 1 Mol Trimethylolpropan (durchschnittliches Molekulargewicht ca. 850) in Ethylacetat werden in30 g of a 75% by weight solution of the reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane (average molecular weight approx. 850) in ethyl acetate are dissolved in

67 g Methylisobutylketon gelöst.67 g of methyl isobutyl ketone dissolved.

In diese Lösung werden 7,0 g Butanonoxim gegeben, wobei die Temperatur auf 60 bis 70° C ansteigt. Bei dieser Temperatur wird anschließend 20 Minuten gerührt und IR-spektrographisch geprüft, ob noch NCO-Banden vorhanden sind. Solange derartige Banden noch nachweisbar sind, werden portionsweise je 0,1 g Butanonoxim zugegeben, bis keine NCO-Gruppen mehr nachweisbar sind.7.0 g of butanone oxime are added to this solution, the temperature rising to 60 to 70.degree. The mixture is then stirred for 20 minutes and checked by IR spectrography whether NCO bands are still present. As long as such bands are still detectable, 0.1 g butanone oxime is added in portions until no more NCO groups can be detected.

b) Emulgierung des blockierten niedermolekularen Polyurethans zusammen mit perfluormodifiziertem Polyurethanb) emulsification of the blocked low molecular weight polyurethane together with perfluoromodified polyurethane

  • 97,8 geiner 50%-igen Lösung eines perfluoralkylmodifizierten Polyurethans (siehe US-PS 3 968 066, Beispiel 8) in Butylacetat sowie97.8 g of a 50% solution of a perfluoroalkyl modified polyurethane (see US Pat. No. 3,968,066, Example 8) in butyl acetate as well
  • 1,7 g Eisessig werden zusammengerührt und die Mischung auf 70°C erwärmt.1.7 g of glacial acetic acid are stirred together and the mixture is heated to 70.degree.
  • In einem separaten Gefäß werdenBe in a separate jar
  • 8,8 g des Acetats eines ethoxylierten Fettamins (ca. 10 Mol Ethylenoxid je Mol Fettamin mit C 16- bis C 18-Alkylrest) sowie8.8 g of the acetate of an ethoxylated fatty amine (approx. 10 moles of ethylene oxide per mole of fatty amine with a C 16 to C 18 alkyl radical) and
  • 245,0 g Wasser auf 70° C unter Rühren erwärmt. In diese Lösung wird mittels eines Schnellrührers die Lösung des blockierten niedermolekularen Polyurethans und des perfluormodifizierten Polyurethans einturbiniert. Anschließend wird diese Voremulsion bei 70°C auf einer Hochdruckhomogenisiermaschine bei 300 bar bis zum Erreichen der gewünschten Feinteiligkeit homogenisiert. Diese Emulsion wird dann zur Entfernung des Lösungsmittels einer azeotropen Vakuumdestillation unterworfen, und zwar bei maximal 40° C und mit Wasser auf eine Endmenge von 383 g eingestellt. Nachdem noch 255 g einer 16 %-igen Emulsion eines perfluoralkylmodifizierten Methylolmelaminethers (siehe EP-OS 073 364, Beispiel 1) zugesetzt sind, erhält man eine Emulsion mit ca. 20 Gew.-% Feststoffgehalt, die 4,8 Gew.-% an verkapptem niedermolekularem Polyurethan enthält.245.0 g of water heated to 70 ° C with stirring. The solution of the blocked low molecular weight polyurethane and of the perfluoromodified polyurethane is injected into this solution using a high-speed stirrer. This pre-emulsion is then homogenized at 70 ° C. on a high-pressure homogenizing machine at 300 bar until the desired fine particle size is reached. This emulsion is then subjected to azeotropic vacuum distillation to remove the solvent, at a maximum of 40 ° C. and adjusted to a final amount of 383 g with water. After 255 g of a 16% emulsion of a perfluoroalkyl-modified methylolmelamine ether (see EP-OS 073 364, Example 1) have been added, an emulsion is obtained with a solids content of approximately 20% by weight, which is 4.8% by weight capped low molecular weight polyurethane contains.
c) Ausrüstungc) equipment

Ein blauer Baumwollköper (222 g/m2) wird mit folgender Flotte foulardiert:

  • 30 g/I der nach b) hergestellten Emulsion,
  • 2 g/I 60%-ige Essigsäure,
  • 20 g/I einer wäßrigen ca. 50 %-igen Lösung von Pentamethylolmelaminmethylether,
  • 30 g/1 einer45 %-igen wäßrigen Lösung von Dimethyloldihydroxyethylenharnstoff und
  • 8 g/1 Magnesiumchloridhexahydrat.
A blue cotton twill (222 g / m 2 ) is padded with the following liquor:
  • 30 g / l of the emulsion prepared according to b),
  • 2 g / l 60% acetic acid,
  • 20 g / l of an aqueous approx. 50% solution of pentamethylolmelamine methyl ether,
  • 30 g / 1 of a 45% aqueous solution of dimethyloldihydroxyethyleneurea and
  • 8 g / 1 magnesium chloride hexahydrate.

Die Flottenaufnahme beträgt 78 %. Das so behandelte Gewebe wird anschließend bei 110°C 10 Minuten getrocknet und danach 5 Minuten bei 150°C kondensiert (Ausrüstung A).The fleet intake is 78%. The fabric treated in this way is then dried at 110 ° C. for 10 minutes and then condensed at 150 ° C. for 5 minutes (equipment A).

Zum Vergleich wird eine Ausrüstung B in gleicher Weise durchgeführt, wobei aber die Herstellung der Emulsion in Abwesenheit des blockierten niedermolekularen Polyurethans erfolgt, dafür aber bei dem Flottenansatz 20 g/1 eines handelsüblichen Extenders auf Basis fettmodifizierten Kunstharzes (siehe z. B. DE-PS 12 33 874, Beispiele 1 und 4) mitverwendet werden.For comparison, equipment B is carried out in the same way, but the emulsion is produced in the absence of the blocked low-molecular-weight polyurethane, but with the liquor batch 20 g / 1 of a commercially available extender based on fat-modified synthetic resin (see, for example, DE-PS 12 33 874, Examples 1 and 4) can also be used.

Die technologische Prüfung ergibt für die Öl- und Wasserabweisung folgende Werte:

Figure imgb0001
The technological test reveals the following values for oil and water repellency:
Figure imgb0001

Das Beispiel 1 wird wiederholt unter Verwendung des perfluoralkylmodifizierten Methylolmelaminethers entsprechend Beispiel 2 B der EP-OS 073 364, wobei vergleichbare Ergebnisse resultieren.Example 1 is repeated using the perfluoroalkyl-modified methylol melamine ether according to Example 2 B of EP-OS 073 364, with comparable results.

Beispiel 2Example 2

Mit einer Flotte enthaltend

  • 24 g/I der im Beispiel 1 unter b) hergestellten Emulsion,
  • 10 g/1 einer ca. 50 %-igen wäßrigen Aminoplastvorkondensatlösung (mit Methanol verethertes Pentamethylolmelamin) und
  • 6 g/I Katalysatorlösung (ca. 75 %-ige wäßrige Zinknitrathexahydratlösung mit geringen Mengen Salz- und Essigsäure)
  • werden a) ein Polyacrylnitrilgewebe (214 g/m2) , b) ein Polyester/Baumwollmischgewebe (65/35; 208 g/m2) und c) eine vorgewaschene Wollwebware (180 g/m2) foulardiert (Flottenaufnahme 90 bzw. 60 bzw. 78 %), 10 Minuten bei 110°C getrocknet und 2,5 Minuten bei 150°C kondensiert. Die so ausgerüsteten Gewebe weisen hinsichtlich Öl- und Wasserabweisung hervorragende Anfangswerte auf, die auch einer chemischen Reinigung und einer üblichen Haushaltswäsche in hervorragendem Maße widerstehen.
Containing a fleet
  • 24 g / l of the emulsion prepared in example 1 under b),
  • 10 g / 1 of an approximately 50% aqueous aminoplast precondensate solution (pentamethylol melamine etherified with methanol) and
  • 6 g / l catalyst solution (approx. 75% aqueous zinc nitrate hexahydrate solution with small amounts of hydrochloric and acetic acid)
  • a) a polyacrylonitrile fabric (214 g / m 2 ), b) a polyester / cotton blend (65/35; 208 g / m 2 ) and c) a pre-washed woolen fabric (180 g / m 2 ) are padded (pick up 90 or 60 or 78%), dried at 110 ° C for 10 minutes and condensed at 150 ° C for 2.5 minutes. The fabrics treated in this way have excellent initial values with regard to oil and water repellency, which also withstand chemical cleaning and normal household washing to an outstanding degree.

Beispiel 3Example 3

In der im Beispiel 1 beschriebenen Weise werden nacheinander mit Butanonoxim folgende Polyisocyanate blockiert: trimeres lsophorondiisocyanat (A), DESMODUR RF der Fa. Bayer (B), trimeres Hexamethylen-1,6-diisocyanat (C), Hexamethylen-1,6-diisocyanat (D) und Naphthylen-1,5-diisocyanat (E).The following polyisocyanates are blocked in succession with butanone oxime in the manner described in Example 1: trimeric isophorone diisocyanate (A), DESMODUR RF from Bayer (B), trimeric hexamethylene-1,6-diisocyanate (C), hexamethylene-1,6-diisocyanate (D) and naphthylene-1,5-diisocyanate (E).

Von den so hergestellten blockierten Polyisocyanaten wird wie unten beschrieben eine 25 %-ige Emulsion bereitet und dabei folgendes Ergebnis erhalten:

Figure imgb0002
A 25% emulsion of the blocked polyisocyanates thus prepared is prepared as described below and the following result is obtained:
Figure imgb0002

Die obige Aufstellung zeigt, daß nur die erfindungsgemäß verwendeten Polyisocyanate mit einem Molekulargewicht von über 450 in blockierter Form ohne weiteres emulgierfähig sind und damit nur diese Produkte ohne Schwierigkeiten erfindungsgemäß eingesetzt werden können.The above list shows that only the polyisocyanates used according to the invention with a molecular weight of more than 450 in blocked form are readily emulsifiable and therefore only these products can be used according to the invention without difficulty.

In 100 g Methylethylketon werden bei ca. 60°C 100 g des wie nachfolgend beschrieben hergestellten blockierten Polyurethans zugegeben und auf 60°C erwärmt. Die Flüssigkeit besteht aus zwei nichtmischbaren schichten. Sie wird in eine Lösung von 10 g des im Beispiel 1 beschriebenen Emulgators in 290 g Wasser von einer Temperatur von 60°C einturbiniert und anschließend auf einer Hochdruckhomogenisiermaschine homogenisiert, ebenfalls bei einer Temperatur von 60°C. Danach wird das Lösungsmittel im Vakuum bei 30 bis 40° C unter Rühren abdestilliert und die Emulsion auf 25 Gew.-% Trockensubstanzgehalt mit Wasser eingestellt.In 100 g of methyl ethyl ketone, 100 g of the blocked polyurethane prepared as described below are added at about 60 ° C. and heated to 60 ° C. The liquid consists of two immiscible layers. It is turbinated in a solution of 10 g of the emulsifier described in Example 1 in 290 g of water at a temperature of 60 ° C. and then homogenized on a high-pressure homogenizing machine, likewise at a temperature of 60 ° C. The solvent is then distilled off in vacuo at 30 to 40 ° C. with stirring and the emulsion is adjusted to 25% by weight dry matter content with water.

490 g des im Beispiel 1 beschriebenen niedermolekularen Polyurethans werden in 375 g Methylethylketon in einem Dreihalskolben, versehen mit Thermometer, Rührer und Rückflußkühler vorgelegt und bei Zimmertemperatur 135 g Butanonoxim zugegeben. Dabei steigt die Temperatur auf 60 bis 70°C an. Nach 20- minütigem Rühren wird IR-spektrographisch geprüft, ob noch NCO-Banden vorhanden sind. Solange solche noch nachweisbar sind, wird weiterhin Butanonoxim in Mengen von ca. 3 g zugegeben. Man erhält auf diese Weise 1000 g einer 50 %-igen Lösung des blockierten Polyurethans.490 g of the low molecular weight polyurethane described in Example 1 are placed in 375 g of methyl ethyl ketone in a three-necked flask equipped with a thermometer, stirrer and reflux condenser and 135 g of butanone oxime are added at room temperature. The temperature rises to 60 to 70 ° C. After stirring for 20 minutes, an IR spectrographic test is carried out to determine whether NCO bands are still present. As long as such are still detectable, butanone oxime is still added in amounts of approx. 3 g. In this way, 1000 g of a 50% solution of the blocked polyurethane are obtained.

Werden von den blockierten Produkten A) bis C) 15 g/I unter zusätzlicher Verwendung vonAre blocked products A) to C) 15 g / I with the additional use of

30 g/I der Emulsion eines perfluormodifizierten Polyurethans entsprechend Beispiel 11 A der US-PS 3 968 06630 g / l of the emulsion of a perfluoromodified polyurethane according to Example 11 A of US Pat. No. 3,968,066

(lösungsmittelfrei durch azeotrope Vakuumdestillation),

  • 10 g/I Mischpolymerisat-dispersion (siehe DE-AS 1 419 505, Beispiel 1),
  • 40 g/I ca. 50 %-ige wäßrige Dimethylolethylenharnstofflösung,
  • 12 g/I Essigsäure 60 %-ig,
  • 12 g/I Zirkonoxychloridlösung (22 % Zr02) und
  • 6 g/I kristallisiertes Natriumacetat
(solvent-free by azeotropic vacuum distillation),
  • 10 g / l of copolymer dispersion (see DE-AS 1 419 505, Example 1),
  • 40 g / l approx. 50% aqueous dimethylolethylene urea solution,
  • 12 g / l 60% acetic acid,
  • 12 g / l zirconium oxychloride solution (22% Zr0 2 ) and
  • 6 g / l crystallized sodium acetate

Ausrüstungsflotten hergestellt und ein oliver Baumwollatlas (ca. 300 g/m2) in bekannter Weise (Flottenaufnahme ca. 72 %, Trocknung und Kondensation wie im Beispiel 1) behandelt, so werden hervorragende Ausrüstungseffekte erhalten, die auch Kochwäschen nach DIN 83 892 sehr gut widerstehen.Equipment liquors produced and an olive cotton atlas (approx. 300 g / m 2 ) treated in a known manner (liquor absorption approx. 72%, drying and condensation as in Example 1), excellent treatment effects are obtained, which are also very good, according to DIN 83 892 resist.

Beispiel 4Example 4

Der in Beispiel 1 c) beschriebene Baumwollköper wird in der dort angegebenen Weise mit folgender Behandlungsflotte ausgerüstet:

  • 24 g/I der unter Beispiel 1 b) hergestellten Emulsion, die aber anstelle des blockierten niedermolekularen Polyurethans die gleiche Menge eines in gleicher Weise blockierten technischen Gemisches von Diphenylmethandiisocyanaten enthält,
    • 2 g/I 60 %-ige Essigsäure,
    • 30 g/I einer etwa 60 %-igen wäßrigen Lösung von Dimethyloldihydroxyethylenharnsoff und
    • 8 g/I Magnesiumchloridhexahydrat.
    • Das so ausgerüstete Gewebe zeigt folgende Effekte:
      Figure imgb0003
The cotton twill described in Example 1 c) is equipped in the manner given there with the following treatment liquor:
  • 24 g / l of the emulsion prepared under Example 1 b), but which instead of the blocked low molecular weight polyurethane contains the same amount of an equally blocked technical mixture of diphenylmethane diisocyanates,
    • 2 g / l 60% acetic acid,
    • 30 g / l of an approximately 60% aqueous solution of dimethyloldihydroxyethylene urea and
    • 8 g / l magnesium chloride hexahydrate.
    • The fabric equipped in this way has the following effects:
      Figure imgb0003

Beispiel 5Example 5

Ein Baumwoll/Polyester-Mantelpopeline (35/65; 200 g/m2) wird in der im Beispiel 1 angegebenen Weise behandelt (Flottenaufnahme ca. 65 %):

  • 25 g/l der Emulsion des Beispiels 1 der EP-OS 073 364,
  • 6 g/I der im Beispiel 3 beschriebenen Emulsion des blockierten Polyurethans, die zusätzlich 50 g Paraffin (Schmelzpunkt 52 - 54° C) enthält,
  • 2 g/I 60 %-ige Essigsäure,
  • 30 g/I Aminoplastharzlösung (ca. 52 %-ige wäßrige Lösung von Dimethylolethylenharnstoff und mit Methanol verethertem Pentamethylolmelamin im Verhältnis 2,5 : 1 ) und
  • 8 g/I Katalysatorlösung nach Beispiel 2 (Flotte A).
  • Im Vergleich dazu wurde der gleiche Stoff in gleicher Weise ausgerüstet, wobei die Emulsion des Beispiels 3 nur das Paraffin enthielt (Flotte B).
  • Die so ausgerüsteten Gewebe zeigen folgende Effekte:
    Figure imgb0004
A cotton / polyester jacketed poplin (35/65; 200 g / m 2 ) is treated in the manner given in Example 1 (liquor absorption approx. 65%):
  • 25 g / l of the emulsion of Example 1 of EP-OS 073 364,
  • 6 g / l of the emulsion of the blocked polyurethane described in Example 3, which additionally contains 50 g of paraffin (melting point 52-54 ° C.),
  • 2 g / l 60% acetic acid,
  • 30 g / l aminoplast resin solution (approx. 52% aqueous solution of dimethylolethylene urea and pentamethylol melamine etherified with methanol in a ratio of 2.5: 1) and
  • 8 g / l catalyst solution according to Example 2 (fleet A).
  • In comparison, the same fabric was finished in the same way, the emulsion of Example 3 containing only the paraffin (fleet B).
  • The fabrics treated in this way have the following effects:
    Figure imgb0004

Durch den Zusatz der erfindungsgemäßen blockierten NCO-Gruppen enthaltenden Verbindungen (Flotte A) werden die Anfangswerte, vor allem aber die Reinigungsbeständigkeit, deutlich verbessert.By adding the compounds containing NCO groups according to the invention (fleet A), the initial values, but above all the cleaning resistance, are significantly improved.

Claims (11)

1. Process for obtaining wash- and cleaning-resistant textile finishes by impregnating with conventional reactive (co)polymers and/or precondensates containing perfluoroalkyl radicals with at least 4 C-atoms, which contain as reactive groups OH- or respectively OR-groups, in which R denotes an alkyl radical with 1 to 3 C-atoms, in aqueous dispersion, and subsequent heating, characterized in that the dispersions contain compounds containing NCO-groups, which compounds have a molecular weight of at least 450, and/or contain a polyisocyanate mixture on diphenylmethane base, all in blocked form.
2. Process according to Patent Claim 1, characterized in that as compounds containing NCO-groups, the dispersions contain in blocked form those which have a molecular weight of at least 600.
3. Procecss according to Patent Claims 1 to 2, characterized in that the compounds containing blocked NCO- groups are used in quantities of 3 to 25 %-wt., in relation to 100 % reactive (co)polymer and/or precondensate containing perfluoroalkyl groups.
4. Process according to Patent Claims 1 to 3, characterized in that the compounds containing blocked NCO- groups are used in quantities of 7 to 17 %-wt., in relation to 100 % reactive (co)polymer and/or precondensate containing perfluoroalkyl groups.
5. Process according to Patent Claims 1 to 4, characterized in that the compounds containing blocked NCO- groups are used in emulsified, solvent-free form.
6. Process according to Patent Claim 5, characterized in that the compounds containing blocked NCO-groups are emulsified together with a known textile adjuvant, which is insoluble in water, and are used in this form together with Rf-melamine precondensates, in which Rf denotes a perfluoroalkyl radical with 6 to 14 C-atoms.
7. Process according to Patent Claims 1 to 6, characterized in that blocked low-molecular polyurethanes are used as compounds containing blocked NCO-groups.
8. Process according to Patent Claim 7, characterized in that the blocked low-molecular polyurethanes were produced by reaction of low-molecular polyol compounds and polyisocyanates in an equivalent ratio of at least 1 : 1.3 OH-groups to isocyanate groups, and subsequently the NCOgroups were blocked.
9. Process according to Patent Claim 8, characterized in that the equivalent ratio of the OH-groups to the isocyanate groups amounts to 1 : 1.5 to 2.5.
10. Process according to Patent Claims 1 to 6, characterized in that blocked polyisocyanates are used as compounds containing blocked NCO-groups.
11. Process according to Patent Claims 1 to 10, characterized in that conventional textile adjuvants are additionally used.
EP85904458A 1984-09-28 1985-09-17 Method for obtaining wash- and cleaning-resistant textile finishes using reactive perfluoroalkyl rest-containing (co)polymers and/or precondensates Expired EP0196309B1 (en)

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AT85904458T ATE33048T1 (en) 1984-09-28 1985-09-17 PROCESS FOR ACHIEVEMENTS RESISTANT TO WASHING AND CLEANING TEXTILE FINISHES WITH REACTIVE (CO)POLYMERS CONTAINING PERFLUORALKYL RESIDUES AND RESPECTIVELY. OR PRE-CONDENSATE.

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DE3435618 1984-09-28
DE19843435618 DE3435618A1 (en) 1984-09-28 1984-09-28 METHOD FOR OBTAINING WASHING AND CLEANING-RESISTANT TEXTILE EQUIPMENT WITH REACTIVE (CO) POLYMERS OR PRE-CONDENSATE

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EP0196309B1 true EP0196309B1 (en) 1988-03-16

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ES (1) ES8801006A1 (en)
WO (1) WO1986002115A1 (en)

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US4834764A (en) 1989-05-30
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WO1986002115A1 (en) 1986-04-10
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KR920009256B1 (en) 1992-10-15
ES8801006A1 (en) 1987-12-01
DE3561895D1 (en) 1988-04-21
DE3435618A1 (en) 1986-04-10
KR880700124A (en) 1988-02-15

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