EP0491248B1 - Composition for the treatment of fibrous materials - Google Patents

Abstract

Highly effective compositions for the water- and oil-repellent finishing of fibre materials, in particular textile materials, contain at least two components which are aqueous dispersions. One of the dispersions contains a copolymer composed of a fluorine-containing (meth)acrylate, vinyl chloride and a fluorine-free (meth)acrylate, and also ethoxylated alkylphenol. The other dispersion contains either a copolymer composed of a fluorine-containing acrylate, vinylidene chloride and a fluorine-free (meth)acrylate and also ethoxylated fatty acids or an isocyanate blocked by means of an oxime, a fluorine-containing oligo- or polyurethane and an ethoxylated fatty amine (salt). The compositions lead to a pleasantly soft feel of the finished fibre material and in many cases reduce the bleeding of dye in the case of dyed textiles.

Description

The invention relates to an agent for treating fiber materials which contains at least two components which have special compositions. It also relates to the use of such agents for the treatment of fiber materials.

It is known to treat materials which contain natural, regenerated or synthetic fibers with certain agents in order to impart certain desired properties to the materials, for example textiles. The fiber materials are usually in the form of fabrics such as woven fabrics, knitted fabrics or "non-wovens" (nonwovens).
In many cases, the properties that are to be imparted to the fiber materials include, among other things, a pleasantly soft feel and water and / or oil-repellent effect.

Fluorine-containing polymers are widely used to achieve the water- and oil-repellent properties of textiles. This is described, for example, in US Pat. No. 4,742,140 or in EP-A-0 325 918. According to the US patent mentioned, copolymers are used which consist of perfluorinated group-containing acrylates, vinylidene chloride and (meth) acrylates as monomers are built up. These copolymers can be used in the form of aqueous dispersions which contain ethoxylated fatty acids as emulsifiers. If textile fabrics are treated with dispersions of copolymers according to this US Pat. No. 4,742,140, however, it must be noted as a disadvantage that the effectiveness of the oil and water repellency is not satisfactory in all cases. In addition, the textiles finished in this way are not yet optimally soft to the touch.

In addition, in the case of dyed textiles, the resistance of the dye to solvents in which the dye dissolves is insufficient. This is important as soon as the textiles come into contact with appropriate solvents, e.g. when dry-cleaning or when using protective clothing. It has been shown that portions of the dye are dissolved out by the solvent in these cases; this applies in particular to disperse dyes compared to acetone, perchlorethylene and methyl ethyl ketone as solvents. The disadvantage of insufficient fastness to solvents does not only occur in the case of finishing with copolymers according to US Pat. No. 4,742,140, but was also found in textiles which were oil and water repellent with other fluorine-containing products.

The present invention was therefore based on the object to provide a means for the highly effective oil- and water-repellent finishing of fiber materials, which provides the materials equipped with a pleasantly soft handle and which additionally ensures that the colored materials thus equipped have improved solvent resistance the coloring, in particular also with respect to solvents such as acetone, perchlorethylene and / or methyl ethyl ketone.

The object was achieved by a means according to claim 1; preferred embodiments emerge from the subclaims.

It was surprisingly found that the combination of components A) and B) defined in claim 1, especially when using component B1) equipped with colored fiber materials, gives the dyeing excellent resistance to organic solvents, in particular to acetone, perchlorethylene and methyl ethyl ketone. This finding was surprising and unexpected for the person skilled in the art, because, as set out below in the exemplary embodiments, neither component A) nor component B) by itself in all cases lead to satisfactory solvent fastness. In addition, the agents according to the invention obtain a softer feel for the finished fiber materials than with components A) and B) on their own.

The agents according to the invention give the fiber materials such as textiles equipped with them a pleasantly soft feel and very good oil and water-repellent properties. Finishing with these agents shows a very good permanence towards washing processes and against solvents. The aqueous dispersions of components A) and B) can be added to other agents used for textile finishing, such as antistatic agents, without the stability of the dispersions and the finishing effects, such as oil and water repellency or soft feel, being adversely affected.

The agents according to the invention contain at least two components A) and B), each of which is an aqueous dispersion. To achieve fully satisfactory effects with regard to solvent fastness of the dyeing, it is necessary that the weight ratio of component A) to component B) is in the range from 30 to 70 to 70 to 30. Mixing ratios outside this range lead to less good results. The further the mixing ratio is from the range according to the invention, the closer the results regarding solvent fastness approach those which are obtained with the pure components A) or B) and which are not fully satisfactory . Particularly preferred among the agents according to the invention are those in which the weight ratio of component A) to component B) is approximately 50 to 50. With a weight ratio of this size, the synergism between A) and B) is particularly pronounced.

To produce agents according to the invention, it is sufficient to mix the two dispersions (components A) and B)) with one another. Normally, no further homogenization has to be carried out after the mixing.

Component A )

• a) 15 bis 25 Gew.teile
• b) 1 bis 2 Gew.teile
• c) 55 bis 75 Gew.teile

Bestandteil a) ist ein Copolymeres, das aus drei Monomeren aufgebaut ist, nämlich einem Perfluoralkylethylacrylat oder einem Perfluoralkylethylmethacrylat, Vinylchlorid und einem fluorfreien Alkylacrylat oder -methacrylat. Das Perfluoralkylethylacrylat ist zu 50 bis 60 Gew.%, Vinylchlorid zu 2 bis 10 Gew.% und das fluorfreie Alkyl(meth-)acrylat zu 30 bis 40 Gew.% enthalten, wobei die Summe der im Einzelfall vorliegenden Gewichtsprozente immer 100 ist. Das Perfluoralkylethylacrylat ist ein Acrylsäureester der Formel



        CH₂ = CH - COO CH₂ CH₂ - R_f



bzw. der entsprechende Methacrylsäureester, worin R_f einen unverzweigten oder verzweigten Perfluoralkylrest mit 2 bis 14 C-Atomen darstellt.Component A) is an aqueous dispersion which contains at least the components a), b) and c) described below and which can also contain further components.
The components a), b), and c) are contained in the following amounts:

• a) 15 to 25 parts by weight
• b) 1 to 2 parts by weight
• c) 55 to 75 parts by weight

Constituent a) is a copolymer which is composed of three monomers, namely a perfluoroalkylethyl acrylate or a perfluoroalkylethyl methacrylate, vinyl chloride and a fluorine-free alkyl acrylate or methacrylate. The perfluoroalkylethyl acrylate is 50 to 60% by weight, vinyl chloride 2 to 10% by weight and the fluorine-free alkyl (meth) acrylate 30 to 40% by weight, the sum of the weight percentages present in the individual case always being 100. The perfluoroalkyl ethyl acrylate is an acrylic acid ester of the formula



CH₂ = CH - COO CH₂ CH₂ - R _f



or the corresponding methacrylic acid ester, in which R _{f represents} an unbranched or branched perfluoroalkyl radical having 2 to 14 carbon atoms.

The radical R _f is preferably an unbranched radical having 4 to 10 carbon atoms. Due to cost reasons, the perfluoroalkyl ethyl acrylate is not a single product, but a mixture of compounds that differ in the chain length of the R _{f group} . In at least 95% of all compounds contained in the mixture, however, the radical R _{f has} 2 to 14 C atoms; in the majority of the individual molecules, the radical Rf preferably contains 4 to 10 carbon atoms.

The fluorine-free alkyl acrylate or alkyl methacrylate contained as a monomer unit in the copolymer (component a) of component A) is an acrylic or methacrylic acid ester of an aliphatic straight-chain or branched alcohol with an alkyl chain of 10 to 18 carbon atoms. As in the case of the perfluoroalkylethyl acrylates explained above, in the case of the fluorine-free (meth) acrylate there is normally also a mixture of esters which differ in the chain length of the alcohol component. In at least 95% of the individual molecules, however, there is a chain length of the alcohol component of 10 to 18 carbon atoms. The fluorine-free acrylate n-octadecyl acrylate contained as component in component a) is preferred. The copolymers which can be used as component a) of component A) can be prepared from the monomers by customary methods, for example by means of emulsion polymerization.
Component b)
Component b) of component A) is an ethoxylated alkylphenol of the formula



R - C₆H₄ - O (CH₂ CH₂ O) _p - H



The radical R is an unbranched or branched alkyl radical with 4 to 12, preferably 6 to 10, carbon atoms, which is preferably in the p-position to the phenol oxygen. The value for p (degree of ethoxylation) is 6 to 20, preferably 10 to 16.
As in the cases explained above, component b) is normally a mixture of compounds which differ in the length of the radical R and in the degree of ethoxylation. Such mixtures are commercially available products that are on the market as emulsifiers, among other things.

The third component c) of component A) is water

Component B)

Either an aqueous dispersion B1 or an aqueous dispersion B2 is used as component B).

• d) 15 bis 20 Gew.teile
• e) 1 bis 2 Gew.teile
• f) 65 bis 80 Gew.teile

Bestandteil d) ist ein Copolymeres, das aus drei Monomeren aufgebaut ist, nämlich einem fluorhaltigen Acrylat, Vinylidenchlorid und einem fluorfreien Alkylacrylat oder Alkylmethacrylat. Das fluorhaltige Acrylat ist zu 40 bis 75 Gew.%, Vinylidenchlorid zu 10 bis 35 Gew.% und das fluortreie Alkyl(meth-)acrylat zu 10 bis 25 Gew.% enthalten, wobei die Summe der im Einzelfall vorliegenden Gewichtsprozente immer 100 ist.
Das fluorhaltige Acrylat besitzt die allgemeine Formel



        CF₃ - CF₂ - (CF₂)_k - CH₂ - CH₂ - O C(O) - CH = CH₂



In dieser Formel kann k die Werte 1 bis 12 annehmen. Das als Monomerbaustein in dem Copolymeren (Bestandteil d)) enthaltene fluorhaltige Acrylat muß kein einheitliches Produkt sein, sondern ist vielmehr im Normalfall ein Gemisch von Produkten, die unter die oben genannte Formel fallen und sich in der Kettenlänge des fluorierten Restes, d.h. im Wert von k unterscheiden. Besonders bevorzugt für die erfindungsgemäßen Mittel sind hierbei fluorhaltige Acrylate der genannten Formel, bei denen
in 0 bis 10 % der Monomeren k einen Wert von 4 oder weniger besitzt
in 45 bis 75 % der Monomeren k einen Wert von 6 besitzt
in 20 bis 40 % der Monomeren k einen Wert von 8 besitzt
in 1 bis 20 % der Monomeren k einen Wert von 10 besitzt
in 0 bis 5 % der Monomeren k einen Wert von 12 besitzt.Component B1) is an aqueous dispersion which contains at least the components d), e) and f) described below, and also further components may contain. The components d), e), and f) are contained in component B1) in the following amounts:

• d) 15 to 20 parts by weight
• e) 1 to 2 parts by weight
• f) 65 to 80 parts by weight

Component d) is a copolymer which is composed of three monomers, namely a fluorine-containing acrylate, vinylidene chloride and a fluorine-free alkyl acrylate or alkyl methacrylate. The fluorine-containing acrylate is 40 to 75% by weight, vinylidene chloride 10 to 35% by weight and the fluorine-free alkyl (meth) acrylate 10 to 25% by weight, the sum of the weight percentages present in the individual case always being 100.
The fluorine-containing acrylate has the general formula



CF₃ - CF₂ - (CF₂) _k - CH₂ - CH₂ - OC (O) - CH = CH₂



In this formula, k can have the values 1 to 12. The fluorine-containing acrylate contained as a monomer unit in the copolymer (component d)) does not have to be a uniform product, but rather is normally a mixture of products which fall under the above-mentioned formula and differ in the chain length of the fluorinated radical, ie in the value of distinguish k. Fluorine-containing acrylates of the formula mentioned are particularly preferred for the agents according to the invention, in which
in 0 to 10% of the monomers k has a value of 4 or less
has a value of 6 in 45 to 75% of the monomers k
has a value of 8 in 20 to 40% of the monomers k
has a value of 10 in 1 to 20% of the monomers k
in 0 to 5% of the monomers k has a value of 12.

As in the case of the fluorine-containing acrylates, it also applies to the fluorine-free alkyl (meth) acrylates that a mixture of compounds which differ in the chain length of the alkyl radical is normally present as the monomer unit. In any case, however, these are compounds whose alkyl chain has 2 to 18 carbon atoms. These alkyl chains can be branched or unbranched.

Copolymers which (as component d) of component B1) are suitable for the preparation of agents according to the invention are described in US Pat. No. 4,742,140. Methods for the production of such copolymers are also given there, for example by means of emulsion polymerization.
Component e)
Ingredient e) is a mixture of ethoxylated fatty acids, which can be obtained in a known manner by reacting a mixture of fatty acids with ethylene oxide. Since a mixture of fatty acids of different chain lengths is normally used in the synthesis for cost reasons, the products obtained are a mixture of compounds which differ in the chain length of the fatty acid residues and in the degree of ethoxylation. Mixtures of compounds whose fatty acid residues contain 8 to 18, preferably 12 to 18 C atoms and whose degree of ethoxylation is 6 to 20, preferably 10 to 16, are used for the agents according to the invention. The degree of ethoxylation is the average number of - CH₂ - CH₂ - O - units attached to a fatty acid residue. Component e) acts as a dispersant for component d)
Component f) of component B1) is water.

US Pat. No. 4,742,140 describes suitable product mixtures which can serve as component B1) for the preparation of agents according to the invention.

Instead of component B1) described, component B2) explained below can also be used.

• g): 4 bis 8 Gew.teile
• h): 10 bis 25 Gew.teile
• i): 1 bis 5 Gew.teile
• k): 50 bis 80 Gew.teile

Bestandteil g) ist ein Isocyanat, das mittels eines Oxims blockiert ist. Damit ist gemeint, daß die -NCO-Gruppen des zugrunde liegenden Isocyanats durch Umsetzung des Isocyanats mit einem Oxim R1 R2 C = NOH blockiert wurden, wobei R1 und R2 im Normalfall Alkylreste mit 1 bis 4 C-Atomen sind. Unter "Isocyanat" werden in diesem Zusammenhang Produkte verstanden, welche mindestens eine, vorzugsweise aber zwei oder mehr -N = C = O-Gruppen enthalten. Geeignet als zugrundeliegende Isocyanate sind beispielsweise 2.2.4- oder 2.4.4-Trimethylhexamethylendiisocyanat oder ein Gemisch dieser Isomerer. Die zugrunde liegenden Isocyanate sind bevorzugt aliphatische oder cycloaliphatische Di-/oder Triisocyanate, auch Polyisocyanate können verwendet werden; unter Polyisocyanaten werden Produkte mit mehr als drei -N = C = O-Gruppen verstanden. Mindestens 90, vorzugsweise 100 % der -N = C = O-Gruppen des Isocyanats liegen blockiert durch ein Oxim vor, insbesondere durch ein aliphatisches Oxim, d.h. ein Oxim der Formel R1 R2 C = NOH, worin R1 und R2 unabhängig voneinander einen Alkylrest mit 1 bis 4 C-Atomen bedeuten. Geeignet ist beispielsweise Butanonoxim. Ein geeignetes blockiertes Isocyanat ist Desmodul® L 75 (Fa. Bayer AG, DE) Weitere geeignete blockierte Isocyanate sind in der EP-A-196 309 beschrieben.Component B2) is an aqueous dispersion which contains at least the components g) to k) described below in the following amounts:
Component g): 2 to 10 parts by weight
Component h): 10 to 40 parts by weight
Component i): 0.5 to 10 parts by weight
Component k): 40 to 90 parts by weight
Particularly favorable results are obtained if component B2) contains the following amounts of constituents g) to k):

• g): 4 to 8 parts by weight
• h): 10 to 25 parts by weight
• i): 1 to 5 parts by weight
• k): 50 to 80 parts by weight

Component g) is an isocyanate which is blocked by means of an oxime. This means that the -NCO groups of the underlying isocyanate were blocked by reacting the isocyanate with an oxime R1 R2 C = NOH, where R1 and R2 are normally alkyl radicals with 1 to 4 carbon atoms. In this context, “isocyanate” is understood to mean products which contain at least one, but preferably two or more -N = C = O groups. Suitable as the underlying isocyanates are, for example, 2.2.4- or 2.4.4-trimethylhexamethylene diisocyanate or a mixture of these isomers. The underlying isocyanates are preferably aliphatic or cycloaliphatic di- or triisocyanates; polyisocyanates can also be used; polyisocyanates are understood to mean products with more than three -N = C = O groups. At least 90, preferably 100% of the -N = C = O groups of the isocyanate are blocked by an oxime, in particular by an aliphatic oxime, ie an oxime of the formula R1 R2 C = NOH, where R1 and R2 independently of one another have an alkyl radical 1 to 4 carbon atoms. For example, butanone oxime is suitable. A suitable blocked isocyanate is Desmodul® L 75 (Bayer AG, DE). Further suitable blocked isocyanates are described in EP-A-196 309.

• a) Umsetzung eines Diols der allgemeinen Formel I
  
  worin m = 1, 2 oder 3 ist
  n = 0 oder 1 ist
  die Einheit -CH₂-X- für -CH₂-S-, -CH₂-N(R)-SO₂- oder für -CH₂-N(R)- C(O)- steht, worin R für Wasserstoff oder für eine Alkylgruppe mit 1 - 6 C-Atomen steht, R_f für einen geradkettigen oder verzweigten Perfluoralkylrest mit 1 bis 18 C-Atomen steht, in dem ggf. ein Fluoratom durch eine Perfluoralkoxygruppe mit 2 bis 6 C-Atomen substituiert sein kann,
  worin E ein verzweigter oder geradkettiger Alkylenrest mit 1 bis 10 Kohlenstoffatomen ist, der gegebenenfalls durch 1 bis 3 Gruppen unterbrochen ist, nämlich durch jeweils zweiwertige Brückenglieder der Formel
  -NR-,-O-,-S-,SO₂-,-COO-,OOC-,-CONR-,-NRCO-,-SO₂NR- und -NRSO₂-, und der gegebenenfalls an einem Ende eine -SO₂NR- oder eine -CONR-Gruppe aufweist, wobei der Rest R_f mit dem Schwefelatom oder dem Kohlenstoffatom dieser Gruppe verknüpft ist, wobei R für Wasserstoff oder eine Alkylgruppe mit 1-6 C-Atomen steht, wobei das Diol im Gemisch mit Nebenprodukten vorliegen kann, die bei seiner Herstellung anfallen,
  mit einem aliphatischen, cycloaliphatischen oder aromatischen Di-, Tri- oder Polyisocyanat, wobei diese Umsetzung gegebenenfalls in Gegenwart eines mindestens 2 Hydroxylgruppen enthaltenden Kettenverlängerungsmittels durchgeführt wurde.
  Als mindestens 2 Hydroxylgruppen enthaltendes Kettenverlängerungsmittel ist insbesondere N-Methyldiethanolamin geeignet.

Component h) of component B2) is an oligo- or polyurethane, the units derived from the diol component contain substituents with perfluoroaliphatic groups. Such products can be obtained by reacting diols containing perfluoroaliphatic groups with products which have at least two iocyanate groups. Suitable products and processes for their manufacture are shown in US-A-3 968 066 and US-A-4 054 592.
Products as described in EP-A-0 348 350, among others, are particularly preferred as component h) of component B2). The German patent applications with the file numbers P 40 16 329.6-44 (filing date May 21, 1990) and P 40 22 443.0 (filing date July 14, 90) also describe products which are particularly preferred as component h). In the case of patent application P 40 22 443.0, this relates to the intermediates (before reaction with siloxane) which are obtained by reacting the diols mentioned there with compounds which contain two or more -N = C = O groups. Products which are particularly suitable as component h), component B2) of the agents according to the invention can be obtained by

• a) implementation of a diol of the general formula I.
  
  where m = 1, 2 or 3
  n = 0 or 1
  the unit -CH₂-X- stands for -CH₂-S-, -CH₂-N (R) -SO₂- or for -CH₂-N (R) - C (O) -, where R is hydrogen or an alkyl group with 1 to 6 carbon atoms, R _{f represents} a straight-chain or branched perfluoroalkyl radical having 1 to 18 carbon atoms, in which a fluorine atom can optionally be substituted by a perfluoroalkoxy group having 2 to 6 carbon atoms,
  wherein E is a branched or straight-chain alkylene radical having 1 to 10 carbon atoms, which is optionally interrupted by 1 to 3 groups, namely by divalent bridge members of the formula
  -NR -, - O -, - S-, SO₂ -, - COO-, OOC -, - CONR -, - NRCO -, - SO₂NR- and -NRSO₂-, and possibly at one end a -SO₂NR- or a -CONR group, the radical R _{f being} linked to the sulfur atom or the carbon atom of this group, where R is hydrogen or an alkyl group having 1-6 C atoms, it being possible for the diol to be present in a mixture with by-products which are present in its manufacture,
  with an aliphatic, cycloaliphatic or aromatic di-, tri- or polyisocyanate, this reaction optionally being carried out in the presence of a chain extender containing at least 2 hydroxyl groups.
  N-methyldiethanolamine is particularly suitable as a chain extender containing at least 2 hydroxyl groups.

The products obtainable in this way are distinguished by the fact that high effectiveness with regard to oil and water repellency is achieved when textiles are equipped with compositions which contain these products.

Component i) of component B2) is an ethoxylated fatty amine or the salt which is formed from such a fatty amine and an aliphatic monocarboxylic acid having 1 to 4 carbon atoms. Suitable salts are described below in the section on component D). The same salts as for component D) are suitable for component i) of component B2), but also the underlying ethoxylated fatty amines which are not neutralized with carboxylic acid.
Component k) of component B2) is water
In a preferred embodiment, component B1) or B2) of the agents according to the invention also contains one or two further constituents 1) and / or m), and furthermore no further constituents. The components l) and m) are 5 to 10 parts by weight of acetone or 2 to 6 parts by weight of ethylene glycol or 1,2-popanediol. These values for the parts by weight relate to the numbers given above for the parts by weight of the components d), e), f) and g), h), i), k).

A further constituent (s)) is preferably also present in component A), namely acetone in an amount of 10 to 15 parts by weight, based on the above-mentioned values for the parts by weight of constituents a), b), and c). Component A) preferably contains no further constituents apart from a), b), c) and optionally n).

The parts by weight of the various constituents used for component A) and B) and, if appropriate, C) and D) do not have to add up to 100 parts by weight (unlike when weight percent is stated).

The agents according to the invention can be prepared by combining the two aqueous dispersions (components A) and B)) and used in this form. In certain cases, however, it is advantageous to add further products to the combined dispersions. In this way, the fiber materials treated with agents according to the invention can be given even more special properties. In particular, textile fiber materials can be conveyed even more comfortably if the agents according to the invention contain, in addition to components A) and B), a component C) and / or a component D). Above all, the simultaneous presence of components C) and D) leads to very good effects.

Component C):

This is an aqueous dispersion which is a mixture of a polysiloxane containing Si-H bonds, an ethoxylated alcohol and water.
The polysiloxane in component C) is a polydimethylsiloxane in which a part, usually less than 25%, of the Si-CH3 bonds has been replaced by Si-H bonds. Such polysiloxanes are commercially available products. All corresponding polysiloxanes available on the market can be used for the agents according to the invention, provided the stability of the aqueous dispersions containing them corresponds to the respective requirements.
The ethoxylated alcohol contained in component C) has a degree of ethoxylation (average number of CH₂CH₂O units) of 4 to 12, preferably 6 to 8.
The underlying alcohol is an aliphatic alcohol with an unbranched or branched alkyl chain of 6 to 16, preferably 10 to 12, carbon atoms.
The third component of component C) is water.

Component C) contains 30 to 40 parts by weight of the polysiloxane, 1 to 5 parts by weight of the ethoxylated alcohol and 60 to 65 parts by weight of water.

Component D )

Component D) is also a mixture in the form of an aqueous dispersion. This mixture contains a tetrasubstituted urea, a carboxylic acid salt of a fatty amine ethoxylate, ethoxylated ricinoleic acid and water. In addition, smaller amounts, ie up to 5 parts by weight (based on the weight details given below for component D)) of one or more of the following substances in component D) may also be present:
Ethylene glycol, methanol, acetic acid and isobutanol. The sum of all available amounts of these substances is therefore a maximum of 20 parts by weight.

worin R ein Alkylrest mit 12 bis 18 C-Atomen ist, R', R'' und R''' unabhängig voneinander für Wasserstoff oder einen geradkettigen oder verzweigten Alkylrest mit 1 bis 4 C-Atomen stehen.Component D) contains
15 to 25 parts by weight of the tetrasubstituted urea
1 to 2 parts by weight of the carboxylic acid salt mentioned
1 to 2 parts by weight of ethoxylated ricinoleic acid
60 to 75 parts by weight of water
and optionally also one or more of the substances mentioned above. The tetrasubstituted urea is a compound of the formula

wherein R is an alkyl radical having 12 to 18 carbon atoms, R ', R "and R""independently of one another represent hydrogen or a straight-chain or branched alkyl radical having 1 to 4 carbon atoms.

It is therefore a tris-methylolated N-alkylurea in which one, two or three methylol radicals can be etherified. This urea can also be a mixture of compounds which differ in the chain lengths of one or more of the radicals R, R ', R'',R'''.

The carboxylic acid salt of a fatty amine ethoxylate contained in component D) can be obtained by ethoxylating a fatty amine and reacting the ethoxylation product with an equivalent amount of a carboxylic acid. The salt preferably has the formula



R4 - NH (R₆) ⁺- (CH₂ CH₂ O) _y -H + R5 COO⁻



in which R4 is an alkyl radical having 10 to 18 carbon atoms, R5 is an alkyl radical having 1 to 4 carbon atoms, R6 is hydrogen or (CH₂CH₂O) _y and y has values from 2 to 16. The salt in this case is normally a mixture of salts which differ in the chain length of the radicals R4, R5 and / or in the value of y. The radicals R4 and R5 can be branched, but are preferably unbranched.

The ethoxylated ricinoleic acid contained in component D) has a degree of ethoxylation of 2 to 12. Here too there is normally a mixture of compounds which differ in the degree of ethoxylation, i.e. differ in the number of - CH₂ - CH₂ - O - units.

The agents according to the invention preferably contain components A) to D) in a weight ratio
40 to 50% A
40 to 50% B
0 to 10% C
0 to 10% D.

The agents according to the invention are aqueous dispersions which are outstandingly suitable for the water- and oil-repellent finishing of fiber materials, in particular textile fabrics, and which impart good color fastness to solvents and a pleasantly soft feel. The textile fabrics are preferably those which consist of cellulose fibers, for example cotton, or which contain cellulose fibers in a mixture with other fibers such as polyester fibers.
The agents can be applied in known amounts for textile finishing using known methods, such as, for example, using a padder.

The invention is now illustrated by means of exemplary embodiments.

• a, Die ölabweisende Wirkung wurde nach AATCC 118-1978 bestimmt.
  Hierbei wurde die Benetzung durch 8 verschiedene flüssige Kohlenwasserstoffe geprüft; die Bewertungsskala dieser Testmethode umfaßt Noten von 1 bis 8, wovon Note 8 die beste (höchster Abweisungseffekt) ist.
• b, Die wasserabweisende Wirkung wurde sowohl nach AATCC 22-1980 (sog. Spraytest) als auch nach DIN 53888 (sogenannter Bundesmann-Beregnungstest) durchgeführt. Bei diesem letzteren Test wird die Wasseraufnahme in Gew.% bestimmt und der sog. "Abperleffekt" visuell beurteilt, wobei Noten von 1 (schlechteste Note) bis 5 (beste Note: Wasser perlt ohne Benetzung ab) vergeben werden. Beim Spraytest wird ebenfalls die Benetzung visuell beurteil, die Notenskala reicht von 0 bis 100 (100 = beste Note, d.h. geringste Benetzung).
  Die obengenannten AATCC-Testmethoden sind dem "AATCC (American Association of Textile Chemists and Colorists) Technical Manual" Vol 58, 1983, Seiten 248, 270, 271 entnommen.
• c, Die Lösemittelechtheit von Färbungen wurden an gefärbten Gewebeproben nach folgender Methode bestimmt (siehe Broschüre Nr. 7/84 vom Juni 1983 der Chemischen Fabrik Pfersee, Augsburg, "Glasplattentest zur Ermittlung der Ausblutungsneigung von Färbungen"):
  Die zu prüfende gefärbte Gewebeprobe wird zusammen mit weißem Filterpapier auf eine Glasplatte gelegt, wobei das Filterpapier zwischen Gewebe und Glasplatte liegt. Auf das Gewebe legt man eine zweite Glasplatte, die in der Mitte eine Meine Öffnung aufweist. Durch diese Öffnung wird mittels einer Pipette ca. 0,2 ml Lösungsmittel (z.B. Aceton oder Perchlorethylen) auf das Gewebe aufgebracht. Nach 60 Sekunden wird das Filterpapier entnommen und bei Raumtemperatur getrocknet. Die Menge an Farbstoff auf dem Filterpapier (= Maß für das Ausbluten von Farbstoff aus dem Gewebe) wird visuell beurteilt.

The test methods described below were used to assess the results:
Before carrying out the tests a to c, the samples were after the treatment for 24 hours at 20 ° C / 65% rel. Moist stored.

• a, The oil-repellent effect was determined according to AATCC 118-1978.
  The wetting was checked by 8 different liquid hydrocarbons; the rating scale of this test method comprises grades from 1 to 8, of which grade 8 is the best (highest rejection effect).
• b, The water-repellent effect was carried out both according to AATCC 22-1980 (so-called spray test) and according to DIN 53888 (so-called Bundesmann irrigation test). In this latter test, the water absorption is determined in% by weight and the so-called "beading effect" is assessed visually, with grades from 1 (worst grade) to 5 (best grade: water pearls off without wetting). In the spray test, the wetting is also assessed visually, the grading scale ranges from 0 to 100 (100 = best grade, ie lowest wetting).
  The above-mentioned AATCC test methods are taken from the "AATCC (American Association of Textile Chemists and Colorists) Technical Manual" Vol 58, 1983, pages 248, 270, 271.
• c, The fastness to solvents of dyeings was determined on dyed tissue samples according to the following method (see brochure No. 7/84 from June 1983 of the Chemische Fabrik Pfersee, Augsburg, "glass plate test for determining the tendency towards bleeding of dyeings"):
  The colored tissue sample to be tested is placed together with white filter paper on a glass plate, the filter paper lying between the tissue and the glass plate. A second glass plate is placed on the fabric, which has a my opening in the middle. About 0.2 ml of solvent (eg acetone or perchlorethylene) is applied to the tissue through this opening using a pipette. After 60 seconds the filter paper is removed and dried at room temperature. The amount of dye on the filter paper (= measure for the bleeding of dye from the fabric) is assessed visually.

example 1

Samples from a microfiber fabric made of 100% polyester (Trevira® Finesse), dyed blue, were equipped with the liquors described below using a padding process. For this purpose, the tissue samples were immersed, squeezed, immersed, squeezed one after the other. The liquor absorption after the second squeezing was about 60% by weight. The samples were then dried under tension on a frame (10 min, 100-120 ° C) and condensed (5 min, 150 ° C).

Fleet 1 (according to the invention):

• a, eine wäßrige handelsübliche Dispersion (entsprechend der in Patentanspruch 1 bzw. 4 genannten Komponente B1) einer Konzentration von ca. 28 %, die etwa 15 Gew.% Copolymer, 1-2 Gewichtsteile ethoxilierte Fettsäuren, 7,5 Gew.% Aceton und ca. 4 Gew.% Ethylenglykol enthielt. Das Copolymer war, wie in Patentanspruch 1 (Bestandteil d) von Komponente B1) angegeben, zusammengesetzt, wobei das Maximum der Kettenlänge des Perfluoralkylrests bei etwa 8 C-Atomen lag und das Maximum der Alkylkettenlänge des fluorfreien Acrylats bei etwa 16 bis 18 C-Atomen lag.
• b, eine handelsübliche wäßrige Dispersion (entspechend Komponente A) von Patentanspruch 1 bzw. 7), welche ca. 70 Gew.teile Wasser, 10 Gew.teile Aceton, 18 Gew.teile Copolymer und 2 % ethoxiliertes (ca. 13-16 EO) Alkylphenol (hauptsachlich 8 bis 10 C-Atome in der Alkylkette) enthielt. Das Copolymer war, wie in Patentanspruch 1 (Bestandteil a) von Komponente A) angegeben, aufgebaut, wobei die Monomeren etwa im Gewichtsverhältnis 58:37:5 von Perfluoralkylethylacrylat: fluorfreiem Acrylat (ca. 16-18 C-Atome in der Alkylkette): Vinylchlorid vorlagen.
• c, eine wäßrige Dispersion, die etwa 35 Gew.% eines Gemischs aus einem Siloxan mit Si-H-Bindungen (Polydimethylsiloxan, bei dem ein Teil der Si-CH₃-Bindungen durch Si-H-Bindungen ersetzt ist) und einem ethoxilierten Alkohol (durchschnittlich 10 bis 12 C-Atome mit ca. 6 EO-Einheiten) und 65 Gew.% Wasser enthielt. (Das genannte Gemisch entspricht der Komponente C) von Patentanspruch 10).
• d, eine wäßrige Dispersion, die etwa 70 Gew.% Wasser und 30 Gew.% eines Gemischs enthielt, wie es oben und in Patentanspruch 10 als Komponente D) beschrieben ist.

The fleet contained in 1 liter of water:
1 ml of 60% acetic acid and
25 g of an approximately 20% aqueous dispersion, which had been prepared by mixing the following individual products a to d:

• a, an aqueous commercially available dispersion (corresponding to component B1 mentioned in claim 1 or 4) of a concentration of approximately 28%, the approximately 15% by weight of copolymer, 1-2 parts by weight of ethoxylated fatty acids, 7.5% by weight of acetone and contained about 4% by weight of ethylene glycol. The copolymer was composed as stated in claim 1 (component d) of component B1), the maximum of the chain length of the perfluoroalkyl radical being about 8 C atoms and the maximum of the alkyl chain length of the fluorine-free acrylate being about 16 to 18 C atoms lay.
• b, a commercially available aqueous dispersion (corresponding to component A) of claim 1 or 7), which contains about 70 parts by weight of water, 10 parts by weight of acetone, 18 parts by weight of copolymer and 2% of ethoxylated (about 13-16 EO ) Alkylphenol (mainly 8 to 10 carbon atoms in the alkyl chain) contained. The copolymer was structured as specified in claim 1 (component a) of component A), the monomers being approximately in the weight ratio 58: 37: 5 of perfluoroalkylethyl acrylate: fluorine-free acrylate (approx. 16-18 C atoms in the alkyl chain): Vinyl chloride templates.
• c, an aqueous dispersion containing about 35% by weight of a mixture of a siloxane with Si-H bonds (polydimethylsiloxane, in which part of the Si-CH₃ bonds is replaced by Si-H bonds) and an ethoxylated alcohol ( contained an average of 10 to 12 carbon atoms with approx. 6 EO units) and 65% by weight of water. (The mixture mentioned corresponds to component C) of claim 10).
• d, an aqueous dispersion containing about 70% by weight of water and 30% by weight of a mixture as described above and in claim 10 as component D).

The quantitative ratio in fleet 1 was chosen so that the products a and b mentioned here (components A) and B1) of claim 1) were used in approximately the same weight ratios, the sum of a and b being approximately 90% by weight. % of the 20% aqueous dispersion formed, and the components c) and d) each only amounts of less than 10%.

Fleet 2 (comparison, not according to the invention):

The fleet contained in 1 liter of water:
1 ml of 60% acetic acid
25 g of product a, from fleet 1 (products b, c, and d, from fleet 1 were not present)

Fleet 3 (comparison, not according to the invention):

Composition like fleet 2, but with product b, from fleet 1 (instead of product a,)

Fleet 4 (comparison, not according to the invention):

Like fleet 3, but instead of product b, another commercially available dispersion, but with a similar composition to product b,

Fleet 5 (not according to the invention):

Like fleet 3, but instead of product b, the commercial product Scotchgard® FX 3563

Fleet 6 (according to the invention):

Composition like fleet 1, but without the addition of products c) and d)
Spray tests and Bundesmann tests (water absorption in% by weight and water repellency grade) were carried out on the finished and post-treated fabrics as described, and the oil-repellent effect was determined, in each case on the original sample, after 5 machine washings (household washing machine) at 40 ° C and after dry cleaning. The results are shown in Table 1. 3 values are given for the pearl effect. These relate (in the given order) to assessments after 1.5 or 10 minutes.
In the Bundesmann test according to DIN 53888, the amount of water passing through the tissue in ml was also determined (see Table 1 under c). These values strongly depend on the density of the tissue structure. The lower these water flow values on the same fabric, the better the water-repellent effect.
The value marked with *) in Table 1 means that the corresponding fabric was completely wetted with water (poor water repellency during the run test)

Example 2

With the liquors Nos. 3, 4 and 5 described in Example 1, fabric samples made from dyed polyester microfibers (warp) and dyed viscose fibers (weft) were treated and treated as described in Example 1. The following fleet 7 was also used:

Fleet 7 (according to the invention):

Like fleet 1, but instead of product a (component B1) according to claim 1), a composition according to component B2) of claim 1 was used as product e. The product e was an aqueous dispersion which contained approximately (in% by weight) 73% water, 3% 1,2-propanediol, 2% of an acetate of a fatty amine ethoxylate (Marlowet® 5401) 7% of an isocyanate blocked with butanone oxime (Desmodul® L 75) and 15% of a urethane with perfluoroalkyl groups (corresponding to component h) of component B2).

The results are shown in Table 2

Example 3: Testing for resistance of the staining to solvents:

• 0 (beste Note): kein Farbstoff erkennbar
• 1 : sehr wenig Farbstoff
• 2 : geringe, aber deutlich wahrnehmbare Menge an Farbstoff
• 3 : mittlere Menge an Farbstoff
• 4 : starke Anfärbung des Filterpapiers

Die für den Test verwendeten Lösungsmittel waren Aceton (Ac), Perchlorethylen (Pe) und Methylethylketon (Me).For this purpose, tissue samples of 100% polyester, dyed with 2.5% Terasilrot 3 BL or with 6% Terasildarkblue RB or with 7% Terasilschwarz LBS, were treated with liquors as described in Example 1. The following changes have been made to the equipment and post-treatment conditions listed above:
The liquors contained not 25 g of the corresponding aqueous dispersions in 1 l of water, but 40 g, and the condensation was carried out at 180 ° C. for 40 seconds rather than at 150 ° C. A colored tissue sample, but not equipped with an aqueous liquor, was also examined. After performing the solvent fastness test described above, the filter paper samples were visually rated using the following scale:

• 0 (best grade): no dye recognizable
• 1: very little dye
• 2: small but clearly noticeable amount of dye
• 3: medium amount of dye
• 4: strong staining of the filter paper

The solvents used for the test were acetone (Ac), perchlorethylene (Pe) and methyl ethyl ketone (Me).

The results are shown in Table 3.

Claims (12)

1. The use of an agent for treating fibre materials, containing at least two components A) and B) in a weight ratio of A):B) of from 30:70 to 70:30, of which component A) is an aqueous dispersion which contains the following constituents a), b) and c):

   a) from 15 to 25 parts by weight of copolymer composed of the following monomers: from 50 to 60 % by weight of a perfluoroalkylethyl acrylate or perfluoroalkylethyl methacrylate, from 2 to 10 % by weight of vinyl chloride, from 30 to 40 % by weight of a fluorine-free alkyl acrylate or methacrylate having an alkyl chain of from 10 to 18 carbon atoms,

   b) from 1 to 2 parts by weight of an ethoxylated alkylphenol having an alkyl chain length of from 4 to 12, preferably from 6 to 10, carbon atoms and a degree of ethoxylation of from 6 to 20, preferably from 10 to 16,

   c) from 55 to 75 parts by weight of water, and component B) is either an aqueous dispersion B1) which contains the following constituents d), e) and f):

   d) from 15 to 20 parts by weight of a copolymer composed of the following monomers: 40 - 75 % by weight of fluorine-containing acrylates of the formula
   
   
   
           CF₃ - CF₂ - (CF₂)_k - CH₂ - CH₂ - OCO - CH = CH₂
   
   
   
   where k is from 1 to 12, from 10 to 35 % by weight of vinylidene chloride, from 10 to 25 % by weight of an alkyl acrylate or alkyl methacrylate having an alkyl chain of from 2 to 18 carbon atoms,

   e) 1-2 parts by weight of a mixture of ethoxylated fatty acids, the fatty acids having from 8 to 18, preferably from 12 to 18, carbon atoms and the degree of ethoxylation being from 6 to 20, preferably from 10 to 16,

   f) from 65 to 80 parts by weight of water or an aqueous dispersion B2) which contains the following constituents g) to k):

   g) from 2 to 10 parts by weight of an oxime-blocked isocyanate, preferably from 4 to 8 parts by weight,

   h) from 10 to 40 parts by weight, preferably from 10 to 25 parts by weight of an oligo- or polyurethane whose diol derived units contain substituents having perfluoroaliphatic groups,

   i) from 0.5 to 10 parts by weight, preferably from 1 to 5 parts by weight, of an ethoxylated fatty amine or of the salt formed between this ethoxylated fatty amine and an aliphatic monocarboxylic acid of from 2 to 4 carbon atoms,

   k) from 40 to 90, preferably from 50 to 80, parts by weight of water.
2. A use of an agent according to claim 1, characterised in that the weight ratio of A:B is about 50:50.
3. A use of an agent according to Claim 1 or 2, characterised in that in the fluorine-containing acrylates of constituent d) of component B1)
   in from 0 to 10 % of the monomers k is 4 or less,
   in from 45 to 75 % of the monomers k is 6,
   in from 20 to 40 % of the monomers k is 8,
   in from 1 to 20 % of the monomers k is 10,
   in from 0 to 5 % of the monomers k is 12.
4. A use of an agent according to one or more of claims 1 to 3, characterised in that component B1) or B2), in addition to the constituents d), e) and f) or g), h), i) and k) contains

   l) from 5 to 10 parts by weight of acetone and/or

   m) from 2 to 6 parts by weight of ethylene glycol or 1,2-propanediol
   and in that the sum total of the constituents d), e), f), l) and m) on the one hand or g), h), i), k), l) and m) on the other accounts for 100 % by weight of component B).
5. A use of an agent according to one or more of claims 1 to 4, characterised in that in constituent a) of component A) the fluorine-free alkyl acrylate or methacrylate is octadecyl acrylate.
6. A use of an agent according to one or more of claims 1 to 5, characterised in that the perfluoroalkylethyl acrylate of constituent a) of component A) is a mixture of compounds of the formula
   
   
   
           CF₃ - (CF₂)_x - CH₂ - CH₂ - O - CO - CH = CH₂
   
   
   
   where x is from 3 to 9.
7. A use of an agent according to one or more of claims 1 to 6, characterised in that component A), in addition to the constituents a), b) and c), also contains

   n) from 10 to 15 parts by weight of acetone and in that the sum total of the constituents a), b), c) and n) accounts for 100 % by weight of component A).
8. A use of an agent according to one or more of claims 1 to 7, characterised in that constituent g) of component B2) is an aliphatic or cycloaliphatic di- or triisocyanate whose isocyanate groups are blocked by an aliphatic oxime.
9. A use of an agent according to one or more of claims 1 to 8, characterised in that constituent h) of component B2) is an oligo- or polyurethane which is obtainable by

   a) reacting a diol of the general formula 1

   

   where m is 1, 2 or 3, n is 0 or 1, the unit -CH₂-X- is -CH₂-S-, -CH₂-N(R)-SO₂ or -CH₂-N(R)-C(O)-, where R is hydrogen or an alkyl group of from 1-6 carbon atoms, R_f is a straight-chain or branched perfluoroalkyl radical of from 1 to 18 carbon atoms in which a fluorine atom may be replaced by a perfluoroalkoxy group of from 2 to 6 carbon atoms, and E is a branched or straight-chain alkylene radical of from 1 to 10 carbon atoms which may be interrupted by from 1 to 3 groups, namely by respectively divalent bridge members of the formula -NR-, -O-, -S-, SO₂-, -COO-, OOC-, -CONR-, -NRCO-, -SO₂NR- and -NRSO₂-, and which may have at one end an -SO₂NR- or a -CONR- group, the radical R_f being linked to the sulphur atom or the carbon atom of this group, and R is hydrogen or an alkyl group of 1-6 carbon atoms, which diol may be present in a mixture with by-products, obtained in its preparation, with an aliphatic, cycloaliphatic or aromatic di-, tri- or polyisocyanate, which reaction was carried out in the presence or absence of a chain extender which contains at least 2 hydroxyl groups.
10. A use of an agent according to one or more of claims 1 to 9, characterised in that the agent in addition to the components A) and B) also contains a component C) and/or a component D), of which component C) is a mixture which contains from 30 to 40 parts by weight of polydimethylsiloxane in which some of the Si-CH₃ bonds have been replaced by Si-H bonds, from 1 to 5 parts by weight of an ethoxylated alcohol having from 6 to 16, preferably from 10 to 12, carbon atoms and a degree of ethoxylation of from 4 to 12, preferably from 6 to 8, and from 60 to 65 parts by weight of water, and component D) is a mixture which contains the following constituents: from 15 to 25 parts by weight of

    

    where R is an alkyl radical of from 12 to 18 carbon atoms and R', R'' and R''' are each independently of the others hydrogen or a straight-chain or branched alkyl radical of from 1 to 4 carbon atoms, 1-2 parts by weight of a carboxylic acid salt of a fatty amine ethoxylate having a degree of ethoxylation of from 2 to 16, preferably of the formula
    
    
    
            R4NH(R6)⁺- (CH₂CH₂O) -_yH+R5COO⁻
    
    
    
    where R4 is an alkyl radical of from 10 to 18 carbon atoms, R5 is an alkyl radical of from 1 to 4 carbon atoms, R6 is hydrogen or -(CH₂CH₂O)-_y and y is from 2 to 16, 1-2 parts by weight of ethoxylated ricinoleic acid with from 2 to 12 ethylene oxide units, and 60-75 parts by weight of water, and which optionally contains ethylene glycol, methanol, acetic acid and/or isobutanol, each in amounts of up to 5 parts by weight.
11. A use of an agent according to claim 10, characterised in that the agent contains the components A), B), C) and D) in a weight ratio of A:B:C:D of (from 40 to 50):(from 40 to 50):(from 0 to 10):(from 0 to 10).