HK1037380B - Blocked oligomeric isocyanates, their production and use - Google Patents

Description

Blocked isocyanate oligomers, their preparation and use

Technical Field

A common method of providing oil-and/or water-repellent finishes to textile materials is to use fluorocarbon polymers that have some air and vapor permeability and provide a permanent press finish to make, for example, water impermeable and breathable finishes. For general applications, it is desirable to impart a certain fastness, especially a clean fastness, to the finish. Wherein the fastness to washing, in particular the washing durability, plays a particular role; the problem here is that the oleophobic and/or hydrophobic effect of the finish is impaired by the use of usual household detergents, such as washing or shampooing, which require a thermal after-treatment, for example at 140 ℃ or more (e.g. ironing), to partially recover-provided that there is still product on the substrate after cleaning. It is therefore particularly desirable that the original properties (in particular oil-and water-repellency as well as vapour permeability or easy care properties) are substantially not impaired after one or more cleaning or washing operations, if possible even without thermal after-treatment.

Background

DE19615116a1 describes blocked polyisocyanates as crosslinker resins for organic polyhydroxyl compounds for clearcoat stoving lacquers, which are prepared by reacting (cyclo) aliphatic polyisocyanates containing isocyanurate groups with nonionic hydrophilic components (for example polyethylene glycols), monofunctional blocking agents and hydrazide-containing stabilizer components and optionally certain chain extenders in a quantitative ratio, reacting the starting polyisocyanate first with the hydrophilic component in a non-dissipative manner, then with the blocking agent, then with the stabilizer and optionally with the chain extender.

EP0537578A2 describes the use of blocked polyisocyanates and fluorinated compounds. The blocked polyisocyanate contains a polyalkylene ether and has an internal ionic group that renders the textile finish hydrophobic and oleophobic. Such ionically modified products have the disadvantage that they are not necessarily compatible with other products of opposite ionic character, such as anionically modified products and synthetic resin components having cationic properties, which can lead to precipitates in aqueous media.

The subsequent us patent 5714082 describes a water and oil repellent and stain repellent finish with fluoride, and example 42 describes the use of a hydrocarbon urethane type chain extender (non-ionic product HCT-3), where it is believed that there is a "deficiency".

It has now been found that, surprisingly, the use of a mixture (G) of blocked polyisocyanate oligomers, as defined below, makes it possible to improve the oil-and water-repellent properties of the finishes mentioned initially and to increase their fastnesses.

Disclosure of Invention

The invention relates to the defined mixtures (G), to compositions containing these mixtures, to the production of these mixtures and to their use.

The invention provides a process for preparing a mixture (G) which is self-dispersible in water and is obtained by reacting an isocyanate prepolymer (C) partly with a polyethylene glycol monoalkyl ether (A) and completely blocked with a pyrazole (B) which is used to block isocyanates, characterized in that in a first preparation stage (a) the isocyanate groupsof the isocyanate prepolymer (C) are reacted in the absence of a protic solvent with the polyethylene glycol monoalkyl ether (A) in a molar equivalent ratio of (C): (A) of from 50: 1 to 2: 1 to form a product (U1), where the polyethylene glycol monoalkyl ether (A) may optionally contain propylene oxide units, and the product (U1) is then optionally converted into the product (U2) by heating to 60 to 95 ℃ and/or by reaction with a chain extender, this product (U2) has a higher equivalent weight based on NCO and still contains reactive NCO groups, and in the second preparation stage (B) the remaining isocyanate groups are then completely blocked by the isocyanate-blocking pyrazoles (B), which do not contain reactive NCO groups after reaction with the blocking agents.

The preparation method is characterized in that the equivalent ratio of (C) to (A) is 40: 1-4: 1.

The invention provides a process for the preparation, which is characterized in that, in the preparation stage (a), the treatment of (U1) is carried out at 60 to 95 ℃ until the equivalent weight of the product (U2) based on isocyanate groups is 1 to 20% higher than the equivalent weight corresponding stoichiometrically to a urethane structure in (U1).

The preparation method provided by the invention is characterized in that the equivalent weight of the product (U2) based on isocyanate groups is 3-12% higher than the equivalent weight corresponding to the urethane structure in (U1) in stoichiometric terms.

The preparation process of the present invention is characterized in that in the preparation stage (a), (U1) is reacted with a chain extender (K).

The present invention provides a mixture (G) prepared by the preparation method described above.

The present invention provides an aqueous dispersion (D) of the mixture (G) self-dispersible in water as described above.

The invention provides aqueous dispersions (D) which further comprise a non-ionogenic, surface-active stabilizer (E) and/or a solubilizer (L) and/or an additive (Z) to control the destruction of microorganisms.

The invention provides a process for the preparation of the aqueous dispersion (D) as described above, characterized in that the mixture (G) is mixed with water and with at least one further additive.

The present invention provides an aqueous composition (P) containing (G) and (F), wherein (G) is as defined above and (F) is a polymer containing a perfluorohydrocarbon group.

The present invention provides the use of (G) as described above, as an auxiliary, for the finishing of fibrous materials together with an oleophobic and/or hydrophobic finish (F) which is a polymer containing a perfluorinated hydrocarbon group.

The invention provides the use of (G), wherein (G) is used in the form of the aqueous dispersion (D).

The invention provides the use, wherein (G) and (F) are used in the form of an aqueous composition (P) containing 0.1 to 70 wt% of (G) and (F).

The invention provides the use, for finishing of fibre materials, by the dipping method using an aqueous solution, which is an aqueous dispersion comprising (G) and (F), optionally together with a synthetic resin coating based on optionally cyclic methylolureas or methylolmelamines or precondensates thereof, and by thermal curing.

A process for the preparation of the self-dispersible mixture (G),

in the first preparation stage

(a) A small portion of the isocyanate groups in the ester oligomer (C) are reacted in the absence of a proton-donating solvent with a polyethylene glycol monoalkyl ether (A) which may optionally contain propylene oxide units, to form a product (U1), which is then optionally converted (U1) to a product (U2), which has a higher equivalent weight based on NCO and still contains reactive NCO groups,

and in the second preparation stage

(b) The remaining isocyanate groups are then completely blocked by the isocyanate-blocking pyrazoles (B).

For the preparation of the aqueous dispersion (D), the mixture (G) thus prepared can, and preferably is, mixed directly after its preparation with water and optionally further additives.

The isocyanate oligomers (C) are suitable isocyanates known in general, advantageously having 2 to 10 NCO groups, e.g. oligomers of hydrocarbon oligoisocyanates or hydrocarbon diisocyanates, especially

(C₁) Oligomers of aliphatic diisocyanates

Or (C)₂) Diphenylmethane diisocyanate or polyphenylene polymethylene polyisocyanate.

Can derive the oligomer (C)₁) The aliphatic diisocyanate monomer of (a) preferably has at least one methylene-bonded isocyanate group. Isocyanate oligomer (C)₁) May be, for example, a greaseAliphatic, optionally cyclic diisocyanates having, for example, 2 to 16, preferably 4 to 10, carbon atoms in the basic hydrocarbon skeleton, dimers, trimers or tetramers thereof. Among these, hexamethylene diisocyanate, isophorone diisocyanate and 2, 4, 4-trimethylhexamethylene-1, 6-diisocyanate are preferred, and hexamethylene diisocyanate is particularly preferred. These oligomers may be cyclic or open chain; suitable trimers include in particular those having an isocyanurate or biuret structure, suitable dimers include in particular those having a uretidione structure; optionally, it is also possible to use oligomers thereof.

(A) The alkyl groups which can form ethers can in principle be chosen arbitrarily, but low molecular weight groups are preferred; preferably, it contains 1 to 4 carbon atoms. If desired, (A) may also contain propylene oxide units, in which case, however, it is preferred that there are more ethylene oxide groups than propylene oxide groups.

Polyethylene glycol monoalkyl ether (A) optionally containing propylene oxide units, preferably according to the average formula

R-(O-CH₂-CH₂)_n-OH (I)

Wherein R is C_1-4-alkyl- (O-propylene)_m-，

n is 5 to 30

And m is 0 to 10, with the proviso that m is less than or equal to 1/3 of n.

n is preferably 8 to 24, and particularly preferably 12 to 20.

Preferably, m is 1/4 where m is less than or equal to n, for example m is 0 to 4, preferably 0.

In the first preparation stage (a), the oligomer (C) is first reacted with an oligoethylene glycol monoalkyl ether (A), optionally containing propylene oxide units, in such a way that the quantitative ratio of (A) to (C) is selected such that only a portion of the available isocyanate groups is reacted with (A). It is advantageous to select the mixing ratio of (A) to (C) in such a way that more than one molar equivalent of (C) is used per mole of (A). One equivalent of (C) refers to weight, which can be determined by titration, which corresponds to one NCO group. One molar equivalent of (C) is in grams. Thus, the equivalence ratio of (A) to (C) refers to the ratio of the number of moles of (A) to the number of molar equivalents of (C). The ratio is mainly 1/50-1/2, preferably 1/40-1/4, and particularly preferably 1/30-1/10.

(A) The reaction with (C) can be carried out in the presence of a solvent or in the absence of a solvent, and when a solvent is used, suitable solvents are aprotic solvents, such as acrylic acid carbonate, acetone, methylhexanones or methylisobutylketone. If (K) is not used, the reaction is preferably carried out in the absence of a solvent. The reaction is carried out at elevated temperature, advantageously at a temperature of greater than 30 ℃, for example at a temperature of from 60 to 95 ℃, and preferably under an inert atmosphere, such as argon or preferably nitrogen.

(A) The reaction with (C) first leads to the formation of an alkyl polyglycol ether urethane product (U1), which alkyl polyglycol ether urethane product (U1) comprises urethane groups, which are obtained from the reaction of the hydroxyl groups in (a) with a proportion of the isocyanate groups in (C), and which preferably correspond to the formula:

R-(O-CH₂-CH₂)_n-O-CO-NH- (u)

the content of urethane structure in (U1) may vary depending on the molar ratio of (A) to (C), and therefore, in addition to containing urethane structure, the reaction product (U1) contains unreacted structure containing no urethane group derived from (A), that is, unreacted structure is a portion of (C) which does not substantially react with (A).

The isocyanate group-containing product (U1) is optionally converted to an isocyanate group-containing product (U2) which has a higher equivalent weight based on NCO before further reaction with (B) (U2).

The reaction for conversion into (U2) is advantageously influenced by further reactions within and/or between the molecules of (U1) or by the addition of suitable, preferably low molecular weight, chain extenders (K).

The intermolecular or intramolecular further reaction of (U1) can be carried out by heating, for example, at a temperature of 60 to 95 ℃, so that as the reaction time for the preparation of (U1) at high temperature is prolonged, the equivalent weight based on NCO will gradually increase to exceed the equivalent weight corresponding to the single urethane structure (U1) by stoichiometry. As a result, for example, more NCO groups are forced to be converted into the stated types by forming allophanate, uretdione and/or isocyanurate structures. The progress of the reaction can be observed by determining the equivalent weight based on the isocyanate groups.

Suitable chain extenders (K) for the reaction of (U1) with the chain extenders (K) are the customary difunctional compounds, i.e. compounds which contain at least two (e.g. 2 to 5) active hydrogen atoms which are capable of reacting with isocyanate groups, most hydroxyl groups and/or primary amino groups, in particular without introducing any ionic groups. Suitable (K) for use in the present invention include primarily aliphatic diols, diamines or aminoalcohols containing 2 to 6 carbon atoms, and also specifically water. Wherein, if they contain 4 to 6 carbon atoms, the aliphatic hydrocarbon radicals can optionally be interrupted by oxygen, which, in the case of the water contained in the chain extender (K), will take part in the two-step reaction (CO elimination) according to the usual reaction scheme₂)

This in turn leads to the formation of urea bridges. (K) Examples of (B) are ethylene glycol, propylene glycol, butylene glycol, 1, 4-butanediol, hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine,hexamethylenediamine, ethanolamine, isopropanolamine and water, preference being given to diols, in particular ethylene glycol and propylene glycol, and particular preference to water.

The reaction with (K) in the presence of a solvent can advantageously take place, preferably at a temperature of from 20 to 95 ℃ and temperatures of from 20 to 60 ℃ are suitable if the reaction is carried out in the presence of a catalyst, the catalyst being of a known type for the preparation of polyurethanes, for example dibutyltin dilaurate, diacetate or dioctoate.

The use of the reaction product (U2) according to the invention is particularly advantageous, the equivalent weight based on isocyanate in the reaction product (U2) being greater than the equivalent weight stoichiometrically corresponding to a single urethane structure in the reaction product (U1). The equivalent weight of (U2) based on isocyanate is 1 to 20%, preferably 2 to 15%, more preferably 3 to 12% higher than the equivalent weight corresponding to the stoichiometric equivalent weight of the single urethane structure in (U1). For certain combinations of starting materials (a) with (C) and optionally with (K), the desired or optimum conversion can be determined by means of a few preliminary experiments. If chain extender (K) is used for the preparation of (U2), the ratio of the number of moles of (K) to the number of molar equivalents of (U1) falls within a corresponding and suitable range which enables the aforementioned amount of increase in equivalent weight based on NCO, in particular from 0.01 to 0.16 moles of (K) per molar equivalent (U1), preferably from 0.02 to 0.12 moles of (K) per molar equivalent (U1), preferably from 0.03 to 0.1 moles of (K) per molar equivalent (U1), to be obtained.

The reaction products (U1) and (U2) are usually both mixtures. The product (U1) may be, for example, any mixture of different conversion products, for example, when the equivalent ratio (C)/(A) is greater than the oligomeric degree of polymerization of (C), (U1) becomes a mixture of products containing groups derived from (A) and products not containing groups derived from (A). The corresponding mixture is also formed in (U2).

The reaction product (U1) or preferably (U2) is then reacted with (B).

The pyrazoles (B) used for blocking isocyanates are generally any pyrazoles known and used for blocking or masking polyisocyanates, for example those described in EP-A-0500495, in particular those in which the substituents optionally substituted on the pyrazole ring are non-ionizable and NCO-inert, (i.e.they do not react with NCO groups and therefore do not interfere with the blocking reaction). As the pyrazole (B), a substance represented by the average formula (II),

wherein R is₁，R₂And R₃Each independently of the others hydrogen, alkyl, allyl, aralkylRadical, aryl or alkoxy, or R₂And R₃And the carbon atoms to which they are bonded form a benzene ring which is immediately adjacent to the pyrazole ring and which may optionally be substituted by alkyl, aryl or alkoxy groups.

In the formula (II), the alkyl and alkoxy groups contain 1-3 carbon atoms, the aryl group is preferably phenyl, and the aralkyl group is preferably benzyl; r₂And R₃And together with the carbon atoms to which they are bonded form a immediately adjacent benzene ring, which is preferably unsubstituted. Preferably, R₂Is hydrogen, C_1-3-alkyl, benzyl or allyl. R₁And R₃Each independently is hydrogen or C_1-3-an alkyl group. C_1-3Alkyl is preferably methyl. R₂Hydrogen is preferred.

Particularly preferred pyrazoles (B) are those of the formula (II) in which R is₁Is hydrogen or methyl, R₂Is hydrogen and R₃Is methyl.

The reaction of pyrazole (B) with (U1) or preferably with (U2) can be carried out directly after their synthesis by simple mixing of the reactants, for example by adding (B) to the reaction product (U1) or preferably (U2). The blocking of the isocyanate groups with the pyrazole (B) can be carried out in the presence of a catalyst, such as dibutyltin dilaurate, dioctoate or diacetate, or in the absence of a catalyst, preferably in the absence of a catalyst. The reaction is exothermic and the initial slight heat is sufficient to drive the reaction down. Advantageously, the reaction is carried out at a temperature of 15 to 60 ℃. The amount of pyrazole (B) used is readily sufficient to completely block the isocyanate groups present in the product (U1) or (U2) -the amount of pyrazole used can be determined, for example, by titration. Advantageously, the reaction with (B) is carried out under an inert atmosphere, for example argon or preferably nitrogen, as described above for the synthesis of (U1).

The product thus obtained is a mixture (G) -at least (U1) or (U2) is a mixture-and is practically non-ionising and self-dispersible in water, that is to say by addition to or by stirring into water, it is possible to form very fine aqueous dispersions even without the use of emulsifiers or other surfactants. The aqueous dispersion (D) of the mixture (G) forms part of the object product of the invention. They can be prepared in a conventional manner by simply stirring (G) into water or vice versa; it is also possible to add further additives, if desired, for example nonionizing, surface-active stabilizers (E) and/or solubilizers (L).

Suitable nonionizing stabilizers (E) are primarily the addition products of ethylene oxide with polypropylene glycols or with aliphatic and/or aromatic alcohols having, for example, from 9 to 24 carbon atoms, preferably from 11 to 18 carbon atoms, the degree of ethoxylation preferably being such that the HLB is greater than or equal to 8, preferably from 10 to 18. Block copolymers of ethylene oxide and propylene oxide having the appropriate HLB are also suitable. If a non-ionogenic stabilizer (E) is used, it is used in an amount less than (G), for example in an amount of 0.5 to 40%, preferably 1 to 20%, based on (G).

The concentration of (G) in the aqueous dispersion (D) is optional; the concentrated dispersion (D) is preferably used in a concentration of 5 to 70% by weight, preferably 10 to 60% by weight, based on the total weight of the dispersion (D).

Examples of suitable solubilizers (L) are mono-or oligoalkylene glycols and their C1-4 alkyl monoethers (e.g.ethylene glycol, propylene glycol, hexylene glycol, dipropylene glycol monomethyl ether, ethylene glycol monobutyl ether or diethylene glycol monobutyl ether), ethylene carbonate, propylene carbonate or N-methylpyrrolidone.

When the solubilizer (L) is used, the concentration of (L) in (D) may vary within wide limits, for example 1 to 30% by weight of (D) based on the total weight, but it is preferred that the concentration of the solubilizer (L) is less than the concentration of (G), for example 5 to 80% by weight of the concentration of (G).

If desired, the dispersion (D) may comprise additives for protecting it from microorganisms, in particular microbicides and/or additives capable of inhibiting the growth of fungi and/or bacteria. Suitable agents for this are the products which are generally commercially available and it is recommended here to use these in smaller amounts (e.g. less than 2% by weight).

In particular, the aqueous dispersion (D) of the invention has a very fine particle size. The particles of the dispersion have a particle size of, for example, 0.01 to 1 μm, preferably 0.05 to 0.5. mu.m. Dispersions (D) are also very stable on storage-especially those containing (E) and/or (L) -and can be injected. They retain their application and physical properties even after long-term storage.

The mixtures (G) according to the invention, advantageously in the form of their aqueous dispersions (D), are used as an aid in the oil-and/or water-repellent finishing of fiber materials with fluorocarbon polymers (F).

Suitable fluorocarbon polymers (F) are generally any of those copolymers which contain perfluoroalkyl groups ("fluorocarbon groups") and are commonly used in oil-and/or water-repellent finishes. Fluorocarbon groups are predominantly perfluoroalkyl groups, in particular monovalent groups of the formula RF,

-C_pF_(2p+1)(f)

wherein p is 3-21, preferably 4-16; fluorocarbon groups may also be those in which one fluorine atom is replaced by one chlorine atom.

These radicals R_FMay be linear or branched; preferably it is linear. It is preferably a radical of the formula,

or

Wherein q is 3 to 15, preferably 5 to 13,

r is 2 to 12, preferably 2 to 8.

They may be directly pendant from the polymer backbone or attached to the polymer backbone via a low molecular weight aliphatic group and optionally via ester or ether linkages; optionally, they mayalso be attached to the low molecular weight aliphatic group via an amide group. The polymer backbone generally refers to a hydrocarbon chain prepared by free radical polymerization of ethylenically unsaturated monomers, such as from suitable vinylic or (meth) acrylic monomers.

Radical R_FThey can be bonded via a bridge, for example to condensation polymers of aldehydes and ureas or melamines, primarily to methylol derivatives of etherified ureas or heterocyclic nitrogen compounds, especially, optionally, methylol derivatives of cyclic ureas (such as N, N '-dimethylol urea, N, N' -dimethylol ethylene urea, N, N '-dimethylol propylene urea or N, N' -dimethylol dihydroxyethylene urea or precondensates thereof) or methylolmelamines (such as trimethylol or hexamethylolmelamine), among the condensates which are thermally curable in the presence or absence of suitable catalysts.

The fluorocarbon polymer (F) is mainly

(F_A) Containing component with fluorocarbon group R_FA copolymer of the comonomer units of (a),

(F_B) Fluorocarbon group R_FA nitrogen-containing polycondensate of (a).

Fluorocarbon group R_FCopolymer (F) of_A) Are known and are described in the technical literature, for example in U.S. Pat. Nos. 3849521, 4742140, 5057577 and 5344903 and EP-A-0198252 and EP-A-0294648. Fluorocarbon group R_FCopolymer (F) of_B) Are likewise known and described in the technical literature, for example in U.S. Pat. Nos. 3362782 and 3510455 and EP-A-0073364.

The process of the invention is preferably carried out using (F)_A) Fluorocarbon polymers of type (la). They are predominantly fluorocarbon-group-containing monomers of the formula (M1) with further ethylenically unsaturated non-ionogenic monomersIn particular with (M2) and optionally (M3), wherein (M1) is of formula

R_F-CH₂-CH₂-O-CH₂-CH₂-O-CH＝CH₂(V)

Or

Wherein R is₄Is C_1-12-an alkyl group,

R₅is hydrogen or a methyl group, or a mixture thereof,

R₆is hydrogen or an acetyl group, and the compound is,

x is-CO-or-SO₂-，

Y is C_2-3-an alkylene group,

z is C_1-12-an alkylene group,

x is 0 or 1, and x is,

y is a number of 0 or 1,

and z is 0 or 1.

(M2) is an oleophilic hydrocarbyl group-containing ethylenically unsaturated non-ionogenic monomer, e.g. (meth) acrylic acid C_9-24Alkyl esters, preferably (meth) acrylic acid C_12-20-an alkyl ester,

(M3) is a further non-ionogenic ethylenically unsaturated monomer, preferably having a molecular weight lower than that of the first two, for example C (meth) acrylic acid_1-8Alkyl esters (with 6 to 8 of them)Alkyl of carbon atoms may be cyclic), vinyl chloride, dichloroethylene, styrene, ethylene or propylene.

If necessary, (F)_A) Also containing a minor proportion of (M4) as polymerized units,

(M4) is an ethylenically unsaturated non-ionogenic comonomer containing a proportion of reactive groups, mainlyactive hydrogen atoms, bonded via heteroatoms such as nitrogen, sulphur or oxygen, or epoxy groups.

These reactive moieties are in particular those which, after copolymerization of the corresponding monomers, are capable of crosslinking with the rest of the polymer and/or with the matrix, for example hydroxyl, thiol or epoxy groups, each being bonded via a hydrocarbon radical and/or a secondary amide radical.

Suitable comonomers (M4) are predominantly comonomers of the formula (VII) (M4a) and comonomers of the formula (VIII) (M4b) and allyl ethers thereof, for example (C)_2-8-alkyl) ethers.

CH₂＝CR₅-CO-O-R₇(VII)

Wherein R is₇Is hydrogen-C_2-4-alkyl, - (CH)₂-CH₂-O)_t-H, dihydroxy-C_3-5-alkyl, 3-chloro-2-hydroxypropyl or glycidyl, and t is 1 to 20.

CH₂＝CH-CO-NH-CHR₈-OH (VIII)

Wherein R is₈Is hydrogen, C_1-3-alkyl, or omega-acetoxy-C_2-4-an alkyl group.

Preferred radicals R₇For example, 2-hydroxyethyl, 2-hydroxypropyl, 2, 3-dihydroxypropyl, glycidyl, 3-chloro-2-hydroxypropyl and of the formula- (CH)₂-CH₂-O)_t-H, wherein t is 1-10, preferably 1-5.

R₈Preferably hydrogen or 3-acetoxy-2, 2-dimethyl-1-hydroxy-propyl-1.

(M1) may be a single compound or a mixture, for example, a technical grade mixture or an arbitrary mixture, as described in U.S. Pat. Nos. 3849521, 4742140 or 5344903.

The comonomer (M4) contains an active ingredient, which is partially crosslinkable after radical polymerizationand attachment to the substrate. Unlike the comonomer (M4), the comonomers (M2) and (M3) do not contain such active ingredients.

As (M2) one or more compounds may be used, for example the compounds described in us patent 5344903. Especially preferred are lauryl (meth) acrylate and stearyl (meth) acrylate.

As (M3) it is also possible to use one or more compounds, for example those described in U.S. Pat. Nos. 3849521 and 5344903 or EP-A-0294648, of which (meth) acrylic acid C is particularly preferred_2-8Alkyl esters (in particular ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate), vinyl chloride and ethylene dichloride.

As (M4) it is also possible to use one or more comonomers, such as, for example, the compounds described in U.S. Pat. Nos. 3849521 and 5344903 or EP-A0294648, preferably at least one comonomer (M4a) and at least one comonomer (M4 b).

The choice of the weight ratio of the monomers will influence the desired water and oil repellent effect of the copolymer. Based on the total comonomer weight (that is to say in particular (M1) and (M2), if present also (M3) and/or (M4)), the comonomers (M1) are used in amounts of from 25 to 90% by weight, preferably from 40 to 90% by weight, particularly preferably from 40 to 75% by weight. The comonomer (M2) is preferably used in an amount of 5 to 50% by weight, preferably 15 to 35% by weight, based on the total comonomer. The comonomer (M3) is preferably used in an amount of 5 to 50% by weight, preferably 5 to 25% by weight, based on the total comonomer weight. Preferred embodiments also use small amounts of comonomer (M4) up to 20 wt%, based on total comonomer weight, of comonomer (M4). The amount of (M4) used is preferably 0.1 to 20% by weight, particularly preferably 2 to 15% by weight, for example 0.2 to 5%by weight of (M4a) and 1.5 to 12% by weight of (M4 b). The copolymerization can be carried out in a manner conventional per se, in the presence of suitable emulsifiers and optionally solubilizers, in the form of aqueous emulsions. Any suitable emulsifier may be used, in particular non-ionogenic and/or cationic emulsifiers. Suitable non-ionogenic emulsifiers are, for example, addition products of ethylene oxide with higher fatty alcohols (for example with fatty radicals containing from 9 to 24 carbon atoms) or with fatty acid partial esters of oligoalkanols, where the fatty acid radical contains from 12 to 24 carbon atoms, such as glycerol, sorbitol or sorbitan. The HLB value of the non-ionizing surfactant is 10 or more, preferably 12 to 18. Examples of cationic surfactants are simple fatty amines whose fatty group contains 12 to 24 carbon atoms or their protonation products or their quaternary ammonium reaction products. A smaller amount of emulsifier is sufficient for the polymerization in aqueous emulsion, for example from 1 to 20% by weight, preferably from 2 to 15% by weight, based on the total monomer weight or, respectively, on the weight of (F).

If a solubilizer is used, it is used in a concentration of 5 to 50% by weight, based on the weight of the total monomers or (F). Suitable solubilizers are, for example, the customary compounds described above under (L), such as monoalkylene glycols or oligoalkylene glycols and their lower alkyl ethers. If desired, other customary additives may also be used for the polymerization, for example polymerization regulators and/or catalysts.

The polymerization is advantageously carried out at elevated temperatures, for example in the range from 40 to 90 ℃ and preferably under an inert gas, for example nitrogen. The weight ratio of water used in the emulsion polymerization is selected so as to obtain the dispersion (F) in a desired concentration of 5 to 50% by weight, preferably 10 to 40% by weight, and more preferably 15 to 30% by weight. The desired form of the emulsion can also be conveniently obtained by appropriate stirring.

The mixtures (G) according to the invention are used as additives for improving the oil-and water-repellent effect of the (F) finishes and their fastnesses, in particular in the wash. Suitable substrates for the finish of the invention include any known material which is oil-and water-repellent finished with fluorocarbon polymers, for example fibrous materials composed of natural, semisynthetic or fully synthetic materials, in particular optionally modified celluloses (such as cotton, hemp, jute, viscose, cellulose acetate), and mixtures thereof with synthetic fibers (in particular cotton/polyester, cotton/polyamide, cotton/polyurethane, cotton/viscose, cotton/polyester/polyurethane), and synthetic fibers (such as polyamide, polyester, polyacrylonitrile). The fibrous material may be present in any desired and suitable form of processing to be used for finishing with fluorocarbon polymers, in particular knits, carpets, felts, meshes and nonwovens, or other textile products coated with a polymer film, for the manufacture of weatherproof products such as (raincoats, hooves, windcoats, tents, tarpaulins, etc.) or products cleaned by washing with detergents (e.g. carpets, upholstery covers). Finishing may be performed before or after packaging of the fabric.

Advantageously, the mixtures (G) and (F) according to the invention are painted together onto a substrate; for this purpose, it is possible to combine them, advantageously in the form of their aqueous dispersions (D) with (F) in the form of a suitable treatment liquor, or (D) can be formulated beforehand with (F) as a concentrated tanning liquor, or (D) can be formulated with the polymer (F) during or after the synthesis of (F) as an aqueous concentrate composition. The polymers (F) are preferably used in the form of aqueous dispersions which may comprise conventional additives such as emulsifiers and solubilizers, the concentration of (F) being from 5 to 50% by weight, preferably from 10 to 40% by weight. Aqueous compositions (P), in particular concentrated compositions (P1), compositions before dilution (P2), in particular concentrated tanning liquors, and diluted compositions (P3), in particular treatment liquors, comprising (G) and (F) may also give part of the desired products of the invention. Advantageously, these compositions, in particular (P1), comprise at least one component (L) and/or (Z), each derived from the corresponding (F) dispersion product and/or (D) product, or they can also be added separately to the composition.

The weight ratio of (G) to (F) is chosen such that the effect of (F) in the finish can be significantly improved. The weight ratio (G)/(F) is preferably 5/100 to 120/100, more preferably 10/100 to 90/100, and particularly preferably 20/100 to 70/100.

The concentration of [ (G) + (F)]in the aqueous composition (P) can vary within wide limits, for example from 0.1 to 70% by weight.

The concentration of [ (G) + (F)]in the concentrated aqueous composition (P1) comprising (G) and (F) is from 10 to 70% by weight, preferably from 15 to 50% by weight, based on the total composition (P1). In the aqueous composition (P2) before dilution containing (G) and (F), the concentration of [ (G) + (F)]is from 0.3 to 30% by weight, preferably from 1.5 to 15% by weight, based on the total composition (P2). In the aqueous treatment liquid containing (G) and (F), i.e., the composition (P3), the concentration of [ (G) + (F)]is 0.1 to 10% by weight, preferably 0.2 to 5% by weight, based on the total composition (P3).

If desired, this finish can be combined with another customary synthetic resin finish, for example a synthetic resin finish based on optionally cyclic methylolureasor methylolmelamines or precondensates thereof, for example as described above for the preparation of (FB). If the finishing is carried out in the presence of a synthetic resin, the corresponding synthetic resin precursor and any desired catalyst may also be present in (P3).

The pH of the treatment liquid can vary within wide limits, for example from 2.5 to 8, preferably from 4 to 7.5, wherein a suitable or optimum pH can be selected depending on the coating agent selected.

Finishing can be carried out in a manner conventional per se, mainly by means of injection-type processes, such as filling, dipping, spraying, knife coating or curtain coating, and similar continuous or discontinuous processes. According to the invention, the presence of the additive (G) or respectively (D) makes it possible to reduce the amount of polymer (F) required to the extent of practical use, in particular to the minimum or optimum amount necessary to obtain an effective action. The concentration of (F) is, for example, 0.1 to 5% by weight, preferably 0.2 to 3% by weight, based on the dry substrate. Applying the treatment liquid to the substrate, followed by subjecting the corresponding polymer (F) and optionally the synthetic resin to a desired suitable heat-fixing operation, for example at a temperature of 110 to 220 ℃, preferably 120 to 200 ℃, for example for 10 seconds to 2 minutes, the optimum fixing temperature and time being selected from the following conditions: the type of functional group and the identity of the matrix, the presence or absence of synthetic resin, the presence or absence of composition, and the concentration of the solution. It is further advantageous to carry out the preliminary drying before the heat-fixing, for example at a temperature of 100 to 140 ℃ for a period of 30 seconds to 5 minutes.

The presence of the additive (G) according to the invention or of (D) correspondingto (G) makes it possible to enhance the effect of the (F) finish and to increase its fastness, or, correspondingly, to reduce in practice the amount of polymer (F) required in order to obtain a certain effect. This means that (G), preferably in the form of (D), can be used as an effective admixture or admixture for (F), so that a minimum amount of fluorocarbon polymer (F) can be used to obtain oil-and water-repellent finishes which have a marked fastness, in particular fastness to cleaning (mainly fastness to shampooing and washing), while their specific properties are virtually unimpaired or even improved. Because of their particularly good cleaning fastness, the materials to be finished (such as windcoats or raincoats and the like) are washed with a domestic washer and dried or spun, or the materials to be finished (such as carpets, upholstery and the like) are cleaned in the manner of shampooing, and drying is possible without subsequent heat treatment, such as ironing, which is absolutely required in general.

Detailed Description

In the following examples, parts and percentages refer to parts and percentages by weight, and temperatures are given in degrees Celsius.

Examples 1 to 5[ preparation of mixture (G) and Dispersion (D) ]]

Example 1

222.1 parts of hexamethylene diisocyanate/biuret prepolymer (viscosity 10,000mPas at 23 ℃ C., functionality 3.7, equivalent weight based on isocyanate 192) were reacted with 40.5 parts of polyethylene glycol monomethyl ether (hydroxyl number 75) at 70 ℃ C. under nitrogen until the equivalent weight (based on NCO) reached 267. The product is then cooled to 40-50 ℃ and 97.4 parts of 3, 5-dimethylpyrazole are added. At 50 ℃ for 3 hours until free and titratable isocyanate groups are notpresent. Then 830 parts of water were added to obtain 1190 parts of a fine milky dispersion.

Example 2

47.45 parts of methylene-phenyl isocyanate prepolymer having a viscosity of 600mPas at 25 ℃ and a functionality of 2.9, equivalent weight based on isocyanate of 138, are reacted with 12.55 parts of polyethylene glycol monomethyl ether having a hydroxyl number of 75 at 80 ℃ under nitrogen until an equivalent weight (based on NCO groups) of 193 has been reached. Simultaneously, 203.88 parts of hexamethylene diisocyanate polyisocyanurate polyisocyanate (trimer viscosity 3000mPa at 23 ℃, functionality 3.7, equivalent weight 197.5) were reacted with 36.12 parts of polyethylene glycol monomethyl ether (hydroxyl number 75) at 80 ℃ under nitrogen until the equivalent weight (based on NCO groups) reached 252. The two reaction products are then mixed together and admixed with 125 parts of 3, 5-dimethylpyrazole at 40 to 50 ℃. After 3 hours, no titratable isocyanate groups remained, and then 21 parts of an ethylene oxide/propylene oxide block copolymer having a hydroxyl number of 25.5, a molecular weight of 4400 and 10% by weight of polyethylene glycol were added. 957 parts of water are subsequently added at 50 ℃ and the batch is then cooled. 1403 parts of a finely milky dispersion were obtained.

Example 3

237 parts of hexamethylene diisocyanate polyisocyanurate (trimer having a viscosity of 3000mPas at 23 ℃, a functionality of 3.7 and an equivalent weight based on NCO groups of 197.5) are reacted with 42 parts of polyethylene glycol monomethyl ether (hydroxyl number 75) at 70 ℃ under nitrogen until the equivalent weight (based on NCO groups) reaches 268. The batch is then cooled to 40-50 ℃ and 103 parts of 3, 5-dimethylpyrazole are added and the reaction is completed after 3 hours. 19 parts of isooctylphenol poly-10-ethanediol ether are then added, 545.5 parts of water are subsequently added at 50 ℃ and the batch is cooled to room temperature. 947.5 parts of a very fine and storage-stable dispersion are obtained.

Example 4

512.2 parts of hexamethylene diisocyanate polyisocyanurate (trimer and pentamer and heptamer) (viscosity 3650mPas at 23 ℃ C., equivalent weight based on NCO groups 195.3) were mixed at 50 ℃ with 90 parts of polyethylene glycol monomethyl ether (hydroxyl number 75) and then 144 parts of acetone were mixed in. A clear solution was obtained at a temperature of 31 ℃. After this time 0.59 parts of dibutyltin diacetate were added and the temperature was raised to 37 ℃ over a few minutes. Then 3.2 parts of water are added and the temperature is raised to 36 ℃. Then the temperature is increased to 41-43 ℃, and CO is found₂And (4) generating. Once no more gas is formed, the addition of 206.1 parts of 3, 5-dimethylpyrazole is started after about 60 minutes from the addition of water. The addition of 3, 5-dimethylpyrazole took 1 hour, during which time the temperature was kept below 53 ℃. The batch is then heated to 60 ℃ at which point the acetone is distilled off. A clear, viscous mass is obtained, which is mixed with 40.3 parts of tridecanol poly-6, 5-ethanediol ether and cooled to 45 ℃. 1168 parts of water are added over about 60 minutes at 45 ℃ with vigorous stirring. Thereby obtaining a finely milky dispersion which was cooled to room temperature.

Example 5

512.2 parts of hexamethylene diisocyanate polyisocyanurate (trimer and pentamer and heptamer) (viscosity 3650mPas at 23 ℃ C., equivalent weight based on NCO groups 195.3) were mixed at 50 ℃ with 90 parts of polyethylene glycol monomethyl ether (hydroxyl number 75) and then 144 parts of acetone were mixed in. A clear solution was obtained at a temperature of 31 ℃. After this time 0.59 parts of dibutyltin diacetate were added and the temperature was raised to 37 ℃ over a few minutes. 11.02 parts of anhydrous ethylene glycol dissolved in 66 parts of acetone are then added and the temperature is raised to 50 ℃. The batch was reacted at 50 ℃ until the ethylene glycol had completely reacted with the polyisocyanate, which took about 60 minutes. 206.1 parts of 3, 5-dimethylpyrazole are then added at 45-50 ℃ over 1 hour, so that the temperature remains below 53 ℃. The batch is then heated to 60 ℃ at which point the acetone is distilled off. A clear, viscous mass is obtained, which is mixed with 40.3 parts of tridecanol poly-6, 5-ethanediol ether and cooled to 45 ℃. 1168 parts of water are added at 45 ℃ for about 60 minutes with vigorous stirring. A fine and soft milky dispersion was thus obtained which was cooled to room temperature.

Examples 6 to 10[ preparation of product (F) and dispersions thereof]

Example 6

The flask was charged with a mixture of the following compounds:

125 g of molecular formula CF₃-(CF₂)_q-(CH₂)₂-O-CO-C(CH₃)＝CH₂Monomers (where q is 7, 9 and 11, the weight ratio of the three compounds is 5: 3: 1),

100 g CH₂＝CH-CO-O-C₁₈H₃₇，

1 g CH₂＝CH-CO-O-C₁₂H₂₅，

17 g of N-methylolmethacrylamide,

6 g of glycidyl methacrylate in the form of a solution,

10 g of N-butoxymethylmethacrylamide,

586 grams of deionized water,

120 g of dipropylene glycol methyl ether,

1 g of n-dodecyl mercaptan is added,

15 g of the acetate salt of octadecylamine,

and 5 g of poly- (20) -oxyethylene sorbitan monooleate,

the mixture was initially stirred at 60 ℃ for 1 hour under a stream of nitrogen to form a fine emulsion. After addition of 9 g of azobisisobutyramidine hydrochloride dissolved in 25 g of water, the batch is stirred at 55 ℃ for 4 hours under a stream of nitrogen, while the polymerization is carried out. Gas chromatography confirmed a conversion of greater than 99%. The resulting dispersion contained fluorocarbon copolymer at a concentration of 25.8 weight percent.

Example 7

The procedure of example 6 was repeated, except that example 7 used a mixture of the following compounds:

43.5 g of formula CF₃-(CF₂)_q-(CH₂)₂-O-CO-C(CH₃)＝CH₂Monomers (where q is 7, 9 and 11, the weight ratio of the three compounds is 5: 3: 1),

8 g CH₂＝CH-CO-O-C₁₈H₃₇，

8 g CH₂＝CH-CO-O-C₁₂H₂₅，

5.28 g of N-methylolmethacrylamide,

1.76 g of glycidyl methacrylate,

0.88 g of N-butoxymethylmethacrylamide,

262.8 grams of deionized water was added,

32 g of dipropylene glycol were added to the solution,

0.2 g of n-dodecyl mercaptan,

3.2 g of the acetate salt of octadecylamine,

and 1.6 g of poly- (20) -oxyethylene sorbitan monooleate.

The resulting dispersion contained 17.8 wt% fluorocarbon copolymer.

Example 8

The flask was charged with a mixture of the following compounds:

125 g of molecular formula CF₃-(CF₂)_q-(CH₂)₂-O-CO-C(CH₃)＝CH₂Monomers (where q is 7, 9 and 11, the weight ratio of the three compounds is 5: 3: 1),

35 g CH₂＝CH-CO-O-C₁₈H₃₇，

17 g of N-methylolmethacrylamide,

5 g of glycidyl methacrylate, and a reaction product thereof,

11 g of N-butoxymethylmethacrylamide,

580 grams of deionized water was added to the reaction mixture,

120 g of dipropylene glycol methyl ether,

0.8 g of n-dodecyl mercaptan,

10 g of the acetate salt of octadecylamine,

and 15 g of poly- (20) -oxyethylene sorbitan monooleate,

the mixture was initially stirred at 60 ℃ for 1 hour under a stream of nitrogen to form a fine emulsion. Then, 50 g of dichloroethylene were added and, after addition of 9 g of azobisisobutyramidine hydrochloride dissolved in 25 g of water, the batch was stirred at 55 ℃ for 4 hours under a stream of nitrogen gas while carrying out the polymerization. Gas chromatography confirmed a conversion of greater than 99%. The resulting dispersion contained fluorocarbon copolymer at a concentration of 25.8 weight percent.

Example 9

21% of an aqueous dispersion of a copolymer of 14% of perfluoroacrylic acid ester as described in example 6, 5% of vinyl chloride and 2% of 2-ethylhexyl acrylate, optionallycontaining 1% of an emulsifier.

Example 10

An aqueous dispersion containing 30% of a copolymer of 21% of perfluoroacrylate as described in example 6, 6% of vinyl chloride and 3% more of the components (emulsifier and crosslinkable monomer) and 15% of dipropylene glycol.

Examples 11 to 25[ preparation of composition (P) ]]

Example 11

200 parts of the fluorocarbon polymer dispersion prepared in example 6 were mixed with 40 parts of the dispersion prepared in example 1. The resulting formulation is storage stable.

Examples 12 to 15

200 parts of the fluorocarbon polymer dispersion prepared in example 6 were mixed with 40 parts of the dispersion prepared in example 2, 3, 4 or 5. The resulting formulation is storage stable.

Examples 16 to 25

Similar to examples 11 to 15, except that the fluorocarbon polymer dispersion prepared in examples 7 to 10 was used in place of the fluorocarbon polymer dispersion prepared in example 6. The resulting formulations are also storage stable.

Application example A

122g/m²Printed cotton fabric (bleached) was filled into a Mathis HVF 41496 laboratory stuffer-mangle (pad-mangle) and an aqueous solution of the following composition was added:

5 g/l of the product from example 1, 2, 3, 4 or 5

20 g/l fluorocarbon copolymer dispersion prepared in example 6

2 ml/l of 60% acetic acid,

after reaching 80% uptake (pick-up), drying and flash-baking (180 ℃/30 seconds active time) was carried out with a Mathis LTE 21496 laboratory dryer. The sample was then left in condition (24 hours, 65% relative humidity, 20 ℃). Half of the samples were washed five more times (40 ℃, ISO standard 6330), then dried (1 minute, 140 ℃, mathis lte 24196 laboratory dryer) and pressed at 160 ℃ for 20 seconds (schroderpress).

The oil test and spray test ratings of the washed samples were determined according to standard test methods AATCC 22 and AATCC 118, which were significantly higher than the ratings of the corresponding blank test (i.e., without the products of examples 1, 2, 3, 4, or 5).

Application example B

Using the same procedure as in application example A, 122g/m²Filling and using printed cotton fabric (bleached)Aqueous solutions of the following compositions:

10 g/l of the product from example 1, 2, 3, 4 or 5

30 g/l fluorocarbon copolymer dispersion prepared in example 6

20 g/l dihydroxyethylene-N, N' -dimethylol urea

5 g/l magnesium chloride hexahydrate

2 ml/l of 60% acetic acid,

the oil test and spray test ratings of the washed samples were determined according to standard test methods AATCC 22 and AATCC 118, which were significantly higher than the ratings of the corresponding blank test (i.e., without the products of examples 1, 2, 3, 4, or 5).

Application example C

In the same manner as in application example a, polyester/cotton scrim (67/33) was filled and added to an aqueous solution of the following composition:

20 g/l fluorocarbon copolymer dispersion prepared in example 6

10 g/l of the product from example 1, 2, 3, 4 or 5

2 ml/l 60% acetic acid

After reaching 80% uptake (pick-up), drying and flash-baking (180 ℃/30 seconds active time) was carried out with a Mathis LTE 21496 laboratory dryer. The sample was then left in condition (24 hours, 65% relative humidity, 20 ℃). Half of the samples were washed five more times (40 ℃, ISO standard 6330), then dried (1 minute, 140 ℃, mathis lte 24196 laboratory dryer) and pressed at 160 ℃ for 20 seconds (schroderpress).

The fastness ratings of the washed samples were determined according to the standard DIN 5388 method (Bundesmann short rain test — bead-off effect over 1 minute and over 10 minutes) and were significantly higher than those of the corresponding blank experiments (i.e. without the products of examples 1, 2, 3, 4 or 5).

Application example D

In the same manner as in application example a, a polyamide taffeta was filled and treated with an aqueous solution of the following composition:

30 g/l of the mixture prepared in example 11

2 ml/l 60% acetic acid

The oil test and spray test ratings of the washed samples were determined according to standard test methods AATCC 22 and AATCC 118, which were significantly higher than the ratings of the corresponding blank test (i.e., without the product of example 11).

Application examples A, B and C can also be used with corresponding amounts of the fluorocarbon copolymer dispersions of examples 7, 8, 9 or 10 or commercially available fluorocarbon copolymer dispersions such as: oleophobal S (Pferse Chemie, Germany), Zepel 8070 (DuPont, USA), Asahi Guard AG 310, 915 or 923 (Asahi Glass, Japan) or Rucogard AFS or AFC (Rudolf Chemie, Germany), without using the fluorocarbon copolymer of example 6.

Thus, oil test and spray test grades were obtained for the washed samples, which grades were significantly higher than those of the corresponding blank experiments (i.e. without the products of examples 1, 2, 3, 4 or 5).

In application example D, it is also possible to use the mixtures of examples 12 to 25 in corresponding amounts, instead of the mixture of example 11.

Claims (14)

1. A process for the preparation of a mixture (G) self-dispersible in water obtained by reacting an isocyanate prepolymer (C) partially with a polyethylene glycol monoalkyl ether (A) and completely blocked with a pyrazole (B) which is useful for blocking isocyanates, characterized in that,

in the first preparation stage

(a) The isocyanate groups in the isocyanate prepolymer (C) are reacted in the absence of a protic solvent with polyethylene glycol monoalkyl ether (A) in a molar equivalent ratio of (C): (A) of from 50: 1 to 2: 1 to form product (U1), wherein the polyethylene glycol monoalkyl ether (A) may optionally comprise propylene oxide units, and then, optionally, the product (U1) is converted by heating to 60-95 ℃ and/or by reaction with a chain extender into product (U2), which product (U2) has a higher equivalent weight based on NCO and still contains reactive NCO groups,

and in the second preparation stage

(b) The remaining isocyanate groups are then completely blocked by the isocyanate-blocking pyrazole (B), and after reaction with the blocking agent no reactive NCO groups are present.

2. The process according to claim 1, wherein the equivalent ratio of (C) to (A) is 40: 1 to 4: 1.

3. The process according to claim 1, wherein, in stage (a), the treatment of (U1) is carried out at 60 to 95 ℃ until the equivalent weight of the product (U2) based on isocyanate groups is 1 to 20% higher than the equivalent weight corresponding stoichiometrically to urethane structures in (U1).

4. The process according to claim 3, wherein the equivalent weight of the product (U2) based on isocyanate groups is from 3 to 12% higher than the equivalent weight corresponding stoichiometrically to urethane structures in (U1).

5. A process according to claim 3 or 4, wherein in stage (a), (U1) is reacted with a chain extender (K).

6. The mixture (G) prepared by the process according to claim 1.

7. An aqueous dispersion (D) of a mixture (G) self-dispersible in water according to claim 6.

8. The aqueous dispersion (D) of claim 7, further comprising a non-ionogenic, surface-active stabilizer (E) and/or a solubilizer (L) and/or an additive (Z) to control microbial destruction.

9. A process for the preparation of the aqueous dispersion (D) according to claim 7, characterized in that the mixture (G) according to claim 6 is mixed with water and with at least one further additive.

10. An aqueous composition (P) containing (G) and (F), wherein (G) is as defined in claim 6 and (F) is a polymer containing a perfluorohydrocarbon group.

11. Use according to claim 6 of (G) as an aid to the finishing of fibrous materials together with an oleophobic and/or hydrophobic finish (F) which is a polymer containing a perfluorinated hydrocarbon group.

12. Use of (G) according to claim 11, wherein (G) is used in the form of an aqueous dispersion (D) according to claim 7 or 8.

13. Use according to claim 11, wherein (G) and (F) are used in the form of an aqueous composition (P) comprising from 0.1 to 70% by weight of (G) and (F).

14. Use according to claim 11 or 12 for finishing of fibre materials by dipping using an aqueous solution, optionally together with a synthetic resin coating, based on optionally cyclic methylolureas or methylolmelamines or precondensates thereof, and by thermal curing, wherein the aqueous solution is an aqueous dispersion comprising (G) and (F).