FR2749309A1 - Fluorinated urethane oligomers - Google Patents

Abstract

Fluorinated oligomeric urethanes obtained by reaction of at least one polyisocyanate with (a) at least one fluorocarbon compound containing a perfluoroalkyl radical and a nucleophilic group (I) with a labile hydrogen; (b) at least one polyol with a fatty aliphatic chain of at least 16C and (c) one or more additional compounds containing a group (II) which is reactive with NCO groups, wherein (i) the compounds (a), (b) and (c) are present in amounts such that the total equivalents of groups (I), groups (II) and OH groups is at least equal to the number of equivalents of NCO in the polyisocyanate; (ii) the proportion of fluorinated compound (a) is such that the oligomer contains at least 15 wt.%, preferably at least 25 wt.% F and the ratio of the number of equivalents of groups (I) in (a) to the number of equivalents of NCO group in the polyisocyanate is 0.2-0.8 (0.35-0.65); (iii) the proportion of polyol (b) being such that the ratio of the number of equivalents of OH group s in (b) to the number of equivalents of NCO in the polyisocyanate is 0.2- 1.8 (0.4-0.8); and (iv) the proportion of compound (c) is such that the ratio of the number of equivalents of groups (II) to the number of equivalents of NCO group in the polyisocyanate is 0-0.45 (0-0.4).

Description

DESCRIPTION
The present invention relates to the field of fluorinated products intended for the water-repellent and oil-repellent treatment of substrates such as textiles, carpet-carpets, wall coverings, wood, building materials, metals, plastics and more particularly for products that can be used for the protection leather whose finishing and maintenance must have the following characteristics: flexibility, appearance and pleasant touch.

As fluorinated products more especially adapted to the leather, it has been proposed products that are soluble or dispersible in water, such as, for example:
- chromium complexes of fluorinated carboxylic acids (patents
US 2,934,450, 3,651,105, 3,907,576 and 3,574,518) which effectively confer good properties, but have the drawback of being strongly colored in green and of imparting this color to the substrates to which they are applied, limiting so their job
fluorinated carboxylic acids (US Pat. No. 3,382,097) and polyfluoroalkylthio-dicarboxylic acids (US Pat. No. 3,471,518);
acrylic copolymers such as those described in the patent
FR 2 579 211, but the use of these products in aqueous medium requires a very long drying time.

 Polymers or copolymers of fluorinated acrylates have also been proposed (US Pat. No. 3,524,760). However, these synthesized or diluted products, for their use, in chlorinated solvents present a danger for the environment.

Also known are products comprising perfluorinated groups and urethane linkages: see, for example, US Patents 3,468,924,
US 3,503,915, US 3,528,849, US 3,896,035, US 3,896,251, US 4,024,178, US Pat.
FR 2 062 244, DE 1 620 965, CA 1 071 225, EP 103 752, CH 512 624 and
CH 520 813. Unfortunately, these products have the disadvantage:
- to contain chlorinated solvents,
- either to call for synthesis to intermediaries difficult to prepare,
- to confer relatively weak water-repellent and oil-repellent properties,
- Or still be able to be presented in aqueous media because of their low solubility in organic solvents.

Recently, have been described in the patent application WO 93/17165, aqueous emulsions of fluorocarbamates obtained by autoemulsification of a polyisocyanate adduct having at least three isocyanate functions with:
an alcohol (or a thiol or an amine) with a perfluorinated group,
a primary alcohol derived from ethylene oxide, and
an agent blocking excess isocyanate functions (for example an epoxy alcohol or an oxime).

 It has now been found, in the services of the Applicant, new fluorinated products which are soluble in many solvents (alkanes, isoparaffins, hydrofluoroalkanes, alcohols, esters), which can also be presented in aqueous medium and which are particularly well suited for the treatment of hides and building materials to which they confer outstanding hydrophobic and oleophobic properties.

The products according to the invention are fluorinated urethane oligomers resulting from the addition reaction of at least one polyisocyanate with:
(a) at least one fluorocarbon compound containing a perfluoroalkyl radical and a nucleophilic group with labile hydrogen (GNHL),
(b) at least one fatty aliphatic chain polyol of at least 16 carbon atoms, and optionally
(c) one or more other compound (s) having at least one reactive group (GR) with respect to the NCO functions, the components (a), (b) and (c) being in sufficient proportion to the total number of GNHL, OH and GR equivalents is at least equal to the number of NCO equivalents of the polyisocyanate.

The proportions of the components (a), (b) and (c) must further be such:
the weight content of fluorine of the oligomer is at least 15%, preferably at least 25%, and the ratio of the number of GNHL equivalents of the fluorocarbon compound (a) to the number of NCO equivalents of the polyisocyanate is included; between 0.2 and 0.8, preferably between 0.35 and 0.65;
the ratio of the number of OH equivalents of the polyol (b) to the number of NCO equivalents of the polyisocyanate is between 0.2 and 1.8, preferably between 0.4 and 0.8, and
that the ratio of the number of GR equivalents of component (c) to the number of NCO equivalents of the polyisocyanate is between 0 and 0.45, preferably between 0 and 0.4.

 In the context of the present invention can be used any polyisocyanate or mixture of polyisocyanates. These polyisocyanates may be of aliphatic, cycloaliphatic, araliphatic or aromatic nature, and have a biuret, isocyanurate or uret-dione structure.

 As examples of polyisocyanates which may be used according to the invention, mention may be made more particularly and without limitation of toluene diisocyanate (isomers 2,4 and 2,6 or their mixture), aliphatic diisocyanate with a fatty alkyl chain (empirical formula C38H70N2O2 ) marketed by the company Henkel under the designation DDI-1410, N, N ', N "-tris (6-isocyanatohexyl) biuret and N, N', N" -tris (6-isocyanatohexyl) isocyanurate.

 The fluorocarbon compounds (a) that can be used in the context of the invention must have a reactive functional group allowing the grafting on one of the isocyanate functions of the polyisocyanate and a hydrophobic and oleophobic group consisting of a perfluoroalkyl radical, linear or branched, containing at least two carbon atoms. The reactive function is a nucleophilic group with labile hydrogen (abbreviated to GNHL) capable of condensing with an isocyanate function; examples of reactive functional groups are the primary alcohol, primary amine, secondary amine or thiol functions. Fluorocarbon compounds with an alcohol or thiol function are preferably used. It is possible to use a mixture of fluorocarbon compounds whose total fluorine content is greater than 10% by weight, preferably greater than 30% by weight.

The fluorocarbon compounds (a) may in particular be chosen from the alcohols and thiols of formula (I) to (IV) below:
Rf - (CH2) m -X- (CH2) n-OH (I)
Rf- (CH2) n (oCH2CH2) p-OH (II)
Wherein Rf represents a perfluoroalkyl radical, linear or branched, containing from 2 to 20 (preferably 4 to 16) carbon atoms; X represents a direct bond, an oxygen or sulfur atom or a -COO-, -SO2-, -CONR- or -SO2NR- group, where R represents an alkyl radical containing 1 to 4 carbon atoms; m represents an integer ranging from 0 to 20, preferably equal to 0 or 2; n is an integer from 1 to 20, preferably 2 or 4; and p is an integer from 1 to 5.

 As polyfluorinated alcohol or thiol of particular interest in the context of the present invention, there may be mentioned compounds corresponding to the following formula: RfrC2H4-QH (V) in which Rf has the same meaning as above and Q represents an atom of oxygen or sulfur.

 In the polyol (b) which may contain 2 or 3 or more alcohol functions, the fatty chain may be saturated or unsaturated and preferably contains at least 18 carbon atoms.

As examples of polyols that may be used in the present invention, mention may be made without limitation of:
The ester of glycerol with ricinoleic acid, of formula:

dans laquelle R' désigne un radical aliphatique d'au moins 16 atomes de carbone et les symboles x et y, identiques ou différents, sont des nombres entiers allant de 1 à 5.the condensates of ethylene oxide on a fatty amine of general formula:

in which R 'denotes an aliphatic radical of at least 16 carbon atoms and the symbols x and y, which are identical or different, are integers ranging from 1 to 5.

dans laquelle R', x et y ont les mêmes significations que précédemment et z est un nombre entier allant de 1 à 5 ; - les polyols quaternaires de formule générale:

dans laquelle R', x et y ont les mêmes significations que ci-dessus, et
- les polyols obtenus par réduction des polyacides résultant de la dimérisation ou trimérisation d'acides gras insaturés.the condensates of ethylene oxide on a fatty-chain diamine of general formula:

wherein R ', x and y have the same meanings as before and z is an integer from 1 to 5; the quaternary polyols of general formula:

in which R ', x and y have the same meanings as above, and
polyols obtained by reduction of the polyacids resulting from the dimerization or trimerization of unsaturated fatty acids.

The possible constituent (c) can be:
an agent blocking isocyanate functional groups such as butanone oxime, phenol, caprolactam, diethyl malonate, 3,5-dimethylpyrazole, a primary alcohol or a primary thiol,
a compound which promotes the aqueous emulsification of the oligomer and which has both a reactive functional group (alcohol or thiol or amine) and a hydrophilic function of a nonionic nature (for example the monomethyl ether of polyethylene glycol with an average molecular mass close to 1000) or of anionic nature (for example a carboxylic acid such as glycolic acid or thioglycolic acid with addition of an amine) or of cationic nature (for example N, N-dimethylethylenediamine with the addition of formic acid or 'acetic acid),
a compound possessing at the same time an alcohol, thiol or amine functional group for reacting with an isocyanate, and a function that can be crosslinked thermally (for example diacetone alcohol) or catalytically (for example, an epoxy alcohol or glycerol with a diamine and glycolic acid).

 The addition reaction of the compounds (a), (b) and optionally (c) on the polyisocyanate can be carried out according to methods known per se, for example those described in KIRK-OTHMER, 3rd edition, p 789 to 818. The compounds (a), (b) and (c) are preferably added to the polyisocyanate by first introducing the compounds (a) and (c) and finally the polyol (b).

 The reaction can be carried out continuously, discontinuously or gradually, at a temperature which can range from room temperature to the boiling point of the reaction medium. It operates preferably between 50 and 1300C. The total concentration of the reagents (polyisocyanate and compounds a, b and c) can vary from 5% to 100% by weight. When the addition reaction is carried out in a solvent, it may be chosen from ketones (for example acetone, methyl ethyl ketone, methyl isobutyl ketone), esters (for example methyl acetate, Ethyl acetate, isopropyl acetate, butyl acetate), ethers (eg ethyl ether, tetrahydrofuran, dioxane), aliphatic, aromatic or isoparaffinic hydrocarbons, or N- methyl-2-pyrrolidone. Only one of these solvents or mixtures can be used.

 Although the addition without catalyst is possible, it is preferred to carry out the reaction in the presence of a catalyst, added at a concentration ranging from 0% to 1% by weight relative to the total weight of the reactants. As catalysts, all those well known to those skilled in the art such as dibutyltin dilaurate, sodium phenate trihydrate and 1,4-diazabicyclo [2.2.2] octane can be used.

 The reaction product can optionally be diluted with the synthesis solvent or, subject to mutual miscibility, with another solvent or mixture of solvents. If desired, the oligomer can also be isolated by removal of the solvent (s).

 As substrates that can be rendered oleophobic and hydrophobic with the fluorinated oligomers according to the invention, mention may be made mainly of leathers (milling, finishing or maintenance) and building materials (stone, cement, terracotta, sandstone). There may also be mentioned other very diverse materials such as, for example, papers, woven or non-woven articles based on cellulose or regenerated cellulose, natural, artificial or synthetic fibers such as cotton, cellulose acetate. , wool, silk, polyamide fibers, polyester, polyolefin, polyurethane, or polyacrylonitrile, plastics, glass, wood, metals, porcelain.

The fluorinated oligomers according to the invention may be applied to the substrates to be treated after dilution with a solvent identical to or miscible with the solvent used for the synthesis. The amount of oligomer to be used varies within wide limits depending on the nature of the support and the fluorine content of the oligomer. On leather, this quantity is generally between 1 and 10 g / m2
The application of the diluted products can be carried out according to different techniques, for example by spraying or brush coating. Depending on their nature, the treated substrates can be dried at room temperature or at temperatures up to 200 ° C. The leathers are preferably dried at room temperature or at a moderate temperature up to about 60 ° C.

The fluorinated oligomers according to the invention may also be applied in aqueous form. To prepare an aqueous dispersion, two cases may occur:
1st case: The oligomer comprises a constituent (c) carrying a hydrophilic function ensuring stabilization; it can therefore form as such a stable aqueous dispersion without the addition of stabilizing agents. In this case, at the time of dispersion, the oligomer must be in solution in a water-miscible organic solvent; this solution is poured into the water with gentle stirring and a dispersion of the oligomer is obtained in a water + solvent mixture. In the case where the organic solvent is more volatile than water, it can be removed from the medium by atmospheric distillation or under vacuum.

 2nd case: The oligomer as such can not form a stable aqueous dispersion without the aid of stabilizing agents. In this case, at the time of passage in aqueous medium, the oligomer must be in solution in an organic solvent immiscible with water and more volatile than water.

To prepare an aqueous emulsion, an organic solution of the fluorinated oligomer is mixed with one or more suitable anionic, cationic or nonionic surfactants, water and optionally a water-miscible auxiliary organic solvent. The emulsification of the organic solution in water is obtained by supplying mechanical energy. The surfactant system may consist of a single surfactant or a mixture of several surfactants. To facilitate emulsification, the procedure is carried out in two stages:
a) In a first step, the organic phase comprising the fluorinated oligomer in solution in the water-immiscible solvent and optionally one or more surface-active agents is mixed with the aqueous phase comprising water, optionally an auxiliary solvent miscible with water and optionally one or more surfactants; it is possible to pour the organic phase into the aqueous phase or vice versa; at least one surfactant must be present either in the aqueous phase or in the organic phase. During mixing, vigorous stirring is maintained using a high shear stirrer of the type
Ultraturrax; a pre-emulsion is obtained.

 b) The second step is to homogenize this pre-emulsion using an ultrasonic probe or a high-pressure homogenizer of the valve homogenizer type; an emulsion is obtained, the average particle size of which is less than or equal to 1clam.

 Generally, the emulsion obtained contains between 10 and 40% by weight of fluorinated oligomer, between 20 and 60% of organic solvent immiscible with water, between 0.2 and 5% of surfactants, between 0 and 20 % of auxiliary organic solvent miscible with water, the complement to 100% water. The water-immiscible organic solvent is then removed from the medium by distillation at atmospheric pressure or under vacuum.

When a water miscible auxiliary organic solvent is used and is more volatile than water, it is removed during the distillation together with the water immiscible organic solvent; in this case the final emulsion is free of any organic solvent.

 The water-miscible auxiliary organic solvents may be chosen from alcohols, polyols, low molecular weight ketones, glycol esters and glycol ethers; preferentially, acetone or ethylene glycol will be chosen.

 The aqueous emulsions of fluorinated oligomers according to the invention can be applied, after dilution with water, by spraying or brush coating as in the case of organic solutions. For the treatment of leather, it is also possible to operate in full bath in a fuller or an elbow during the last stage of the wet process.

 To obtain a particular effect or a better fixation, it may sometimes be advantageous on certain supports to associate the oligomers according to the invention with certain adjuvants, polymers, thermally condensable products, catalysts, anti-UV agents, fungicides, antistatic agents, etc.

The hydrophobic and oleophobic performances of the substrates treated according to the invention are measured by means of the following tests:
Oleophobia tests:
Oleophobia is measured according to the test described in "AATCC Technical
Manual ", test method 118 (1992), which evaluates the non-wettability of the substrate by a series of oily liquids whose surface tensions are increasingly low.

The quotation of the treated substrate is defined as the maximum value of the test liquid which does not wet the support. The test liquids used in the evaluation are listed in the following table:

<tb> Listing <SEP> Test Liquids <SEP> for <SEP> measure <SEP> I <SEP> Surface <SEP> Tensile <SEP> to
<tb><SEP> Iolophobia <SEP> 25 "C <SEP> (mN / m)
<tb><SEP> 1 <SEP> Nujol <SEP> 31.5
<tb><SEP> 2 <SEP> Nujol <SEP> 1 <SEP> n-hexadecane <SEP> 29.6
<tb><SEP> (65/35 <SEP> in <SEP> volume)
<tb><SEP> 3 <SEP> n-hexadecane <SEP> 27.3
<tb><SEP> 4 <SEP> n-tetradecane <SEP> 26.4
<tb><SEP> 5 <SEP> n-dodecane <SEP> 24.7
<tb><SEP> 6 <SEP> n-decane <SEP> 23.5
<tb><SEP> 7 <SEP> n-octane <SEP> 21.4
<tb><SEP> 8 <SEP> n-heptane <SEP> 19.8
<Tb>
Another oleophobic test consists of measuring the penetration time in the material of a drop of dodecane (oil No. 5 of the AATCC 118 test) deposited on the support.

Hydrophobia tests
The hydrophobic effect is measured using test solutions numbered from 1 to 10 and consisting of mixtures of Eulisopropanol (IPA) in the following proportions by weight:

<tb> Test Solutions <SEP> Water <SEP> Isopropanol
<tb><SEP> 1 <SEP> 90 <SEP> 10
<tb><SEP> 2 <SEP> 80 <SEP> 20
<tb><SEP> 3 <SEP> 70 <SEP> C <SEP><SEP> 30
<tb><SEP> 4 <SEP> 60 <SEP> L <SEP><SEP> 40
<tb><SEP> 5 <SEP> 50 <SEP> 50
<tb><SEP> 6 <SEP> 40 <SEP> t <SEP><SEP> 60
<tb><SEP> 7 <SEP> 30 <SEP> 70
<tb><SEP> 8 <SEP> 20 <SEP> 80
<tb><SEP> 9 <SEP> 10 <SEP> 90
<tb><SEP> 10 <SEP> 0 <SEP> 100
<Tb>
The test consists in depositing on the treated substrates drops of these mixtures, then observing the effect produced. The number corresponding to the solution containing the highest percentage of isopropanol and not penetrating or wetting the substrate after 30 seconds of contact is rated.

 Another hydrophobicity test consists of measuring the penetration time in the material of a drop of water deposited on the support.

 In the case of construction materials, it is also measured the water recovery of a surface of 43 cm 2 of the support subjected to a water height of 11 centimeters for one hour.

Water Pocket Test
This test is intended to evaluate the hydrophobic effect brought to the leather for a long time. A square test piece (20 cm x 20 cm) of the substrate to be tested is fixed by its four sides so that the four attachment points are at the same height and that it forms a pocket whose difference in height between the bottom and the four attachment points are sufficient to contain at least 100 ml of liquid. A 250 ml crystallizer is placed under the bag. 100 ml of water are introduced into the bag and the mass (in g) of water collected in the crystallizer is measured after 24 hours and the quantity of water absorbed by the substrate which is given by the ratio of the masses of the substrate after the substrate test before the test.

 The following examples illustrate the invention without limiting it. Unless otherwise indicated, the percentages given are percentages by mass.

EXAMPLE I
a / Preparation:
A reactor with a capacity of 1.5 liters, equipped with a stirrer, a thermometer, a reflux condenser, a heating funnel, an anhydrous nitrogen inlet, is used. and a heater. The reactor air is flushed with a stream of dry nitrogen, and then 61 g of TDI (90% toluene diisocyanate as isomer 2.4 and 10% as 2,6-isomer; NCO: 11.5 meq / g). The reactor air was again flushed with a stream of dry nitrogen and heated to 80 ° C.

In the dropping funnel heated to 80 ° C., 128 g of fluorinated alcohol are introduced.
CgF17C2H4OH (OH number: 2.15 meq / g), 150 g of isopropyl acetate and 0.5 g of dibutyltin dilaurate. The mixture of the dropping funnel is then introduced in 30 minutes into the reactor, the contents of which are then maintained at 80 ° C. for about 30 minutes, until consumption of 0.276 moles of isocyanate.

 In the dropping funnel heated to 80 ° C, is introduced 123 g of isopropyl acetate and 83 g of NoramoxB S2 (polyol of formula VII with R '= tallow radical and x + y = 2, marketed by the Company CECA, OH number: 5.75 meq / g) The mixture of the dropping funnel is then introduced in 30 minutes into the reactor, the contents of which are then maintained at 80 ° C. for 2 hours, until total consumption isocyanate functions. This gives a fluid solution (S1) of oligomer according to the invention at 50% solids, which solidifies by cooling at room temperature.

 By diluting the solution S1 by addition of isopropyl acetate to 10% of dry extract, a clear, light yellow solution (S1 ') is obtained, the fluorine content of which is 3.2% and which remains fluid. at room temperature.

b / Application on leather:
The above solution S1 'is diluted to room temperature with isopropyl acetate up to 2% active ingredients and the clear solution thus obtained is deposited on the surface of leather samples by cross-sputtering at the same time. using a Volumair T21 sprayer. The average amount of 2% solution deposited per unit area is 250 g / m 2.

Spraying is carried out on three different leather qualities: vegetable veal, nappa lamb and velvet lamb. After drying at room temperature for 24 hours, the hydrophobic and oleophobic resistance of the treated leathers was evaluated in comparison with that of untreated leathers. The results summarized in the following table demonstrate the effectiveness of the fluorinated oligomer according to the invention.

<Tb>

<SEP> Test
<tb><SEP> Quality <SEP> of <SEP> leather <SEP> AATCC <SEP> 118 <SEP> Test <SEP> water / lPA
<tb> vachette <SEP> plant
<tb><SEP> - <SEP> no <SEP> processed <SEP> 0 <SEP> 0
<tb><SEP> processed <SEP> - <SEP> towed <SEP><SEP> 4 <SEP> 5
<tb> lamb <SEP> nappa
<tb><SEP> - <SEP> no <SEP> processed <SEP> 0 <SEP> 1
<tb><SEP> -treated <SEP> 4 <SEP> 6
<tb> lamb <SEP> velvet
<tb><SEP> - <SEP> no <SEP> processed <SEP> 0 <SEP> 1
<tb><SEP> -treated <SEP> 6 <SEP> 4
<Tb>
cI Application on terracotta:
The solution S1 'described above is diluted at room temperature with isopropyl acetate to 2% of active ingredients and the clear solution thus obtained is deposited on the surface of terracotta blocks by spraying. The average amount of 2% solution deposited per unit area is 90 g / m 2.

After drying at room temperature for 24 hours, the hydrophobic and oleophobic resistance of the treated blocks is evaluated. The following table gathers the results obtained according to the tests described above with untreated blocks (controls) and pavers treated according to the invention.

<Tb>

<SEP> Recovery <SEP> in <SEP> Time <SEP> of <SEP> Time <SEP> of
<tb><SEP> TEST <SEP> water <SEP> penetration <SEP> AATCC <SEP> 118 <SEP> penetration
<tb><SEP> (g / m) <SEP> drop <SEP> of water <SEP> of a <SEP> drop
<tb><SEP> of <SEP> dodecane
<tb> keypad <SEP> no <SEP> processed <SEP> 14000 <SEP> 0 <SEP> 0 <SEP> 0
<tb><SEP> Treated <SEP> Treated <SEP> 30 <SEP>><SEP> 8 <SEP> Hours <SEP> 8 <SEP>><SEP> 8 <SEP> hours
<Tb>
EXAMPLE 2 Preparation
In the same reactor as in Example 1 purged with a stream of anhydrous nitrogen, 116 g isocyanurate DesmodurB LS2025 [N, N ', N "-tris (isocyanatohexyl) -isocyanurate sold by the company BAYER; index of
NCO: 5.36 meq / g] then the reactor air is again flushed with a stream of dry nitrogen and heated to 80 ° C.

In the dropping funnel heated to 80 ° C., 126 g of fluorinated alcohol are introduced.
CgF17C2H4OH, 200 g of isopropyl acetate and 0.35 g of dibutyltin dilaurate.

The mixture of the dropping funnel is then introduced in 30 minutes into the reactor, the contents of which are then maintained at 80 ° C. for 30 minutes, until consumption of 0.271 mol of isocyanate function.

 In the casting funnel heated to 80 ° C., 130 g of castor oil (OH number: 2.93 meq / g) and 172 g of isopropyl acetate, and the mixture of the ampoule are introduced. is then introduced into the reactor in 30 minutes, the contents of which are then maintained at 80 ° C. for 5 hours, until the isocyanate functions are completely consumed. This gives a fluid solution (S2) of fluorinated oligomer at 50% solids, which solidifies by cooling to room temperature.

 By diluting the solution S2 by addition of isopropyl acetate to 10% of dry extract, a clear yellow solution (S2 ') is obtained whose fluorine content is 2.3% and which remains fluid at ambient temperature.

b / Application on leather
The solution S2 'above is diluted to room temperature up to 2% of active ingredients in isopropyl acetate and the clear solution thus obtained is applied, according to the procedure described in Example 1-b on two grades. of different leather: nappa lamb and velvet lamb. After drying at room temperature for 24 hours, the hydrophobic and oleophobic resistance of the treated leathers was evaluated in comparison with that of untreated leathers. The following table gathers the results obtained.

<Tb>

<SEP> Quality <SEP> of <SEP> leather <SEP> Test <SEP> Test
<tb><SEP> AATCC <SEP> 118 <SEP> eaullPA
<tb> lamb <SEP> nappa
<tb><SEP> - <SEP> no <SEP> processed <SEP> 0 <SEP> 1
<tb><SEP> -treated <SEP> 4 <SEP> 5
<tb> lamb <SEP> velvet
<tb><SEP> - <SEP> no <SEP> processed <SEP> 0 <SEP> 1
<tb><SEP> -treated <SEP> 7 <SEP> 10
<Tb>
EXAMPLES 3 to 42
a / Preparation:
By operating as in Example 1 with the reagents indicated in the following table, a series of oligomers according to the invention was prepared in solution at -50% solids.

 The catalyst (dibutyltin dilaurate) is used at a molar milliequivalent per molar equivalent NCO.

 The solvent used is isopropyl acetate in an amount equal to the total weight of the reagents (polyisocyanate, fatty polyol and fluorinated alcohol).

The fatty polyols used are defined below:
. Pripol # 2033 (diol marketed by UNICHEMA International and obtained by reduction of C36 dimer acids, OH number: 3.51 meq / g)
. Dinoramox # S3 (triol of formula VIII with R '= tallow radical and x + y + z = 3, marketed by CECA, OH number: 6.68 meq / g)
. Dinoramox # S7 (triol of formula VIII with R '= tallow radical and x + y + z = 7, marketed by CECA, OH number: 4.80 meq / g)
. Ethomeen # S / 12 (diol of formula VII with R '= oleyl and x = y = 1, sold by AKZO, OH number: 5.75 meq / g)
. Ethoduomeen # T / 13 (triol of formula VIII with R '= tallow radical and x = y = z = 1, marketed by AKZO, OH number: 6.72 meq / g) <RTI ID = 1

<Tb>

<SEP> Polyol <SEP> Fat <SEP> Quantity <SEP> (g) <SEP> Quantity <SEP> (g) <SEP> of <SEP>% <SEP> Fluorine
<tb> Example <SEP> of fluorinated <SEP> alcohol <SEP> polyisocyanate <SEP> danp <SEP>
<tb><SEP> Nature <SEP> Quantity <SEP> C8F17C2H40H <SEP> Desmodur <SEP> TDI <SEP> The <SEP> Oligomer
<tb><SEP> (9) <SEP> LS2025 <SEP> I <SEP> sec
<tb><SEP> Noramox <SEP> 102 <SEP> 261 <SEP> 94 <SEP> 39.7
<tb><SEP> 4 <SEP> Noramox <SEP> S2 <SEP> 71 <SEP> 182 <SEP> 65 <SEP> 39.8
<tb><SEP> 5 <SEP> Noramox <SEP> S2 <SEP> 73 <SEP> 152 <SEP> 61 <SEP> 37
<tb><SEP> 6 <SEP> Noramox <SEP> S2 <SEP> 95 <SEQ> 146 <SEP> 71 <SEP> 32.6
<tb><SEP> Noramox <SEP> 101 <SEP> 96 <SEP> 60 <SEP> 26
<tb><SEP> 8 <SEP> Noramox <SEP> S2 <SEP> 93 <SEP> 96 <SEP> 60 <SEP> 26.8
<tb><SEP> 9 <SEP> Noramox <SEP> S2 <SEP> 131 <SEP> 334 <SEP> 120 <SEP> 39.7
<tb><SEP> 10 <SEP> Noramox <SEP> S2 <SEP> 95 <SEP> 242 <SEP> 87 <SEP> 39.7
<tb><SEP> 11 <SEP> Noramox <SEP> S2 <SEP> 108 <SEP> 111 <SEP> 69 <SEP> 26.8
<tb><SEP> 12 <SEP> Pripol <SEP> 2033 <SE> 63 <SE> 206 <SE> 119 <SEP> 37
<tb><SEP> 13 <SEP> Pripol <SEP> 2033 <SEP> 98 <SEP> 166 <SEP> 59 <SEP> 35.8
<tb><SEP> 14 <SEP> Pripol <SEP> 2033 <SEP> 180 <SEP> 124 <SEP> 76 <SEP> 22.7
<tb> 15 <SEP> comp. <SEP> Prisorin <SEP> 3515 <SEP> 94 <SEP> 166 <SEP> 59 <SEP> 38.2 <SEP>
<tb><SEP> 16 <SEP> Dinamoxox <SEP> S3 <SEP> 113 <SEQ> 350 <SEQ> 126 <SEQ> 41.4
<tb><SEP> 17 <SEP> Dinamoxox <SEP> S3 <SEP> 33 <SEP> 202 <SEQ> 118 <SEP> 39.7
<tb><SEP> 18 <SEP> Dinamoxox <SEP> S7 <SEP> 47 <SEP> 209 <SEP> 120 <SEP> 38.7
<tb><SEP> 19 <SEP> Dinamoxox <SEP> S7 <SEP> 70 <SEQ> 161 <SEP> 59 <SEP> 38.6
<tb><SEP> 20 <SEP> Ethomeen <SEP> S / 12 <SEP> 37 <SEP> 194 <SEP> 113 <SEP> 39.3
<tb><SEP> 21 <SEP> Ethomeen <SEP> S / 12 <SEP> 107 <SEP> 279 <SEP> 101 <SEP> 39.9
<tb><SEP> 22 <SEP> Ethoduomeen <SEP> n13 <SEP><SEP> 32 <SEP> 192 <SEQ> 112 <SEP> 39.8
<tb><SEP> 23 <SEP> Ethoduomeen <SEP> n13 <SEP> 92 <SEP> 280 <SEP> 101 <SEP> 41.2
<tb><SEP> 24 <SEP> Noramox <SEP> S2 <SEP> 39 <SEQ> 205 <SEP> 116 <SEP> 39.6
<tb><SEP> 25 <SEP> Noramox <SEP> S2 <SEP> 149 <SEP> 381 <SEP> 137 <SEP> 39.8
<tb><SEP> 26 <SEP> Oil <SEP> of <SEP> castor oil <SEP> 74 <SEP> 195 <SEP> 114 <SEP> 35,4
<tb><SEP> 27 <SEP> Oil <SEP> of <SEP> castor oil <SEP> 110 <SEP> 150 <SEP> 115 <SEP> 27,8
<tb><SEP> 28 <SEP> Oil <SEP> of <SEP> castor oil <SEP> 315 <SEP> 151 <SEP> 103 <SEP> 18.5
<tb><SEP> 29 <SEP> Oil <SEP> from <SEP> ricin <SEP> 150 <SEP> 103 <SEP> 118 <SEP> 19.3
<tb><SEP> 30 <SEP> Oil <SEP> of <SEP> castor oil <SEP> 161 <SEP> 87 <SEP> 115 <SEP> 16,7
<tb><SEP> 31 <SEP> Oil <SEP> of <SEP> castor oil <SEP> 137 <SEP> 187 <SEP> 68 <SEP> 33,2
<tb><SEP> 32 <SEP> Oil <SEP> of <SEP> castor oil <SEP> 182 <SEP> 249 <SEP> 90 <SEP> 33.3
<tb><SEP> 33 <SEP> Oil <SEP> of <SEP> ricinus <SEP> 154 <SEP> 207 <SEP> 75 <SEP> 33
<tb><SEP> 34 <SEP> Oil <SEP> of <SEP> castor oil <SEP> 68 <SEP> 169 <SEP> 101 <SEP> 34,8
<tb><SEP> 35 <SEP> Oil <SEP> of <SEP> castor oil <SEP> 125 <SEP> 171 <SEP> 102 <SEP> 29,9
<tb><SEP> 36 <SEP> Oil <SEP> of <SEP> castor oil <SEP> 185 <SEP> 169 <SEP> 101 <SEP> 25,9
<tb><SEP> 37 <SEP> Oil <SEP> of <SEP> castor oil <SEP> 247 <SEP> 170 <SEP> 102 <SEP> 22,8
<tb><SEP> 38 <SEP> Oil <SEP> of <SEP> castor oil <SEP> 161 <SEP> 145 <SEP> 99 <SEP> 24,9
<tb><SEP> 39 <SEP> Oil <SEP> of <SEP> castor oil <SEP> 126 <SEP> 128 <SEP> 102 <SEP> 25
<tb><SEP> 40 <SEP> Ethoquad <SEP> HT25 <SEP> 99 <SEP> 192 <SEQ> 111 <SEP> 33.2
<tb><SEP> 41 <SEP> Oil <SEP> of <SEP> castor oil <SEP> 249 <SEP> 126 <SEP> 101 <SEP> 18.4
<tb><SEP> 49 <SEP> Hllila <SEP> r (o <SEP> ricin <SEP>O;<SEP> 146 <SEP> 1nN <SEP>
<Tb>
In what follows, Sx denotes the 50% solids solution of the oligomer according to Example x and Sx 'means the 10% solids solution of the oligomer, according to Example x.

The following table gathers the results of the AATCC 118 and water / lPA tests carried out on samples of treated nappa lamb, velvet lamb or cowhide leather, according to the procedure described in example 1-b, with 2% solutions of materials. active in isopropyl acetate.

<Tb>

<SEP> Quality <SEP> of <SEP> leather <SEP> Fluorinated <SEP> Oligomer <SEP> AATCC <SEP> 118 <SEP> Test <SEP> water / lPA
<tb><SEP> of <SEP> Example <SEP> n "<SEP>
<tb><SEP> Lamb <SEP> Nappa <SEP> 3 <SEP> 5 <SEP> 7
<tb><SEP> Lamb <SEP> Nappa <SEP> 4 <SEP> 4 <SEP> 7
<tb><SEP> Lamb <SEP> Nappa <SEP> 5 <SEP> 4 <SEP> 7
<tb><SEP> Lamb <SEP> Nappa <SEP> 7 <SEP> 4 <SEP> 7
<tb><SEP> Lamb <SEP> Nappa <SEP> 8 <SEP> 4 <SEP> 7
<tb> Lamb <SEP> velvet <SEP> 12 <SEP> 6 <SEP> 7
<tb> Lamb <SEP> velvet <SEP> 13 <SEP> 6 <SEP> 8
<tb> Lamb <SEP> velvet <SEP> 15 <SEP> comparative <SEP> 3 <SEP> 6
<tb> Vachette <SEP> plant <SEP> 13 <SEP> 6 <SEP> 6
<tb> Vachette <SEP> plant <SEP> 15 <SEP> comparative <SEP> 1 <SEP> 1
<tb><SEP> Lamb <SEP> Nappa <SEP> 13 <SEP> 6 <SEP> 8
<tb><SEP> Lamb <SEP> Nappa <SEP> 14 <SEP> 4 <SEP> 6
<tb><SEP> Lamb <SEP> nappa <SEP> 15 <SEP> comparative <SEP> 4 <SEP> 6
<tb><SEP> Lamb <SEP> Nappa <SEP> 16 <SEP> 4 <SEP> 5
<tb><SEP> Lamb <SEP> Nappa <SEP> 17 <SEP> 5 <SEP> 4
<tb><SEP> Lamb <SEP> Nappa <SEP> 18 <SEP> 5 <SEP> 5
<tb><SEP> Lamb <SEP> Nappa <SEP> 19 <SEP> 6 <SEP> 6
<tb><SEP> Lamb <SEP> Nappa <SEP> 20 <SEP> 2 <SEP> 7
<tb><SEP> Lamb <SEP> Nappa <SEP> 21 <SEP> 6 <SEP> 7
<tb><SEP> Lamb <SEP> Nappa <SEP> 22 <SEP> 2 <SEP> 7
<tb><SEP> Lamb <SEP> Nappa <SEP> 23 <SEP> 5 <SEP> 7
<tb> Lamb <SEP> velvet <SEP> 24 <SEP> 6 <SEP> 6
<Tb>
EXAMPLE 43
a / Preparation:
A reactor with a capacity of 1.5 liters, equipped with a stirrer, a thermometer, a reflux condenser, a heating funnel, an anhydrous nitrogen inlet, is used. and a heater. The air is expelled from the reactor by a stream of anhydrous nitrogen, then 122 g of Desmodur are charged.
LS2025. The reactor air was again flushed with a stream of dry nitrogen and heated to 60 ° C.

In the dropping funnel heated to 70 ° C., 109 g of fluorinated alcohol are introduced.
CgF17C2H4OH, 16.8% glycolic acid (OH number = 2.93 meq / g), 50% acetone and 0.4 g dibutyltin dilaurate. The mixture of the dropping funnel is then introduced in 30 minutes into the reactor, the contents of which are then kept under reflux of acetone for 30 minutes, until consumption of 0.284 mol of isocyanate function.

 In the dropping funnel heated to 60 ° C., 76 g of castor oil and 81 g of acetone are introduced The mixture of the dropping funnel is introduced in 60 minutes into the reactor, the contents of which are then maintained. at reflux of acetone for 2 hours, until total consumption of isocyanate functions.

 The fluorinated oligomer thus obtained is put into the form of an aqueous dispersion by casting the still hot reaction mixture (60 ° C.) in a mixture, brought to 50 ° C. with stirring, with 760 g of water and 24 hours of stirring. 2 g of triethylamine (TEA). Stirring is continued for another hour and a stable dispersion is obtained. The average particle size is 200 nm and the solids content is 25%.

b / Application on leather:
The fluorinated oligomer dispersion obtained above is diluted to 2% of active ingredients in water, then applied according to the procedure described in Example 1-b, but in aqueous medium on two different qualities of leather: nappa lamb and velvet lamb. After drying at room temperature for 24 hours, the hydrophobic and oleophobic resistance of the leathers is evaluated. The following table gathers the results obtained.

<Tb>

<SEP> Quality <SEP> of <SEP> leather <SEP> Test <SEP> AATCC <SEP> 118 <SEP> Test <SEP> water / lPA
<tb> lamb <SEP> nappa
<tb><SEP> - <SEP> no <SEP> processed <SEP> 0 <SEP> 1
<tb><SEP> -treated <SEP> 2 <SEP> 2
<tb> lamb <SEP> velvet
<tb><SEP> - <SEP> no <SEP> processed <SEP> O <SEP>
<tb><SEP> -treated <SEP> 4 <SEP> ~ <SEP><SEP> 2
<Tb>
EXAMPLES 44 to 46
By operating as in Example 43, with the reagents indicated in the following table, three fluorinated oligomers according to the invention were prepared in the form of aqueous dispersions, which were still stable after storage for 6 months at room temperature.

<Tb>

<SEP> EXAMPLE <SEP> 44 <SEP> 1 <SEP> 45 <SEP> 46
<tb> Reagents <SEP> (quantity <SEP> in <SEP> g): <SEP>
<tb><SEP> Isocyanurate <SEP> Desmodur <SEP> LS2025 <SEP> 105 <SEP> 101 <SEP> 113
<tb><SEP> Fluorinated <SEP> alcohol <SEP> CgF17C2H4OH <SEP> 77 <SEP> 96 <SEP> 109
<tb><SEP> Oil <SEP> of <SEP> castor oil <SEP> 67 <SEP> 54 <SEP> 79
<tb><SEP> Glycolic <SEP> Acid <SEP> 17 <SEP> 15.4 <SEP> 18.4
<tb><SEP> Triethylamine <SEP> 24.6 <SEP> 22.2 <SEP> 26.6
<tb> Characteristics <SEP> of <SEP> dispersions:
<tb><SEP> Extract <SEP> sec <SEP> (%) <SEP> 25 <SEP> 25 <SEP> 25
<tb><SEP> Size <SEP> of <SEP> particles <SEP> (nm) <SEP> 150 <SEQ> 140 <SEP> 85
<tb><SEP><SEP> acid number <SEP> 50 <SEP> 45 <SEP> 45
<tb><SEP> Content <SEP> in <SEP> fluorine <SEP> of <SEP> product <SEP> sec <SEP> (%) <SEP> 20.1 <SEP> 25 <SEP> 25
<Tb>
EXAMPLE 47
a) Emulsification of the oligomer of Example 2 using a high pressure homogenizer
We prepare:
an organic solution by mixing 500 g of solution S2 with 5 g of
Tween 80 (surfactant with 100% active ingredients marketed by ICI) and
an aqueous solution by mixing 450 g of water, 50 g of ethylene glycol and 22.5 g of a 22% aqueous solution of sodium dodecylbenzenesulphonate.

Both solutions are separately heated to 60 ° C. The hot aqueous solution is stirred vigorously with a high shear stirrer.
Ultraturrax rotating at 8000 rpm. While maintaining stirring, the hot organic solution is poured into the aqueous solution and stirring is continued for 10 minutes; a pre-emulsion is obtained.

 This pre-emulsion is homogenized using a Manton Gaulin Lab 60 type valve homogenizer (inlet pressure: 50 bar - outlet pressure: 250 bar) and the isopropyl acetate is then removed by evaporation. under vacuum at 40 ° C. A stable white emulsion is thus obtained which is adjusted to 25% of dry extract by the addition of water, the mean particle size is 250 nm and the polydispersity is less than at 0.1.

b) Application on Leather of the Emulsion of the Oligomer of Example 2
The emulsion obtained above is diluted to 2% of active ingredients in water and then applied to velvet lamb leather according to the procedure described in Example 1-b. After drying at room temperature for 24 hours, the hydrophobic and oleophobic strength tests gave the following results:

<tb><SEP> Leather <SEP> no <SEP> processed <SEP> Leather <SEP> processed
<tb> TestAATCCII8 <SEP> 0 <SEP> 4
<tb> Test <SEP> water / lPA <SEP> 1 <SEP> 3
<Tb>
EXAMPLE 48
a) Emulsification of the oligomer of Example 2 with the aid of an ultrasound probe
We prepare:
an organic solution by mixing 60 g of solution S2, 40 g of isopropyl acetate and 1.5 g of dodecylbenzenesulphonic acid and
an aqueous solution by mixing 86 g of water and 14 g of ethylene glycol.

Both solutions are separately heated to 60 ° C. The hot aqueous solution is stirred vigorously with a high shear stirrer.
Ultraturrax rotating at 8000 rpm. While maintaining stirring, the hot organic solution is poured into the aqueous solution and stirring is further maintained for 10 minutes. A pre-emulsion is obtained which is homogenized for 8 minutes using a 19 mm diameter ultrasonic probe connected to a 500 watt Vibra Cell generator (Sonics & Materials Inc.) Isopropyl acetate is then removed by evaporation in vacuo at 40 ° C. A stable, white emulsion is obtained which is adjusted to 20% of dry extract by the addition of water.

b) Application on leather of the emulsion of the oligomer of Example 2
The emulsion obtained above is diluted with up to 2% of active ingredients in water, and then applied to two grades of leather: vegetable cowhide and velvet lamb, according to the procedure described in Example 1b. After drying at room temperature for 24 hours, the hydrophobic and oleophobic strength tests gave the results summarized in the following table.

<tb><SEP> Quality <SEP> of <SEP> leather <SEP> AATCC <SEP> 118 <SEP> Testeau / lPA <SEP>
<tb> vachette <SEP> plant
<tb><SEP> - <SEP> no <SEP> processed <SEP> 0 <SEP> 0
<tb><SEP> -treated <SEP> 4 <SEP> 4
<tb> lamb <SEP> velvet
<tb><SEP> - <SEP> no <SEP> processed <SEP> 0 <SEP> 1
<tb><SEP> -treated <SEP> 5 <SEP> 3
<Tb>

EXAMPLE 49
a) Emulsification of the Oligomer of Example 9 Using a Homoz
high pressure generator
We prepare:
an organic solution by mixing 420 g of solution S9, 280 g of isopropyl acetate and 21 g of dodecylbenzenesulphonic acid, and
an aqueous solution by mixing 602 g of water and 98 g of ethylene glycol.

The two solutions are heated separately to 60 ° C. The hot aqueous solution is subjected to vigorous stirring using a high-shear stirrer.
Ultraturrax rotating at 8000 rpm. While maintaining stirring, the hot organic solution is poured into the aqueous solution and stirring is further maintained for 10 minutes. A pre-emulsion is obtained which is homogenized using a Manton Gaulin valve homogenizer (inlet pressure: 50 bar - outlet pressure: 250 bar). The final emulsion thus obtained, which has a pH equal to 5.5, is brought to a pH of 2.5 by addition of formic acid; The final dry extract is 15%.

b) Leather Application of the Emulsion of the Oligomer of Example 9
The emulsion obtained above is diluted to 2% of active ingredients by addition of water, and then applied to velvet lamb leather according to the procedure described in Example 1-b. After drying at room temperature for 24 hours, the hydrophobic and oleophobic strength tests gave the following results:

<tb><SEP> Leather <SEP> Leather <SEP> no <SEP> treated <SEP> Leather <SEP> processed
<tb> it <SEP> TestAATCCll8 <SEP> I <SEP> 5 <SEP><SEP> I <SEP> s <SEP>
<tb><SEP> Test <SEP> water / lPA <SEP> T <SEP> 5
<Tb>
EXAMPLE 50
a) Emulsification of the Oligomers of Examples 3 and 4 Using a High Pressure Homogenizer
We prepare:
an organic solution by mixing 300 g of solution S3, 200 g of isopropyl acetate, 1 g of surfactant Tween 80 (polyoxyethylated sorbitan monooleate 20 units of ethylene oxide) and 4 g of oleic acid, and
an aqueous solution by mixing 430 g of water, 70 g of ethylene glycol and 5 g of diethanolamine.

Both solutions are separately heated to 60 ° C. The hot aqueous solution is stirred vigorously with a high shear stirrer.
Ultraturrax rotating at 8000 rpm. While maintaining stirring, the hot organic solution is poured into the aqueous solution and stirring is continued for 10 minutes. A pre-emulsion is obtained which is homogenized using a Manton Gaulin valve homogenizer (inlet pressure: 50 bar - outlet pressure: 250 bar). The isopropyl acetate is then removed by evaporation under vacuum at 40 ° C. The final emulsion (E3) has a solids content of 23%.

 Working in the same way with 300 g of the S4 solution, an emulsion (E4) of the fluorinated oligomer of Example 4 is prepared.

b) Application on leather of E3 and E4 emulsions
The emulsions E3 and E4 obtained above are used for the fulling process of lambskin on stain according to a process comprising four successive stages defined in the following table where the quantities used are expressed in percentages by weight relative to the weight leather.

<Tb>

- <SEP> Rewet:
<tb><SEP>.<SEP> water <SEP> to <SEP> 45 C <SEP> water <SEP> to <SEP> 450C <SEP> 400 <SEP>% <SEP>
<tb><SEP>.<SEP> ammonia <SEP> 0.2 <SEP>%
<tb><SEP> rotation <SEP> 120 <SEP> minutes
<tb> - <SEP> Dyeing <SEP> and <SEP> Food
<tb><SEP> water <SEP> to <SEP> 50 C <SEP> 200 <SEP>%
<tb><SEP> agent <SEP> from <SEP> tincture <SEP> Blue <SEP> Luganil # NL <SEP> from <SEP><SEP> company <SEP> BASF <SEP> 0.73 <SEP> %
<tb><SEP> rotation <SEP> 30 <SEP> minutes
<tb><SEP> oil <SEP> from <SEP> food <SEP> Lipoderm <SEP> Lickers # SC <SEP> from <SEP><SEP> company <SEP> BASF <SEP> 1,84
<tb><SEP>.<SEP> oil <SEP> from <SEP> food <SEP> Lipoderm <SEP> LickersSK <SEP> from <SEP> the <SEP> company <SEP> BASF <SEP> 0,18
<tb><SEP> rotation <SEP> 40 <SEP> minutes
<tb> - <SEP> Waterproofing
<tb><SEP>.<SEP> emulsion <SEP> E3 <SEP> or <SEP> E4 <SEP> 2.97 <SEP>%
<tb><SEP> rotation <SEP> 40 <SEP> minutes
<tb> - <SEP> Acidification <SEP> and <SEP> rinsing
<tb><SEP>.<SEP> acid <SEP> formic <SEP> 1.5 <SEP>%
<tb><SEP>.<SEP> rotation <SEP> 20 <SEP> minutes
<tb><SEP> .pH <SEP> 4
<tb><SEP> acid <SEP> formic <SEP> 1.5 <SEP>% <SEP>
<tb><SEP> rotation <SEP> 30 <SEP> minutes
<tb><SEP>.<SEP> pH <SEP> 3,3
<tb><SEP> water <SEP> to <SEP> 20 C <SEP> 20 <SEP> minutes
<Tb>
The characteristics of the leathers treated in this way are summarized in the following table:

<tb><SEP> TEST <SEP> Leather <SEP> No <SEP> Leather <SEP> Treated <SEP> Leather <SEP> Treated
<tb><SEP> Processed <SEP> By <SEP> E3 <SEP> By <SEP> E4
<tb> AATCC <SEP> 118 <SEP> 0 <SEP> 4 <SEP> 3
<tb> Water / l <SEP> PA <SEP> 0 <SEP> 7 <SEP> 7
<tb> Test <SEP> to <SEP> the <SEP> pocket <SEP> of water
<tb><SEP>.<SEP> quantity <SEP> of water <SEP> collected <SEP> (in <SEP> g) <SEP> 88 <SEP> 0 <SEP> 0
<tb><SEP> water <SEP> absorbed <SEP> 2.8 <SEP> 1.1 <SEP> 1.18
<Tb>

Claims (12)

 the proportion of component (c) being such that the ratio of its number of GR equivalents to the number of NCO equivalents of the polyisocyanate is between 0 and 0.45.  the proportion of polyol (b) being such that the ratio of its number of OH equivalents to the number of NCO equivalents of the polyisocyanate is between 0.2 and 1.8; and NCO of the polyisocyanate is between 0.2 and 0.8;  the proportion of the fluorocarbon compound (a) being such that the fluorine content by weight of the oligomer is at least 15% and the ratio of the number of GNHL equivalents of the fluorocarbon compound (a) to the number of equivalents  the components (a), (b) and (c) being in proportions sufficient for the total number of GNHL, OH and GR equivalents to be at least equal to the number of NCO equivalents of the polyisocyanate:  (c) one or more other compound (s) having at least one reactive group (GR) with respect to the NCO functions;  (b) at least one fatty aliphatic chain polyol of at least 16 carbon atoms; and eventually  (a) at least one fluorocarbon compound containing a perfluoroalkyl radical and a labile hydrogen nucleophilic group (GNHL);  1. Fluorinated urethane oligomers obtained by reacting at least one polyisocyanate with:  2. Oligomer according to claim 1, the weight content of fluorine is at least equal to 25%.  3. Oligomer according to claim 1 or 2 wherein the polyisocyanate is toluene diisocyanate (isomers 2,4 and 2,6 or their mixture) or N, N ', N "-tris (isocyanatohexyl) isocyanurate.  4. Oligomer according to one of claims 1 to 3 wherein the fluorocarbon compound (a) is selected from alcohols and thiols of formulas:  Rf - (CH2) m -X- (CH2) n-OH (I)  Rf - (CH2) n (OCH2CH2) p-OH (II)  Rf - CH = CH - (CH2) n - OH (III)  Wherein Rf represents a perfluoroalkyl radical, linear or branched, ranging from 2 to 20 (preferably 4 to 16) carbon atoms; X represents a direct bond, an oxygen or sulfur atom or a -COO-, -SO2-, -CONR- or -SO2NR- group, where R represents an alkyl radical containing 1 to 4 carbon atoms; m represents an integer ranging from 0 to 20, preferably equal to 0 or 2; n is an integer from 1 to 20, preferably 2 or 4; and p is an integer from 1 to 5.  An oligomer according to claim 4 wherein the fluorocarbon compound (a) is a compound of the formula:  Rf-C2H4-QH (V) wherein Rf has the same meaning as in claim 4 and Q is oxygen or sulfur.  6. Oligomer according to one of claims 1 to 5 wherein the polyol (b) is selected from compounds of formulas:

 in which R 'denotes a saturated or unsaturated aliphatic radical of at least 16 carbon atoms and the symbols, x, y and z, which are identical or different, each representing an integer ranging from 1 to 5, and the polyols obtained by reduction of the diacids resulting from the dimerization or trimerization of unsaturated fatty acids.

 7. Oligomer according to one of claims 1 to 6 wherein the ratio of the number of equivalents GNHL fluorocarbon compound (a) to the number of equivalents NCO of the polyisocyanate is between 0.35 and 0.65.  8. Oligomer according to one of claims 1 to 7 wherein the ratio of the number of OH equivalents of the polyol (b) to the number of NCO equivalents of the polyisocyanate is between 0.4 and 0.8.  9. Oligomer according to one of claims 1 to 8 wherein the ratio of the number of equivalents GR component (c) to the number of NCO equivalents of the polyisocyanate is between 0 and 0.4.  10. Oligomer according to one of claims 1 to 9 in the form of organic solution or dispersion or aqueous emulsion.  11. Application of an oligomer according to one of claims 1 to 10 water repellent and oil repellent treatment of various substrates, in particular leathers.  12. Articles treated with an oligomer according to one of claims 1 to 10.