IL28569A

IL28569A - Oil-and water-repellent compositions

Info

Publication number: IL28569A
Application number: IL2856967A
Authority: IL
Original assignee: Ucb Sa
Priority date: 1966-09-30
Filing date: 1967-08-27
Publication date: 1971-02-25
Also published as: ES345514A1; DE1619188A1; BE704413A; SE336998B; SU366621A3; FR1557006A; LU54550A1; GB1147169A; NL6713092A; AT280941B

Description

28569/2 ύ»»ν iw ηιππη nianyn and water-repellent compositions UCB (UHION CHI IQUE-OT ISCHE BEDRIJTO) 8.A 0:2711 The present invention is concerned with new oil- and wat r-repellent compositions.

Our Specification No. is concerned with new fluorinated ethylenically unsaturated mixed ester monomers and with their homo-and copolymers with one another or with copolymerizable olefinic compounds.

The homopolymers and copolymers thus obtained have interesting oil-repellent properties which permit the consideration of their use for the treatment of any porous or non-porous material which is to be protected from dirt and rendered resistant to wetting by water, vegetable, animal or mineral oils or fats, hydrocarbons or organic solvents. However, the water-repellent properties of these fluorinated homopolymers and copolymers are not very marked.

There exists, at present, a demand for finishing agents which are capable of rendering porous materials, in particular textile materials, not only water-impermeable but also resistant to soiling by fatty materials. It is also very important, for practical purposes, that such compounds should have a permanent character, i.e. that articles impregnated with the said compounds should remain impermoable to water and fats, even after being subjected to washing in an aqueous bath containing soap and/or detergents or to dry-cleaning with solvents.

By combining the polymerized fluorinated olefinic compounds, which are the subject matter of our above-mentioned Patent Specification, with suitable eubstances, we have succeeded in preparing new compositions which meet the above demands remarkably well with regard to their oil-repellent and water-repellent properties and to their permanent character.

According to the present invention the compositions for rendering porous and non-porous materials oil-repellent and water-repellent comprise as essential components: - a component (A) selected from the group consisting of homopolymers of fluorinated ethylenically unsaturat-jd mixed esters of the general formula: a1 CO -Y-0 CR" in which R'CO^ represents the residue of a perfluoroalkanoic acid, R'OO^ is the residue of a polymerizable alkenoic acid, and Y is the bivalent residue of an organic compound selected from the group consisting of aliphatic, aromatic and aliphatic- aromatic dihydric alcohols, the carbon chain of which may be interrupted by oxygen atoms, and of copolymers selected from the group consisting of copolymers of ttae sa^ fluorinated ethylenically unsaturated mixed esters with one another and of copolymers of the said fluorinated ethylenically unsaturated mixed esters with copolymerizable monomers selected from the group consisting of alkyl acrylates , alkyl methacrylates , acrylamide and methacryla ide, in admixture with at least one polymer selected from - a component (B) which consists of at least one copolymer selected from the copolymers of alkyl acrylates and alkyl methacrylates with an ethylenically unsaturated compound which contains a reactive group selected from N-methylol, N-alkoxymethyl, aldehyde and epoxy groups ,- and - a component (c) which consists of aminoplast resins selected from the polymeric products' obtained by the reaction of amine compounds with aldehydes and eventually alcohols , particularly aminoplast resins obtained by the reaction of an amine selected from melamine and urea with formaldehyde, as well as their reaction products with alcohols , especially alkylated urea-formaldehyde and alkylated melamine-formaldehyde resins .

The compositions according to the present invention contain 1 to 5 j't, preferably 3 to 20Jo, by weight of the component (A) , 0 to 99 >> > preferably 0 to 60>- j by weight of the component (B) , and 0 to ?°> preferably 0 to 60}i, by weight of the component (c) .

The fluorinated ethylenically unsaturated mixed esters and the homo-and copolymers of these compounds (which form the component A in the compositions according to the present invention) , as well as the preparation of these materials , form the subject matter of our ¾¾i¾¾-e& Patent Specification No. 23i£^¾> . Component (A) is present in the form of a solution in organic solvents or of an aqueous emulsion or dispersion which generally contain 1 to 30;'o by weight of homo- and/or co-polymers .

Component (B) in the compositions according to the present invention consists of at leaet one copolymer of acrylates and/or methacrylates of aliphatic hydroxy compounds with an ethylenically unsaturated derivative having an N-methylol, N-alkoxymethyl, aldehyde or epoxy function.

Examples of acrylates and/or methacrylates which can be used for the preparation of these copolymers are hexyl, 2-ethyl-hexyl , n -heptyl, n-octyl and n-nonyl acrylates and the like and butyl, isobutyl, amyl, n-hexyl, n-heptyl, n-octyl , 2-ethyl-hexyl, n-nonyl methacrylates and the like.

As examples of ethylenically unsaturated derivatives with an N-methyloJ¾ N-alkoxymethyl, aldehyde or epoxy function, which can be co polymerized with the stated esters , there may be mentioned N-methylol-acrylamide and its alkylated derivatives such as N-methoxymethyl-acrylaraide, N-methylol-methacryl-amide and its alkylated derivatives such as N-methoxymethyl-methacrylamide , N-methylol-maleimida, acrolein, methacrole n, glycidyl acrylate and methacrylate and the like. Component (B) contains 0 to 99· 5 » by weight of acrylates and/or raethacrylates and 10 to 0.5?o by eight of the ethylenically unsaturated derivative having an N-methylol, N-alkoxymethyl, aldehyde or epoxy function.

Component (B) can be prepared by the methods commonly used for polymerization in an organic solution or in an aqueous emulsion or dispersion in the presence of conventional polymerization catalysts , such as inorganic or organic peroxides , hydroperoxides , peracids , persalts , diazo compounds , redox systems and the like. The polymerization in an aqueous emulsion or dispersion is carried out in the presenCo of anionic , cationic and/or non-ionic surface-active agents , emulsion stabilizers and the like. Component (B) is present in the form of an organic solution or of an aqueous emulsion or dispersion which contains 2 to 40 by weight of dry matter.

Component (C) in the compositions according to the present invention is an aminoplast rjsin selected from polymeric products which are obtained by reacting amino compounds , such as melamine and ur^a, with aldehydes , such as formaldehydes, and possibly alcohols , such as methanol, ethanol, butanol and the like. These resins , which are prepared by thy usual methods , arj preferably used in the form of aqueous solutions or emulsions or in the form of solutions in. organic solvents , these solutions or emulsions containing 20 to 80 t> by weight of dry matter.

As stated above, the compositions according to the present invention contain 1 to ^Cf/o , preferably 3 to 20/i, by weight of component (A) , 0 to 99A > preferably 0 to 60 i, by weight of component (B) , and 0 to 9 ^, preferably 0 to 60/. , by weight of component (C) .

In fact , these compositions usually also contain either solvents or water and surface active agents , emulsion stabilizers and the liko. They are prepared by mixing the solutions , emulsions or dispersions of the components (A) , (B) and (C) in the proportions defined above. Ths compositions thus obtained can be marketed as such or they can be concentrated by eliminating part of the solvent or wat.-¾r by evaporation, or they can be diluted by adding a certain quantity of solvent or water. In general, the total of essential^ ^ components in the solutions, emulsions or dispersions according to the present invention amounts to 0.1 to Q¾ by weight, preferably 0.5 to 3/* by weight.

T ; compositions of the present invention can also be used in th^ form of aerosols.

In order to promote the cross-linking and the adhesion of the water-repellent and oil-repellent coatings to the materials which are to be rendered water- and oil-r pellent,, a catalyst is generally added to the compositions, for example, zinc nitrate hexahydrate, ammonium nitrate, and the like in an amount of 1 to yjfa by weight of the total of the components (A), (B) and (C).

V/ith a view to their use for the impregnation of porous or non-porous materials which are to be rendered water- and oil-repellent, the solutions, emulsions or dispersions according to the present invdntion can be diluted either with an organic solvent or with water. The solutions, emulsions or dispersions thus diluted are called "baths". The concentration of these baths obviously varies in accordance with the nature of the material to be impregnated, the weight of water- and oil-repellent resin which is to be fixed on the material and the like. In general, the total of essential components in the oil- and wat r-repellent baths according to the present invention amounts to 0.1 to 20^, preferably 0.5 to 10 , by weight of the baths.

The porous and non-porous materials which can be treated with the baths according to the present invention in order to be made oil- and water-repellent are, for example, natural or synthetic textile fibres and th fabrics produced therefrom, paper, wood, bricks, asbestos, materials of asbestos cement, concrete, leather, hides and the like. The porous and non-porous materials are rendered impermeable to water and fats by impregnating them with the solutions, emulsions or dispersions according to the present invention. They are then dried at a temperature between 15 and 10Q°C. in order to evaporate the water or solvents, and then subjected to a temperature of I30 to 180eC. for a period varying from minutes to 15 seconds in order to fix th¾ -coating on the porous or non-porous material in a durable manner. ka the most important use of the compositions according to the present invention is to render fabrics oil- and water-repellent, the following statement is particularly concerned with the treatment of this material.

The fabric is padded in the bath described above and then squeezed between rollers. As a result of the pressure under which the fabric is squeezed between the rollers, the fabric absorbs a more or less large amount Of the bat^ If, for example, the weight of the fabric has increased by 70 after padding and squeezing, its squeezing rate is stated to be 70b.

The fabric is subsequently air-dried for about JO minutes or dried in a drying cabinet at 100°C. for a few minutes in order to evaporate the solvent or water.

The fabric is subsequently heated to a temperature of 150. to 180CC. for a period varying from minutes to 15 seconds, the duration of the treatment being the shorter, the higher is the temperature.

Thd compositions according to the present invention offer important advantages in comparison with the known fluorinated compounds. Thus, an excellent oleophobia is achieved while using a substantially smaller amount of fluorinated polymer, the cost of the oil-repellent treatment being thus reduced. On the other hand, the coatings applied exhibit an excellent resistance to washing with soapy water or to dry-cleaning with solvents. Finally, the compositions according to the present invention permit the obtaining of an excellent hydrophobia. These properties will be proved in the following Examples.

The proof of the oleophobic properties of the compositions according to the present invention is carried out by using the scale of E.J. GR ECK and W.H. P2TSRS0N (Textile Research Journal,^, (1962) ,323) . In this test, mixtures of paraffin and hydrocarbon (n-haptane) are first prepared in proportions by volume which are graded from 0/Ό to 100;¾ of paraffin and, correspondingly, from 100 to Qf/o of hydrocarbon, each mixture thus obtained being characterized by an oleophobia coefficient according to the following Table: Oleophobia Paraffin oil Hydrocarbon (n-heptane) coefficient as '/Ό as b 50 100 0 60 90 10 70 80 20 80 70 30 90 60 40 100 50 50 110 40 60 120 30 70 I30 20 80 140 10 90 I50 0 100 The higher the coefficient, the less tendency has the fabric to be soiled by the mixture of oil and solvent. For the test, a drop of one of the above mixtures is placed on the substrate treated with the pleophobic composition and that drop is sought» which is richest in hydrocarbon and yet remains for at least 3 minutes on the substrate, i.e. without penetrating into the latter. The oleophobia test is considered to be satisfactory when the coefficient amounts to at least 90 and it is obviously better to the extent that the coefficient is higher.

In order to prove the hydrophobic properties of the compositions according to the present invention, the following methods are applied: a) Belgian standard 5 3.05 (BUITOESMWJN) for the determination of the percentage of water absorption (this must be as low as possible, the maximum percentage tolerated being 25-30 ¾) and the penetration of water into the fabric, expressed in cc. (this value uepends on the texture of the fabric but, in principle, it should be nil or only slightly above zero) ; b) Belgian standard 593·06 for the determination of the degree of hydrophobia by the spray test; the results are expressed by arbitrary values, the value 80 being the lowest limit tolerated, whereas 0 is an acceptable value and 100 is an excellent value.

Finally, the tests for resistance to washing and dry-cleaning are carried out according to the "Prescriptions de contrSle provisoire pour le symbole d'entretien lavage" ( 25th October 1962) and "Prescriptions de contr61e provisoire pour le symbole d'entretien degraissage" (20th October 1962), respectively, which have been published by the Oomite Technique International d'Stiquetage (C.T.I.E.).

The following Examples are given for the purpose of illustrating the present invention: Example 1.

In this Example, there is used a fabric consisting of 3O70 cotton and 70Ji polyester, which has a weight of 180 g./sq.m. and a density of 0 threads per cm. in the warp and 28 threads per cm. in the weft. Samples of this fabric are impregnated in baths containing various proportions of a homopolymer of 2,2-dimethyl-propane-l, 3*- octyl methacrylate and 1% N- methylolacrylamide (component B). The samples are subsequently squeezed to a squeezing rate of 70 , then air-dried at room temperature for about 30 miute^ and finally treated at 1652C. for 3 minutes.

The following Table indicates the percentage by weight of the compounds (A) and (B) applied to the fabric samples and the content of these components in the bath, stating each time the result obtained in the oleophobia test described above.

TABLE I Component A Component B Oleophobia applied to in the applied to in the the fabric bath the fabric bath 0.05 0.07 0.450 0.64 70 0.07 0.1 0.93 1. 33 80 0.1 0.14 0.9 1. 3 90 0.14 0. 20 1.86 2. 66 100 0.21 0.3 2.8 4 110 0.3 0.43 1.7 2.43 110 0.3 0.43 5.7 8.14 110 0.4 0.57 1.6 2. 3 110 0.6 0.86 5.4 7. 7 110 0.9 1.3 5.1 7. 3 110 It can be seen from this Table that by applying only 0.1$ by weight of the compound (A) to the fabric, there is obtained an oleophobia which corresponds to commercial standards. On the other hand, there is no advantage in applying more than 0. 21% by weight of the compound (A) to the fabric, in order to achieve an oleophobia of 110. It can also be seen that the oleophobia is not affected by strong variations of the compound (B) .

Example 2.

In this Example, the fabric used and the working conditions are the same as in Example 1. Howjver, there are used different polymeric fluorinated esters as compound (A) and different non-fluorinatod copolymers as compound (B) .

The following Table states the percentage by weight of compound (A) (compounds I to IX) reset in the bath and that applied to the fabric, and the percentage by weight of the compound (B) (compounds X to XIII) present in the bath and that applied to the fabric, stating, in each case, the result obtained in the oleophobia test described above.

The compounds (A) are the following: I same polymer as in Example 1; II homopolymer of ethylene glycol perfluorooctanoate acrylate; III homopolymer of ethylene glycol perfluorooctanoate methacrylat e ; IV homopolymer of propylene-glycol perfluorooctanoate methacrylate; V homopolymer of 2-methyl-2-propyl-propane-l, 3-cliol perfluorooctanoate methacrylate; VI homopolymer of 2, 2-diethyl-propane-l, 3-diol perfluorooctanoate methacrylat ; VII homopolymer of diethylene glycol perfluorooctanoate methacrylate; VIII homopolymer of p ntamethylene glycol perfluorooctanoate methacrylate; IX copolymer of 5 ^ 2 , 2-dimethylpropane-l , 3-diol perfluorooctanoate methacrylat^ and 50,1 2, 2-dimethylpropane-l, 3-diol perfluorobutyrate methacrylate; The compounds (B) are the following: X copolymer of 9 ?b octyl methacrylate and 1% N-methylol-acrylamidc ; XI copolymer of $ 2-ethyl-hexyl acrylate and 1% N-methylol-acrylamide; XII copolymer of ?^ butyl acrylate and l>o N-methylol-acrylamide; XIII copolymer of 2-ethyl-hexylmethacrylate and 4>o N-methoxymethyl- acrylamide.

TABLE II Component A Component B Oleophobia in th . bath applied to in the bath applied to the fabric the fabric I (0.36 ) 1 (0.25) XI (3.2) XI ( 2.25) HO I (0.07) I (0.05) XI (1.36) XI (0.95) 90 I (0.36) I (0.25) XII (1.07) XII (0.75) 110 +XI (0.7) +XI (0.5) I (0.36) I (0.25) XII (1.8) XII (^.25 ) 110 I (0.09) I (0.06) XIII (0.46) XIII(0.52) 90 II (1.07) II (0.75) X (3.2) X (2.25) 90 III (0.29) III (0.2) XI (2.6) XI (1.8) 110 in (0.43) III (0.3) XI (1.3) XI (0.9) 100 IV (1.07) IV (0.75) X (3.6) X ( 2.5) 110 V (1.07) V (0.75) X (3-6) X (2.5) 110 V (0.43) V (0.3) X (1.8) X (1.25 ) 110 V (0.14) V (0.1) X (1.8) X (1.25) 90 Component A Component B 1L OleopTobiaj in the bath applied to in the bath applied to the fabric the fabric VI (1.07) VI (0,75) X ( 3.6) X ( 2.5) 110 vi (0.14) VI (0.1) X (1.8) X (1.25) 110 VII ( 0.43) vii (0.3) X (1.8) X (1.25) 110 vii (0.14) VII (0.1) X (1.8) X (1.25) 100 VIII (0.43) viii (0.3) X (1.8) X (1.25) 100 IX (0.86) IX (0.6) X ( 3.6) X ( 2.5) 110 Thia Table shows the extant to which the formulations of the compositions according to the present invention can be modified, while still obtaining an excellent oleophobia which corresponds to the commercial standards.

Example 3» The same mixed cotton/polyester fabric ( 30/70) is used and the working conditions are the same as in Example 1. However, there is used an aqueous impregnating solution which contains, per liter, 36 g. of an emulsion of the homopolymer of 2 , 2-dimethylpropane-l, 3-diol perfluorooctanoate methacrylate containing 10$ dry matter, 10 g. of an emulsion of the copolymer of ethyl- hexyl acrylate and N-methylol-acrylamide (96/4) containing 20 dry matter and 90 g. of an emulsion of the copolymer of ethyl-hexyl methacrylate and N- methylol-acrylamide (96/4) containing 20% dry. matter, as well as g. of zinc nitrate hexahydrate as catalyst. After this treatment, the fabric contains Ο.252 g. of fluorinated compound and I.65 g. in all of resin per 100 g. of fabric.

In the following Table III, column 1 corresponds to the tests carried out on the new fabric, column 2 to the fabric washed according to the C.T.I.E. standard mentioned above and column 3 to the fabric dry-cleaned according to the C.T.I.E. standard also mentioned above.

TABLE III ftydrophobia t st Bundesmann: water absorption as 22 18 20 penetration of water as 0 0 0 Spray test: 100 90 100 Oleophobia test 100 100 100/110 The Table shows that this formulation according to the present invention satisfies the commercial standards of hydrophobia and oleophobia, even after washing and dry-cleaning.

Example 4» The fabric and the working conditions are the same as in Example 3« However, the 10 g. of the emulsion of the copolymer of ethyl-hexyl acrylate with N-methylol-acrylamide containing 2(¾s dry matter and the 0 g. of the emulsion of the copolymer of ethyl-hexyl methacrylate with N-methylol- acrylamide containing 2Co dry matter are replaced by 100 g. of an emulsion containing 202 dry matter of a copolymer obtained from 1.9 g. ethyl-hexyl acrylate, 17·3 g. ethyl-hexyl methacrylate and 0.8 g. N-methylol-acrylamide. As in Example 3, the solution also contains 5 g. of zinc nitrate hexahydrate as catalyst.

After this treatment, the fabric contains 0.252 g. of fluorinated compound and 1.65 g« in all of resin per 100 g. of fabric.

The following Table IV gives the results obtained on the new fabric (column l), on the washed fabric (column 2) and on the dry-cleaned fabric (column 3)· TABLE IV Hydrophobia test 1 _2_ _JL Bundesmann: water absorption as fo 18 16 16 penetration of water as cc. 0 0 0 Spray test: 100 90 100 Oleohobia test 100 100/110110 Example 5» The fabric and the working conditions are the same as in Example 3· However, there is added, in addition to the finishing composition of Example 3> g. per liter of an aqueous solution containing 10 o dry matter of a methylated melaniine-formaldehyde resin which is marketed by us under the name ''Synkamine MP" (component C). ("Synkamine1' is a aogioesad Trade Mark). Here, too, 5 g« of zinc nitrate hexahydrate are added per liter of bath. After the treatment, the fabric contains 0.252 g. of fluorinated compound and 3.12 g. in all of resin per 100 g. of fabric.

The tests for hydrophobia and oleophobia are carried out with new fabric (column l), washed fabric (column 2) and dry-cleaned fabric (column 3)· There are thus obtained the results set out in the following Table V: TABLE V Hydrophobia tast 1 2 Bundesmann: water absorption as fa 26 18 18 penetration of water as cc. 0 0 0 Spray tost: 100 100 100 Oleophobia test 110 100 110 Example 6.

This Example is cotton/polyester fabric is replaced by a fabric o?6^i^oi-^osic^t d^¾ ^? nylon. After the treatment, the fabric contains 0.252 g. of the fluorinated compound and 1.65 g« in all of resin per 100 g. of fabric. The tests refer again to new fabric (column l) , washed fabric (column 2) and dry-cleaned fabric (column 3) . There are obtained the results set out in the following Table VI: TABLE VI Hydrophobia test 1 2 Bundesmann: water absorption as % 25 29 27 penetration of water as cc. 0 0 0 Spray test: 95 85 85 Oleophobia test 100 100 100 Example 7.

This Example is the same as Example 3> except that the cotton/polyester fabric is replaced by a light nylon fabric and that the squeezing rate is 55 instead of "Jf/ After the treatment, the fabric contains 0.2 g. of the fluorinated compound and 1,3 g. in all of resin per 100 g. of fabric. The tests again refer to new fabric (column l), washed fabric (column 2) and dry- cleaned fabric (column 3) . There are thus obtained the results set out in the following Table VII: TABLE VII Hydrophobia test 1 2 Bundesmann: water absorption as % 7 7 3.4 penetration of water as cc. 0 0 0 Spray test: 100 95 100 Oleophobia test 90/100 80/90100 Example 8.

This Example is the same as Example 3, except that the cotton/polyester fabric is replaced by a cotton fabric. After treatment, the fabric contains 0.252 g. of the fluorinated compound and 1.65 g« in all of resin per 100 g. of fabric. The results are shown in the same manner as in Example 3 and 'are set out in the following Table VIII: TABLE VIII Hydrophobia test 1 2 Bundesmann: water absorption as % 33 35 36 penetration of water as cc. 0 0 0 Spray test: 95 85 85 Oleophobia test 100 100 100 Example 9.

The fabric and the working conditions are the same as in Example 3· However, there is used an aqueous impregnating solution which contains , per liter, 11.6 g. of an aqueous emulsion containing 10$> dry matter of a homopolymer o-f 2, 2-dimethyl-propane-l, 3-d.iol perfluorooctanoate methacrylate, 3.2 g. of an aqueous emulsion, containing 20/i dry matter of a copolymer of ethyl-hexyl acrylate and N-methylol-acrylamide { 96% and "4¾ respectively) , 29 g. of an aqueous emulsion containing 20/¾> dry matter of a copolymer of ethyl-hexyl methacrylate and N-methylol-acrylamide (96^ and φί, respectively) , and 30 g. of an aqueous solution containing "JOya dry matter of a methylated melamine-formaldehyde resin (obtained by the reaction of melamine, formaldehyde and methanol) which is marketed by us under the name of "Synkamine MP".

The bath also contains g» of zinc nitrate hexahydrate as catalyst. After this treatment , the fabric contains 0.0813 g. of fluorinated compound and 2 g. in all of resin.

In the following Table, column 1 corresponds to the tests made with the new fabric, column 2 to those with washed fabric and column 3 "to those with dry-cleaned fabric.

TABLE IX Hydrophobia test 1 2 L.

Bundesmann: water absorption as % 24 22 29 penetration of water as cc. 1 0 3 Spray test: 100 100 100 Oleophobia test 100 90 90 Example 10.

In this Example, there is used a Kraft paper with a weight of 80 g./ sq.m. A sample of this paper is impregnated in a bath containing, per liter, 30 g. of an aqueous emulsion containing 1 dry matter of a homopolymer of 2, 2-dimethyl-propane-l, 3-diol perfluorooctanoate methacrylate, JO g. of an aqueous emulsion containing 20 o dry matter of a copolymer of 2-ethyl-hexyl methacrylate and N-methylol-acrylamide ( 6)¾ and 4$, respectively^ 15 g. of an aqueous emulsion containing 20yl dry matter of a copolymer of 2-ethyl-hexyl acrylate and N-methylol-acrylamide (96;¾ and 4/*> respectively) and 54· 4 g« of an aqueous solution containing CFo dry matter of the methylated melamine-formaldehyde resin "Synkamine MP". The bath also contains 8 g. of zinc nitrate hexahydrate as catalyst. The paper thus treated is then squeezed to a squeezing rate of 60>o, air-dried for about 30 minutes and finally treated at 130°C. for 5 minutes. After this treatment , the paper contains 0.18 g. of the fluorinated compound and 2.17 g. in all of resin per 100 g. of paper. The oleophobia thus obtained corresponds to the value 110. Moreover, if a strip of 3 x 10 cm. of treated paper is suspended vertically in such a manner that 3 mm* of the lower end are insnersed in pea-nut oil, it will be found that the oil •has not risen in the paper mass after 24 hours* If, on the other hand, th same test is applied to untreated Kraft paper, an immediate rising of the pea-nut oil in the paper mass will be observed and after 24 hours the paper will be completely impregnated throughout .

Claims

1. HAVING EfOVJ particularly described and ascertained the nature of our said invention and in ¾rhat manner the same is to ' ¾e performed, we declare that what we olaim is 1, Composition for rendering porous and non-porous materials oil-repellent and water-repellent, which comprises as essential components: - a component (A) selected from the group consisting of homopolymers of fluorinated ethylenically unsaturated mixed asters of the general formula: R'CO2-Y-02CR" in which R'CO^ represents the residue of a perfluorcalkanoic acid, R'OOg is the residue of a polymerizable alkenoic acid, and Y is the bivalent residue of an organic compound selected from the group consisting of aliphatic, aromatic and aliphatic- aromatic dihydric alcohols, the carbon chain of which may be interrupted by oxygen atoms, and of copolymers selected from the group consisting of copolymers of the said fluorinated ethylenically unsaturated mixed esters with one another and of copolymers of the said fluorinated ethylenically unsaturated mixed esters with copolymerizable monomers selected from the group consisting of alkyl acrylates, alkyl methacrylates, acrylamide and methacrylamide, in admixture with at least one polymer selected from - a component (B) which consists of at least one copolymer selected from the copolymers of alkyl acrylates and alkyl methacrylates with an ethylenically unsaturated compound which contains a reactive group selected from N-methylol, N-alkoxymethyl, aldehyde and epoxy groups, and - a component (c) which consists of aminoplast resins selected from the polymeric products obtained by the reaction of amine compounds with aldehydes and eventually alcohols.

2. Composition as claimed in claim 1, in which the component (c) consists of an aminoplast resin obtained by the reaction of an amine selected from melamine and urea with formaldehyde, as well as its reaction products with alcohols.

3. Composition as claimed in claim 1, in which the component (c) consists of an aminoplast resin selected from alkylated urea-formaldehyde and alkylated melamine-formaldehyde resins.

4. Composition as claimed in claim 1, in which the component (B) contains by weight 0 to 99·57« of alkyl acrylates and/or methacrylates and 10 to 0.5^ΐ of the ethylenically unsaturated derivative having a reactive group selected from N-methylol, N-alkoxymethyl, aldehyde and epoxy groups. 5· Composition as claimed in claim 1, containing by weight 1 to 50$ of component (A) , 0 to 99$ of component (B) and 0 to 99$ of component (c). 6. Composition as claimed in claim 1, containing by weight 3 to 20$ of component (A), 0 to 60$ of component (B) and 0 to 60$ of component (C). 7» Composition as claimed in claim 1, in which the components (A), (B) and (C) are present in the form of a solution in organic solvents containing 0.1 to 50$ by weight of the components (A) + (B) + (c) and 99»9 to 0 by weight of at least one organic solvent. Θ. Composition as claimed in claim 1, in which the components (A), (B) and (C) are present in the form of a solution in organic solvents containing 0.5 to 3 $ by weight of the components (A) ♦ (Β) + (c) and . to 5$ by weight of at least one organic solvent. 9. Composition as claimed in claim 1, in which the components (A), (B) and (C) are present in the form of an aqueous emulsion or dispersion containing 0.1 to 50$ by weight of the components (A) + (Β) + (c) and 99.9 to 50$ by weight of water. 10· Composition as claimed in claim 1, in which the components (A), (B) and (c) are present in the form of an aqueous emulsion or dispersion containing 0.5 to 35$ by weight of the components (A) + (B) + (c) and 99.5 to 65$ by weight of water. 11. Composition as claimed in claim 1, which comprise 1 to 30 b weight of a cross-linking and adhesion catalyst as referred to the total weight of the components (A) + (B) + (c) . 12. Bath for rendering porous and non-porous materials oil-repellent and water-repellent comprising 0.1 to 20$ by weight of the oomponents (A) + (B) + (C) and 99.9 to 80$ by weight of at least one organic solvent, 13. Bath for rendering porous and non-porous materials oil-repellent and water-repellent comprising 0.5 to 10$ by weight of the components (A) + (B) + (c) and 99.5 to 90$ by weight of at least one organio solvent. 24· Bath for rendering porous and non-porous materials oil-repellent and water-repellent comprising 0.1 to 20$ by weight of the components (A) + (B) + (C) and 99.9 to θσ$ by weight of water. 1

5. Bath for rendering porous and non-porous materials oil-repellent and water-repellent comprising 0.5 to 10 by weight of the components (A) ♦ (B) + (C) and 9.5 to $Ofo of water.. 16· Process for rendering porous and non-porous materials oil-repellent and water-repellent, which comprises impregnating the material in a bath as defined in claims 12 to 15, drying the impregnated material at a temperature comprised between 1 and 100°C« to. evaporate the solvent or water and to form a coating and subjecting the material to a temperature comprised between 130 to 1808(5. 17· Porous and non-porous materials rendered oil-repellent and water-repellent by a composition according to claim 1. Dated this 25th day of August, 1967