CA2106662A1

CA2106662A1 - Fluoroacrylate monomers and polymers, processes for preparing same and their use

Info

Publication number: CA2106662A1
Application number: CA002106662A
Authority: CA
Inventors: Kathy Allewaert; Dirk Coppens; Franceska Fieuws
Original assignee: Individual
Current assignee: 3M Co
Priority date: 1991-04-26
Filing date: 1992-04-21
Publication date: 1992-10-27
Also published as: US5344956A; WO1992019663A1; AU671255B2; EP0582667A1; JP3126734B2; EP0582667B1; US5216097A; KR100210170B1; DE4143390A1; DE69211847T2; AU1990092A; DE4113634A1; JPH06507438A; DE69211847D1

Abstract

The invention provides polymers or copolymers which are prepared by the polymerization of the reaction product of a diisocyanate with a perfluoro compound or an epichlorhydrinadduct thereof and (meth)acrylic esters of a three hydroxyl groups containing compound. Furthermore, the invention relates to fluoroacrylic monomers, a process for preparing the polymers or copolymers and a treatment agent comprising the polymers or copolymers of the invention and an environmentally acceptable solvent. Polymers and copolymers of the invention can be used for making textiles, papers, non-woven articles, leather, plastic, wood, metal, stone and cement water and oil repellent.

Description

WO 92/1~)663 2 i l~ 6 ~ ~ 2 PCr/US92/0~300 FI.UOP~OACRYI~TE PlOMOPlER8 AND POh~S~8, PROCEB8E8 FOR PREPARING ~B 8ANE AND ~9IR ~BE
The present invention relates to polymers or 5 copolymers obtainable by the polymerization of th~
reaction products of diisocyanates with a perfluoro compound or an epichlorhydr~n adduct thereof and methacrylic esters of a compound containing three hydroxyl groups. Furthermore,.th2 invention relates to 10 a fluoroacrylic monomer as an inter~ediate product and to a process for preparing th~ poly~ers or copolymers and its u~2 providing water and oil repellency to textiles, papers, non~wo~en articles, leather, plastic, wood, metal, glass, stone and cement.
. Furthe~more, the invention rPlates tn a :-treatment agent which comprises the polymers or copolymers according to the invention and an .
environmentally acceptable ~olvent.
During the pact years there is a growing 20 market demand for flucrochemical product~ with good oil :.
and water repellency for the treat~ent of various substrate~. The use of ~luoroacrylic polymers for producte with good oil and water repellency for treatment of substrates i6 deRcribed in U.S. Pat. No.
25 4,778,915. This re~erence descri~s fluoroacrylic mono~ers and polymers which are prepared fro~ a diisocyanate, a polyfluoro compound and an acrylic or methacrylic 2ster of a 20alkylaminoethanol, preferably

2-t-butylaminoethyl-methacrylate. These fluoroacrylic 30 polymers can be used for the treatment of textiles or leather.
German Patent Publication No. A-31 19 058 describes a treatment agent for textile filaments consisting of a aqueous dispersion of a perfluoroalkyl 35 ester of a citric acid urethane and a fluorinated alcohol and the reaction product of an epoxy resin, a s2/l~663 ~ PCT/US92/03300 polymer with a carboxyl function and a aqueous solution of a tertiary amine.
u.s. Pat. No. 4,612,356 describes homo- and co-addition polymers of di-perfluoroalkyl carbamyl 5 group- containing ~meth)acrylate monomers and their use as oil and water repellency tre2tment o~ textiles.
European Patent Publication No. 0 lOo 277 describes a coating ~or infrared ~ransparency films consisting o~ a copolymer fo~ned from one fluorocarbon lO monomer preparPd ~rom equimolar amounts of N-ethylperfluorooctyl-sulfonamidoethanol, 2,4-toluene di-isocyanat and hydro~ypLopylma~hacrylate.
U,S. Pat. No. 4,920,l90 di~closes fluorinat~d acrylic monomers praparPd ~y reacting in a first stage 15 toluene 2,4~diisocyanat~ with an equimolar amount of a polyfluorinated compound to îorm a fluorinated urethane-isocyanate and then reacting this urethane-isocyanate with an equimolar amount of an acrylic ester.
The polymers and copolymers which are u~ed for the preparation of treatment a~ent6 for making substratec oil and water repellent have the digad-vantage that they are only soluble in environmentally unacceptable solvents such as l,l,l-trichloroethane and 25 trichlorotrifluoroethane in which they show a good performance. During the past years, there is a growing market demand for fluorochemical products which are soluble in environmentally acceptabliP solve~ts such as isopropanoI. U.S. Pat. No. 4,778,915 describes a 30 fluoroacrylic polymer which is soluble in isopropanol and from which aqueous dispersions can be prepared. The - disadvantage of the treatment agents described in this r reference is that the substances only show a very low performance in comparison to the treatment agents which 35 are dissolved in environmentally unacceptable solvents.
The present invention provides polymers or copolymers comprising the polymerization product of (a) .. ... ,.. .... . . , . , , ~ . . .~. , . . :

~VO92/196h3 21 ~ 6 6 ~ 2 PCT/US92/03300

- 3 -diisocyanate with a perfluoro compound or an epichlorhydrin adduct thereof, said perfluoro compound having a terminal hydroxyl, thiol, primary or 6econdary amino group attached to the perfluoroalkyl group 5 directly via an alkylene brldge or indireatly via an alkylene bridge and a sulphonamido, carbonamide, ether, thioether, sulphonyl or carboxylic ester group between the perfluoroalkyl and thP al~ylene group, and (b) (meth)acrylic esters of a three hydroxyl groups ~
lO containing compound. -The fluoroacrylate polymers of the pre5ent invention can be used as trPatment agents for maXing substrates oil and water repellent and ars easily soluble in environmental acceptable solvents like 15 isopropanol and water and provide good oil and water repellency.
In a preferred embodiment the tmeth)acrylic esters are the reaction products of an equimolar reaction between (me~h)acrylic acid and a three 20 hydroxyl group containing compound.
The reaction product which is used for the preparation of the polymer~i or copolymers according to the in~ention can be represented by the following general formula:
~Rf-Q-Il-NH-Z-NH-C-O 3 x -{-O-C-C=cH~

O n b R 3-n The fluoroaliphatic group is designated 30 herein as Rf. Rf is a stable, inert, nonpolar, preferably saturated mono~alent moiety which is both oleophobic and hydrophobic. A fluorinated oligomer preferably comprises from 2 to about 25 Rf groups and preferably comprises about 5 percent to about 30 35 percent, and more preferably about. 8 percent to about 20 percent fluorine by weight based on the total weight - :
of the oligomer, the loci of the fluorine being :~ .

''; ~''' , wos2/l~663 PCT/US92/0330~

- 4 -essentially in the ~f groups. Rf preferably contains at least a~out 3 carbon atoms, more preferably 3 to about 20 carbon atoms, and most preferably about 6 to about 12 carbon atoms. R~ can contain straiyht chain,

5 branched chain, or cyclic alkyl groups. Rf is preferably ~ree o~ polymerizable olefinic unsaturation and can optionally contain catenary heteroatoms such as oxygen, divalent or hexa~al~nt sulfur, or nitrogen. It is preferred that each Rf contain about 40% to about 10 78% fluorine by weight, mor~ prP~2rably about 50% to about 78~ fluorine by weigh~. The ~e~minal portion of the Rf group contains a fully 'luori~ated ~2rminal group. This terminal ~roup pr~ferably contains at lsast 7 fluorine atoms, e.g., C~3C~2CF2~ (C~3)2CF~ CF2SF5~ or 15 the like. Per~luorinat~ aliphatic groups, i.e., those of the ~ormula CnF2n+l, are the most pre~erred embodiments of Rf.
Linking group Q can be a covalent bond, a heteroatom, such a O or S, or an organic moiety. ~he 20 lin~ing group Q iB preferably an organic motety containing 1 to about 20 carbon atoms, and optionally containinq oxygen, nitrogen-, or sulfur-containing groups or a combination thereof, and preferably free of active hydrogen atomS. Example~ Of structures suitable 25 for linking group Q include straight chain, branched chain, or cyclic alkylene, arylene, aralkylene, oxy, oxo, thio, sulfonyl, sulfinyl, imino, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, and combinations thereof such as sulfonamidoalkylene.
30 Preferred linking groups Q can be selected according to ease of preparation and commercial availability. ~elow is a partially representative list of suitable organic Q groups. For the purposes of this list, each k is independently an integer from 1 to about 20, g is an 3S integer from 0 to about 10, h is an intP-ger from 1 to about 20, R' is hydrogen, phenyl, or alkyl of 1 to W092~19663 2 1 ~ ~ 6 6 2 PCT~US92/03300 about 4 carbon atoms, and R " is alky} of l to about 20 carbon atoms. :.
-S02NR'(CH2)k(O)C--CONR'(CH2)k~)C- :~
-~C~2)k(O)C- . ,, -CH2CH~OH)~H20~0)C~
-CH2CH(OR ")CH20tO)C- : .:
--(CH2)kC(o)o_ , - (CH2) kSc (o) - . :
--(CH2)kOtCH2)kO(O)C
-tCH2)kS(CH2)1~o(o)c- ' - ( CH2 ) k ( CH2 C~2 ) k ( O ) C
- ( CH2 ) kS2 ( CH2 ) X ( O ) C
-S02NR(CH2)X(CH2C~2)k(O)C
-(CH2)kS02NR(CH2)~0(0)C- '~
--( C~2 ) kS~2 -S02NR'(~H2)k OC6H4CH20 (O) C-S02NR(CH2)ho(cH2 ~ O)gCH2CH OC(O) CH2Cl CH2Cl -tCH2)hO(C~2CH O~gCH2CHOC(O~ ' CH2Cl ~2Cl (CH?~hO(cH2cH2o)~ cH2oc(o) ~CH2)h 0 (~HCH20)g1HCH2 OC(O) ~ :
CH3 ~3 -~CH2)h((o)c(~H2)6~)gc(o)(cH2)6~c~o) -(CH2)h((O)C(CH2)6NH)gC(O)(C~2)6NHC(O) , :, . -C(O)O~CH2320C(O)NH(CH2)2C() ,~

: 30 For linking Rf, Q i5 preferably alkyle~e or :' , sulfonamido, or sulfonamidoalkylene. .' : : R is a hydrogen or a methyl group, Z is a :'~
divalent aliphatic, alicyclic or aromatic connecting ,group. """."'~
The divalent organic linking group Z connects .~: ;
successive isocyanate moieties. Illustrative linking ! ' groups Z are alkylene groups, such as ethylene, , ~, WO92/1~63 PCT/US92/03300 ci,~

is~butylene, hexylene, and methylenedicyclohexylene, having 2 to about 20 carbon atoms, aralkylene groups, such as -CH2C6H4CH2- and -CfiH4CH2C6H4-, having up to 20 carbon atoms, arylene groups, such as tolylene, -C6H3(CH3)-, poly(oxyalXylene) groups, such as -(C2H4O)yC2H4~ wh~re y is 1 to about 5, and various y combinations of these groups. Such groups can also include other hetPro moieties (b~sides -O-), including -S- and -N-. How~ver, Z is preferably free of groups 10 with active hydrogen a~oms.
X is a trivalent connecting group. X can be aliphatic, aromatic or cycloalipha~ic. X is preferably an aliphatic group containing at l~ast 3 carbon a~oms and which may be st.aight chain or branched.
15 Particularly prafarred ars rasidues of alkanetriols and nitriloalkanols. Exampl~s o~ ~uch groups include, for example, the residues of trimethanolethane, triethanolamine, 1,3,5-trihydroxybenzene and 1,3,5-triæ(S-hydroxyethyl) cyanurlc acid.
~ is 1 or 2, preferably 2.
The fluorinated (meth)acrylic monomers of the formula (I) a~cording to the invention may be preparad by reacting a diisocyanate of formula O = C = N - Z - N 5 C = O (II) wherein Z is d~fined as above with preferably equimolar quantities of a polyfluoro compound of the formula 30 Rf - Q - H ~III) wherein Rf and Q are defined as above and a (meth~acrylic ester of the formula 35 (HO)n{X-O-fi-l ~ CH2~ (IV) O R 3-n WO92/19663 ~ l 0~ ~ 2 PCT/US92/03300 wherein n is 1 or 2, preferably 2 and R and x are as defined as above.
Examples of diisocyanates which may be used include aromatic diisocyanates such as 2,4 and/or 2,6 5 toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), and tMTMXDI) metatetramethylxylene ~:
diisocyanate. Furthermore, aliphatic diisocyanates such :.
as hexamethylene diisocyanate (HMDI), trimethyl- : :
hexamethylenediisocyanate (TMHMDI), decamethylene lo diisocyanate and Dimer Diisocyanate (DDI 1410 from Henkel) and alicyclic diisocyanates such as 4,4' .
methylene bis ~cyclohexyl isocyanate), trans 1,4-cyclohexyldiisocyanate ( CHDI ), isophorondiisocyanate (IPDI) can be used. Among these diisocyanates, 2,4-15 toluene diisocyanate (TDI) is especially prefPrred by ~: :
itself or mixed with the 2,6 isomer.
As the compound of formula (III), a perfluoro compound or an epichlorhydrin adduct thereof i~ used, the compound having a terminal hydroxyl, thiol, primary 20 or ~econdary amino group attached to the perfluoroalkyl group directly via alkylene bridge or indirectly via an alkylene bridge and a sulphonamido, carbonamide, ether, thioether, sulphonyl or carboxylic ester group betwPen - ~
the perfluoroalkyl and the alkylene group and .
2s (meth)acrylic esters of a three ~ydroxyl groups-containing compound.
Examples of such polyfluoro compounds include, but are not limited to, those of the following formulas~

Rf--(CH2) p--OH (III--a) R" ~ b) Rf -SO2 -I~ ( CH2 ) q~OH
: :
Rl/ (III-Rf-(CH2)p-SO2N-(CH2)-~H

.

,., ~ ..

W~ ~2/19663 PCI'/US~2/03300

6 2 - ~
- 8 - :
Rf--( CH2 ) p--O--( CH2 ) q~OH ( I I I--d ) Rf- (C!H2) p-S--(CH2) q~OH (III-e) S R~- ~ CH2 ) p- ( OCH2CH2 ) ,~-OH ( R~-(CH2)p-SO2 ~CH2)q)~0H ~ g) :

R"
Rf-C N-(CH2)p-OH (III-h) , R~-~-o-(CH2)p-OH (III~
o ~: ~
'' ' ': ",, Rf -CH=CH- ( CH2 ) p-OH ( I I I - j ) -Rf--( CH2 ) p--SH ( I I I--k ) Rf-(C~2)p-NB2 (III-l) - R-SO2-1-(CH2)~-NH2 (III-m) R~
: ' ' R~S02~N~(CX2)q~N~CH3 (III-n) R" H

; in which Rf has the same maaning as defined above and ~: : .:R" is hydrogen or:an al~yl group and the symbols p and:~ 30 q~which can:be identical or different each deno~e an integer ranging from 1 to 20 and preferably e~ual to 2 or 4.~Among these compounds (III),..those with a : ~ hydroxyl~functionality are preferred. Particularly preferred are the N-~; 35 alkyl(perfluorooctane)sulphonamidoal~yl alcohols or : telomer alcohols listed in Table 1 as fluorochemical : alcohols~. :

.

~VO~2/19663 PCT/US9~/0330() 2iO~6~2 _ 9 _ As examples of esters of the formula (IV) which may be employed for the ~ormation of the polymer according to the invention, acrylic and methacryl~c esters of the three hydroxyl group containing compound 5 can be used. Pxeferr~d are alkanetriols or nitrilotri-alkanols. Particularly preferred are the three hydroxyl group containing compounds listed in Table 1 (b1 - b5).
The products referring to ~ormula (IV) can be prepared by known techniques. T~us, equimolar amounts of ..
10 alkanetriol can be reacted with acrylic or methacrylic acid or alternati~ely acryloylchlor~de or methacryloyl-chloride can be reacted with alkanetriol. Preferably, the (meth)acrylic ester mixture of the alkanetriol is prepared ~y reacting 0.8 to 1.5 mol acrylic acid per 15 mol of alkanetriol.
The synthesis of the fluorinated (meth)acrylate monomer (I) according to the invention i6 praferably conducted in an organic solvent such as ketone, ester, ~romat~ ~olvents, alk~ne, halogenatad 20 hydrocarbon6, dimethylformamid2, N-methylpyrrolidone or acetonitrile. E8pecially preferred are methylethylk~tone, methyliso~utylk~tone, ethylaceta~e, butylacetate, toluene, xylene, benzene, hexane, heptane, cyclohexane, tetr~hydrofuran, diethylether, :
25 diethylene glycol dimet~yIet~er, l,1,1-trichloroe~hane, trichlorotrifluoroethane.
The addition reactions of the polyfluoro compound Rf-Q-H (III) and of the ~meth)acrylic esters (IV) to the isocyanate groups are carried out between 30 30OC and 9OoC under an inert atmosphere and in the ;~
absence of water. Since the reaction is very slow, it is preferred to conduct the reaction in t~e presence of a catalyst such as, for example, a tertiary amine, a tin salt and/or a lead salt. Preferably used are 35 triethylamine, triethylenedlamine, N-methylmorpholine, dibutyltindilaurate, tin octanoate, lead naphthonate.

~V~9~/19663 PCT/US9~/03300 The amount of catalyst is usually from 0.05 to 1 % .
based on the total weight of the reactants.
In order to limit the formation of symmetrical diaddition products, in a preferred 5 embodim~nt the perfluoro compound ~-~-H (III) iB added to the isoayanate comppund and react~d under in~rt atmosphere without a cataly6t. The (meth)acrylic ester is added in a second step and r~acts vary readily with the remaining free isocyanate groups when using a lO combination of a tertiary amine and a tin liX2 catalyst.
The invention further relat2s to the pol~mers containing repeating units of the ~ormul~ tI) in which the various symbols have the ~ame meanings as de~ined 15 before. ~he polymers may be prepared ~rom th2 mono~ers of formula (I) by homopolymerization or by c~polymerization with other monomers.
Examples of hydrocarbon and ~luorinated comonomer which may be used in the pxesent invention 20 include moieties derived from vinylethers, vinylester, alylester8, vinylketone~, ~tyrene, vinylamide, acrylamide~ maleates, fumar~tes, acrylates and (meth)-acrylate~. Pre~erably used are comonomers from acrylates and methacrylates. As examples of hydrocarbon 25 comonomers which may be used w~thin the scopa of the present invention the following are included:
Iower (halogenated or otherwise) olefinic hydrocarbon~ such as ethylene, propylene, isobutene, 3-. chloro-1-isobutene, butadiene, isoprene, chloro- and 30 :dichlorobutadiene, fluoro- and difluorobutadienes, 2,5-dimethyl-1,5-hexadiene and diisobutylene;
vinyl, allyl or vinylidene halides such as vinyl or vinylidene chloride, vinyl or vinylidene fluoride, allyl bromide and methallyl chloride;
styrene and its derivatives, such as vinyltoluene, ~-methylstyrene, ~-cyanomethylstyrene, divinyl benzene, and ~-vinylcarbazole;

~.
. . : . , . ~ ., W O 92/19663 P(~r/US92/03300 b/~A ~ ~

vinyl esters such as vinyl acetate, vinyl propionate, vinyl esters of anids known commercially - under the name of "Ver~atic Acidsl', vinyl lso~utyrate, vinyl senecioate, vinyl succinate, vinyl isodecanoate, 5 vinyl stearate and divinyl carbonate;
allyl esters such as allyl acetate and allyl heptanoate;
alkyl vinyl ethers or alkyl allyl ethers (halogenated or otherwise), such as cetyl vinyl ether, lQ dodecyl vinyl ether, isobutyl vinyl ether, ethyl vinyl ~ther, 2-chloroethyl vinyl ether and tPtraallyl oxy ethane; .
vinyl alkyl ketones such as vinyl methyl 15 ketone; unsaturated acids such as acrylic, ~ethacrylic, ~-chloroacrylic, crotonic, maleic, fumaric, itaconic, .:
citraconic and senecioic acids, their anhydrides and their esters such as vinyl, allyl methyl, butyl, isobutyl, hexyl, hep~yl, 2-ethylhexyl, cyclohexyl, 20 lauryl, stearyl or alkoxy ethyl acrylates and msthacryla~e~, dimethyl ~aleate, ethyl crotonat~, methyl hydrogen maleate, butyl hydrogen itaconate, glycol or polya~lkylene glycol diacrylates and dimethacrylates ~uch as ethyle~e glycol dimethacrylate :~ 25 or triethylene glycol dimethacrylate, dichloro-phosphatoalkyl acrylates and methacrylates such as di-chlorophosphatoethyl methacrylate, and bis(methacryl-oyloxyethyl) hydrogen phosphate and methacryIoyloxy : propyltrimethoxysilane;
acrylonitrile, methacrylonitrile, 2- ~
chloroacrylonitrile, 2-cyanoethyl arrylate, methylene ., :~ glutaronitrile, vinylidene cyanide, alkyl : :
cyanoacrylates such as isopropyl cyanoacrylate, tris(acryloyl)hexahydro-s-triazine, :
35 vinyltrichlorosilane, vinyltrimethoxysilane, vinyltri- :
ethoxysilane and N-vinyl-2-pyrrolidone; ;-""' :.' W09~/19663 ~ 31C~ PCT/US92/0330 allyl alcohol, allyl glycolate, isobutenediol, allyloxyethanol, o-allylphenol, divinylcarbinol, glycerol allyl ether, acrylamide, methacrylamide, maleamide and maleimide, N-S (cyanoe~hyl)acrylamide, N-isopropyl acrylamide, di-acetoneacrylamide, N-(hydroxymethyl) acrylamida and methacrylamide, N-(alkoxymethyl)-acrylamides and methacrylamides, glyoxal bisacrylamide, sodium acrylate or methacrylate, vinylsulphonic and styrene-p-sulphonic lO acids and their alkali matal salts, 3-amino-crotononitrile, monoallylamine, vinyl-pyridin2s, glycidyl acrylate or methacrylat~, allyl glycidyl ether, acrolein, N,N-dimethylaminoethyl methacrylat2 o~
N-tert-butylamino ethyl methacrylats ar~ used.
Fluorinated comonomers and methods ~or the preparation thereof are known and disclosed, ror example, in U.S. Pat. No. 2,803,615 (Ahlbrecht et al.).
Examples of ~uch compounds include general clas~es of 20 fluorochemical olefins such as acrylates, methacrylate6, vinyl ether~, and allyl compounds containing fluori~ated ~ulfonamido groups, acrylates or methacrylates derived from fluorochemical telom~r alcohoIs, fluorochemical thiols and the like.
Preferred compounds includ2, ~or example, N-methyl perfluorooctanesulfonamidoethyl acrylate, N-methyl perfluorooctanesulfonamid~ethyl methacrylate, N-ethyl perfluorooctanesulfonamidoethyl acrylate, the reaction product of isocyanatoethyl methacrylate and N-30 methylperfluorooctanesulfonamidoethyl alcohol, perfluorooctyl acrylate, N-methyl perfl~orooctane-sulfonamidoethyl vinyl ether, and N-allyl perfluorooctanesulfonamide, and others such as perfluorccyclohexyl acrylate, and tetrameric 35 hexafluoropropyleneoxide dihydroacrylate.
The fluoro copolymers according to the invention may be prepared in a per se known manner by ,, ....... . ~, . . .. . . . - .

WO92/1966~ PCT/US92/03300 2106~62 polymerization in an organic solvent or in an aqueousemulsion. Since the water and oil repellent agent according to the invention is usually uqed in solution, the sol~ltion polymerization is pre~erred. ~he process is usually carried out between 50C and 110C. The total monomer concentration may vary from 5 to 60% by weight. The polymerization in a ~olvent medium may be performed in the same solvents which are u~ed for the synthesis of the fluorochemical diurethaneacrylic o monomer (I).
The polymerization is carried out in the presence of initiators used in an amount o~ 0.1 to 1.5%
based on the total weight of the monomers employed. It is po~si~le to use peroxides such as benzoylperoxide, 15 lauroylperoxide, ~uccinylperoxide, and tert~butyl perpivalate, or azo compounds such as for example, -~
2,2'-azobisisobutyronitrile, 4,4'-szobis (4-cyanopentanoic acid) and azodicarbonamide. ~f required, the length of the polymer chains may be regulated by 20 means of chain transfer agent~ ~uch as alkylmercaptan, carbon tetrachlorid~ or triphenylmethane, used in a proportion of 0.05 to 1~ based on the total weight of the monomers.
The polymeriz~t~on in agueous emulsion may be 25 carried out according to well known method~. Various -surfactants-such as anionic, cationic, nonionic or amphoteric surfactants ~ay be employed as the dispersant. These surfactants may be used alone or in combination. -To more easily emulsify the monomer it is generally advantageous to u~e organic solvent6 such as, for example, ketones, glycols or ethylene glycol ethers, alcohols or mixtures of this solvents. In general, the quantity of solvent should not exceed the 35 total weight of the monomer. `~
Water soluble products such as inorganic peroxides and persalts or water insoluble initiators , ;

~ 2 14 -such as organic peroxides and the azo compounds referred to be~ore may also be used as polymerization initiator in an aqueous emulsion.
The polymers or copolymers of the invention 5 can be used as treatment agents in a solution of an environmentally acceptable ~olvent. Preferred solvents are alkanoles, ketones, asters or mixtures thereof.
Especially preferred is isopropanol.
Also polymer emul~ions can be prepared by 10 diluting the polymer according to the invention with water.
The polymers or copolymers of the invention and the treatment agents can be used for providing water and oil repellency to taxtiles, papers, non-woven 15 articles, leather, plastics, wood, metals, glass, stone and cement. Thare is no particular restriction on the methods used to apply the polymers or copolymers of the invention to ~he substrates, The application of the diluted produats may be carried out by spraying, 20 dipping or padding followed by drying at ambiQnt temperature or a temparatur~ which ~ay range up to 150C. The quantity of poly~er to be employed may vary within wide limits, dependi~g on the nature ~f the substrate and the ~luorine content of t~e polym r.
In the ~ollowing examples and co~parative -~ examples the water repellency (WR), the oil repellency (OR) and the spray rating (SR) were measured using the following tests.

30 Water Repellency Test The aqueous stain or water repellency of treated sample is measured using a water/isopropyl alcohol test, and is expressed in terms of a water repellency rating of the treated fabric. Treated 35 fabrics which are penetrated by or resistant to a l00 percent water/ zero percent isopropyl alcohol mixture (the least penetrating of the test mixtures) are given :, . :.. - ~-. . .

WO9~/19663 21 3 6 6 ~ 2 PCT/US92/03300 a rating of 100/0, whereas treated fabrics resistant to a zero percent water/100 percent isopropyl alcohol mixture (the most penetrati.ng of the test mixtures) are given a rating o~ 0/100. Other intermediate values are 5 determined by use of other waterti~opropyl alcohol mixtures, in which the percentage amounts of water and , isopropyl alcohol are each multiples of lO. Results are reported as an average of replicate testing. The water repellency rating corresponds to the most penetrating lo mixture which does not penetrate or wet the fabric after 30 seconds contact. In general, a water repellency rating of 90/10 or better, e.g., 80/20, is desirable for fabric.

15 Oil Repellency ~est The oil repellency of treated carpet and textile sample is measured by the American Association of Textile Chemists and Colorists (AATCC) Standard Test Method No. 118-1983, which test i~ based on the 20 resistance o~ treated fabric to penetration by oils of varying ~urface tensions. Treated fabrics resistant only to "Nujo~", a brand of mineral oil and the lea~t -penetrating of the test oils, are given a rating of 1, whereas treated fabrics resi~tant to heptane (the ~ost 25 penetrating of the test oils) are givan a value of 8.
Other intermediate~values are determined by use of :
other pure oils or mixtures of oils, as shown in the following table:
'':-.

, ~'.

wn 92/19663 PC~/US92/03300 ~a~ 2 -16 -5tandard Test Liquids AAT~C OIL
Repellency Rating Number Composition l "Nujol"
2 65:35 ~1Nujol~ n-hexadecane by volume ~ 70 F.(21 C.) 1 n-hexadecane 4 n-tQtraaecane n-dodecane 6 n-decane

7 n-oc~ane

8 n-heptane The rated oil repellency corresponds to the 20 most penetrating oil (or mixture of oils) which does not penetrate or wet the fabric 30 seconds contact.
Higher numbers i~dicate better oil repellency. In general, an oil repellency of 2 or greater is deslrable for ~abr~.
Sprav Ratinq Test The resistance of a treated substrates to wetting with water was measured usin~ a "Water Repellency Spray ~est as d~scribed in American 30 A~sociation of Textile Chemists and Color~sts Technical ~; Manual, 1977, 53, 245. Sample~ are rated o~ a ~cale of o to lOO with 0 indicating complete wetting o~ the upp2r and lower surfaces of the substrate and with a lO0 indicating no wetting.
- Examples The following non-limiting examples show embodiments of the invention. The reactants used in the examples are listed in table 1.

W~ 6~3 2 1 0 ~ 6 6 2 PCT/US92/03300 TABLE l Code Reactant Formulas . .
~olY~e~izahle monomer ~l CH2-CH-COOH ~crylic Acid 5 A2 CH2-C(CH3)-COOH Methacrylic Acid PolYols Bl CH3C(CH~OH)3 B2 CH3CH2C(cH2OH)3 10 B3 N(Cx2cH2OH)3 B4 HOCH2CHtOH)CH2OH -B5 HocH2cx(oH)cH2(cH2)3oH
Isoc~anates ~ NCO
~J "': "
N~O ~ .:
2,4 toluenediisocyanate MDI OCN ~ C~2 ~ NCO
4,4'-diphenyl~ethane diisocyanate 25 Desmodur W OCN ~ CH2 V -NCO
4,4~ me~ ylene ~lS tcyclohexyl i ocyanate) DDI 1410 Dimer Dii~ocyanate MW = 600 (Henkel) Fluorochemical alcohols Cl CgFl7SO2N~Et)CH2CH20H
C2 CaFl7S02N(Me)CH2CH20CH2CH(CH2Cl)oH
C8Fl7S02N~BU)cH2cH20H
C4 C8F17S02N(Me) (CH2)11H
c5 C8Fl7~02N(Me)CH2cH20H -C6 CnF2n+lcH2cH20~ (n is about B) c7 CnF2n~1CH2CH~ (CH2CIHO)nH
CH2Cl W0~2/19663 PCT/US~2//q330n ~ 2 18 -Preparation of the intermediate (Example 1) To a 2 liter 3-necked fla~k equipped with a heating mantle, stirrer, thermometer, dean-stark and re~luxcooler were charyed the following:

1,2,6-trihydroxyhexane 268.3 ~
Methacrylic Acid 172.18 g AMBERLYST 15 dry 13.2 g Heptane 189 g MEHQ O . 66 g phenothiazine 0066 g The mixture was heated to re~lux temperature and stirred for about 5 hours. Analysis by gas 15 chromatography showed that the reaction had ended. A
mixture containing mainly the monomethacrylate component and smaller amounts dimethacrylate and unreacted triol wa~ obtained. Thereafter, the heptane was evaporat~d o~f and a viscous clear product wa~ ob-20 tained. ~f~er dilution to 50% ~olids in i60butylm~thyl~
ketone, the AN~ERLYST beads were filtrated off. ~he product was ~tored unt$1 needed for urther reaction.

Example 2 91.5 g dry isobutylmethylketone and 26.6 g :(0.1 mol) Desmodur W (Bayer, 4,4'-methylene bis(cyclohexylisocyanate)), 64.9 g ~0.1 mol) N~methyl ~perf:luorooctane) sulphonamidoethyl epi(I)alcohol ~C8Fl7so2N~Me)c2H4ocH2cH(cH2cl)oH)/ and 3 drops o~
30 dibutyltindilaurate were charged into a 500 mL 3-necked flask equipped with a heating mantle, stirrer, thermometer, a reflux condenser and nitrogen inlet. Air was purged from the reaction flask with a stream of dry nitrogen, and then the temperature of the reaction 35 mixture was raised to 80C and stirred ~or about 1 hour (analysis by infrared absorption indicated that the reaction had ended). Thereafter, the reaction mixture ' ' :''.~' WO92/19663 2 î a ~ 6 ~ 2 PCT/USg2/03300 was cooled to about 50C and 20.2 g (0.05 mol, 50%
solids content~ of the methacrylate solution prepared in Ex. l, was added. The reaction mixture was again raised ~o 80~C for about 5 hours and was then cooled.
5 Infrared absorption analy5is of a small portlon of reaction mixture indicated that all of the isocyanate groups had been converted to urethane groups. 203.5 g of a yellow solution o~ a monomer according to the invention was obtained in this ~anner. This solution lO contained 50% solids.

Exam~les 3 -Following the general procedures of Examples : :
l and 2, and using react2nts shown in Tables l and 15 additional ~luorochemical (meth)acrylate monomers according to the invention were prepared.
~,:

Ex. Fluorochem. Isocyanate Polyol Polym.
20 No.
monomer :~
.

2 C2 Desmodur W ~5 2 2 5 3 Cl TDI B2 Al 4 C3 MDI . Bl A2 C6 TDI ~2 A
6 Cl MDI B4 A2 30 8 c5 DDI B3 A2

9 C4 TDI B2 A

The general mixtures corresponding to the acrylate monomer mixtures are shown in Table 2A.

WO92~1966~ PCT/US92/03300 ~Z 1~6 6 ~ 2 - 20 -a X~O-C-NH-Z-NH-I-Q-Rf)3 O O

5 b X(O-~-NH-Z-NH-~-Q-R~)2 O-C-C=CH2 'O R

10 c 0 R
X(O-C-C-cH2)2 bCNH-Z-NH-C-Q-Rf O

15 Example 10 Into a dry 500 ml three necXed flask fitted : with stirrer, addition funnel, a condenser, a thermometer, and nitrogen inlet and outlet, were placed 150 g (0.037 ~ol, SO~ ~olids) of the monomer solution :20 of Ex. 2, followed by lOO g isobutyl~ethylkQtone and 0.75 g n-octylmercaptan (1% on ~olids). A~ter purging : the reactor with n~troge~, the temperature of the ~, reaction mixture was ra~sed to about 650C and 0.75 g (0.5% on solids weight) of 2,2'-azobi~i~obutyronitrile (AIBN~ was added. The reaction mixture wa~ refluxed at about 65~oc for 16 hours. The reaction wa~ substantially ~: : complete as indicated ~y gaschromat~graphy. After ~: ~ cooling a yellow solu~ion of homopolymer according to the invention was obtained. The solution contained 30%
30 polymer solids.~ ; :
.: ~
Example 11 Into a reactor flask as described in Example ~ .
10 are added 105 g of the monomer solution, Ex. 2, 22.5 :5 35 g ethylacrylate and 122.5 g isobutylmethylketone and 0.75 g n-octylmercaptan. After purging the reactor with ;.
nitrogen, the temperature of the reaction mixture was ---`

-:
~:

W0 9~19663 2 l a f~ 2 PC'r/US~Z/03300 raised to 65C and 0.75 g AIBN was added. The polymerization was complete after 16 hours. The resulting yellow solution was filtered and contained 30% solids.
`:
Example 1~ - 25 In these examples, homopolymers and cop~lymers according to this inv~ntion, specified in ~ ~.
Table 3, were prepared and diluted to 0.5% solids in 10 isobutylmethylketon~ or isopropanol (see Table 3).
These dilutions were sprayed using "hand 8pray"
equipm~nt onto ta~til~ ~ubst~atQs (0.5~ ~olld~ on fabric (SOP')) and grain laather (0.018 g/m2, 0.2 g/sqft) and w~re le~t to dry for 24 hours at ambient :~
15 temperature b~fore the ~ollowing tests were carried ::
out : oil repellency (OR), water repellency (WR) and res istanc~ to waterspray ( SR) .
The test re~ults are set f orth in Tabl~ 3 .

2 0 TABI~3 Fluoro--monomer Pl:S/ Leather Ex Table 1 Como- Coltton grain No. No~ nomer SolYent OR WR SR OR WR

11 2 EA IPA 3+ 4 80 4 6 80

12 3 MIBK 3 5 70 2 4 70

13 3 isoBMA IPA 6 6 75 5 7 90 - 15 4 ~A NIBK 4 4 80 3 8 75 17 5 BenzMa MIBX 4 6 75 2 5 90 35 19 6 glycidlMA MIBK 1 3 70 3 4 70 23 8 tBA IPA 4 8 80 3 6 80 9 tBAEMA IPA 4 5 8 5 5 9 7 0 ~"O 92/196~3 PCI/US92/03300 Chemical_structure of the comonomers of table 3 EA Ethylacrylate CH2=CH--C~O)OC2Hs isoBMA Isobutylmethacrylate CH2Yc(cH3)-c(o)ocH2cH(cH3)2 LA ~aurylacrylate C~I2=CH-C(0~Ocl2H25 BenzMA Benzylmethacrylate ~ CH20C(0)-C(cH3)=cH2 glycidyl~A Glycidylmethacrylate CH2=C~CH3)-c(O)o~H2~HcH2 o AAEMA AcetoacetoxyethylMA
CH2=C~CH3) C(O) OCH2CH2OC(0) CH~C(0) CH3 tBA t-butylacrylate CH2=CH-C (O) OC ( CH3 ) 3 tBAEMA t-butylaminoethyl~A
CX2=CH-C (O) OCH2CH2NHC (CH3) 3 Solvenks of table 3 IPA = Isopropylalcohol - MIBK = Methylisobuthylketone 20 Example_26 Following th~ ~ame ~ethod used in Example 10, : a copolymer ~a~ prepared using as monomers 75 g (50%
solids solution) fluorochemical monomer Ex. No. 4 and 18.7 g t-butylaminoethylmethacrylate, C8Fl7so2N(Me)cH2cH2osc(CH3)=cH~.
o .
followed by 137.5 g isobutylmethylketone and 0.75 g n- -30 octylmercaptan. After purging the reactor with nitrogen, the temperature of the reaction mixture was raised to 65 C and 0.75 g AIBN was added. After 16 hours, the mixture was permitted to cool and gas chromatography indicated complete conversion. The 35 resulting solution contained about 30% solids.
. :' . .

WO 9~/lg663 ~ 1 0 ~ ~ ~ 2 PCr/US92/03300 This solution was diluted and applied as described in Examples 12 ~ 25 and the following results were obtained: : .
Polyester/Cotton O~ = 2 WR = 4 SR = 70 grain leather OR ~ 3 WR = 8 SR - 75 Example~L~
In Examples 27, 28, 29 and 30, five different - .:
substrates other than textile and leather were treated 10 with polymers corresponding to No. 10, 13, 20 of Table 3 as indicatsd in Table 4. These polymer solutions, . ;.
Nos. 10, 13, 20, ware diluted to 3.4% solids, in the same solvent as mentioned in Table 3, and each time 3 g of the diluted solution was sprayed onto the different 15 surfaces of about 160 cm2.
The substrates were left to dry at room temperature for 24 hours, and evaluated together with an untreated subatrate, Example 30, for oil repellency (OR), water repellency (WR) and spray rating (SR).
~ABLE 4 Polymer Ex No. of Ston~ Wood Pld~tic Gla~ M~tal No. Table 3 OR WR SR ~ OR W~ SR OR WR SR OR WR SR
25 27 I0 4 7 80 6 8 85 ~ 10 90 8 10 90 8 10 85 30 - O O O O 1 50 0^ 0 ~5 0 0 80 0 0 0 * WOOD : Mulitplex * STONE : Red Bric~stone * PLAS~IC : Polyesterfolie ~ ME~AL : Inoxplate :
Examples 31 - 42 In Examples 31 to 42, (0.018 g/m2, 0.2 g/sqft) of 1.5% solids solution of polymer no. 13 of the invention and solutions of prior art fluorochemical compositions were sprayed on~o chromium tanned grain and suede cow leather from Union Gantoise. ~he test results :

wO92/1s663 PCT/~S92/~3300 .
~ 2 - 24 -are shown in table 5, the samples were tested for OR, WR, SR and t~e bally water transfer test (See Scotchgard Leather Protector Manual, published by 3M Protective Chemical Products Division, January 1990).
In Examples 33 - 40, ~luorochemical compositions which contain ~nvironmentally unacc2ptable solvents were used. In Example~ ~1 and 42, compositions were tested~which use isopropanol as solvent. In Examples 31 and 32, the composi~ions according to the invention 10 were testad.
A~ can ~e seen îrom Table 5, the compo~itions according to th~ ln~ention show a similar performance compared to the Examples 33 - 40 which use environmentally unacceptable solYents. In comparison to 15 compositions test~d in Examples 41 and 42 wh$ch also use isopropanol as solvent, the perf ormanca of the compositions according to the invention is much better.

B~I~Y TE~T
W~ltOE~r tran~
D~ ted itur ~orp-Ex. ~ ~ ~n ~ 5he~ t~e o~ ~ ~ ~ ~on 31no. 13 30~ SPA U.G. graln5 4 100 15 ' 169~ . -32 U.¢. au3de 6 6 100 15 ' 30n 16~
33 A 3% IPA/BuAc U.G. graln3 7 90 12 ' 13%
30 34 U.G. ~ued~ S 6 80 12 ' 20~ :
B 253 Elept/ U.G. graln5 7 100 9'34" 26% .-BuAC
36 U.G. su~d~ 5 9 100 8'49" 2995 . .:
3~ C 4096 BuAC U.G. gra~ n 1 150 9 ' 48" 1496 :
3S 38 U.G. sueds 1 1 70 11~45" 28%
39EP-A2-- 40% ~uAc U.G. graln6 7 80+ 9 ' 11~ :~

U.G. ~u~d~ 6 9 100 10'10" 7%
41U. S . 31% IPA U.G. gratn1 3 80 5 ' 99~ ;:
4,778,915 42 U.G. ~uede 2 3 80 7 ' 19~ .
--:.
A = A fluorochemical urethane prepared according to U.s.
Patent No. 3,398,182 using fluorocarbon compound V, :
hydrocarbon compound LI and reactive compound J.
:

, .:

W092/l~663 , PCT/US92/03300 B = A fluorochemical copolymer prepared ac~ording to u.S~ Patent No. 3,341,497 using 65% N-methyl per-fluorooc~anesulfonamidoethyl methacrylate and 35% .
octadecyl methacrylate.
C = A fluoroahemical urethane prepared according to U.S.Patent No. 3,3~8,182 using fluorocarbon compound V, 2-ethyl hexanol as the hydrocarbon compound and reactive compound J.

Examples 43-43 In Example 43, the organic poly~er solution of 15 Example 13 was convert2d to an a~ueous dispersion by adding 200 g of the organic solutlon to an agueous phase (222 g water) which contained anlonic surfactant (14.4 g SE~MUL E~ 146) and 18 g ethylene glycol und~r ultra turax ~reatment at 65~C. This wa~ rollowed by two pas~es 20 through a high shear ho~ogeniz~r. The rei~ulting dispersion wa stripped of the isobutylmethylketone at reduced pre~ure with a water a~ptrator and a pot.
temperature of 65C to yield an anionic emulsion with 22% ..
to~al solids.
In Example 44, the proc~dure de~cribed in Example 43 wa~ u~ed to prepare a cationic emulsion except :; 200 g of the poly~er solution of Exampie 23 was substituted ~or the polymer of Example 13, and instead of the anionic 6ur~actant SERMUL EA 14~, cat~onic surfactan~ :
30 ETHOQUAD HT/25 (4.8'g) was u~ed.
In Examples 43 and 44, two different rainwear fabrics were treated with the cationic and anionic aqueous emulsions of fluorochemical polymer ~f :
composition nos. 13 and 23 of Table 3, as ind~cated in :.
35 Table 6. The fabri~s were treated in a padding operation, dried at 150C for 5 min., and evaluated together with untreated fabrics, Example 45, for initial oil repellency (OR), water repellency (WR) and resistance to a : waterspray (SR). An OR value of 3, a~d a SR of 70 or 40 greater is particulary desirable for this application.
-r ~

Ex. Table 3 Surfactant ~ PES/COTTON Nylon PA 66 no. no. ~3~on.solids SOF OR W~ . SR OR WR SR
43 13 Sermul EA146 o.3 2 4 75 3 2 70 5 44 23 Ethog. HT/25 0.3 3+ 3 75 3~ 3 70 45 / / / O O o O o O

Examples 46 - 47 In Example 46, the anionic aqueous emulsion of 10 composition no. 23 was evaluated for drum treatment on a chrome tanned full grain co~ hide. The purpose of a drum treatmen~ is to incorporate the fluorochamical into the protein structure of the leather. Example 47 was untreated.

Bally Test Absorp-Water- tion ABR ABR transfer ~ After E~. Poly~e~ OR WR SR ~R ~ e 2 hr~
~6 23 2 370 1 3 ~120 75.51 .
47 untreated 0 0 0 0 O 0 0 ~:
.
. .

:' .~

: 35

Claims

CLAIMS:

1. Polymers or copolymers comprising the polymerization product of a) diisocyanates with a perfluoro compound or an epichlorhydrin adduct thereof, said perfluoro compound having a terminal hydroxyl, thiol, primary or secondary amino group, attached to the perfluoroalkyl group directly via an alkylene bridge or indirectly via an alkylene bridge and a sulphonamido, carbonamide, ether, thioether, sulphonyl or carboxylic ester group between the perfluoroalkyl and the alkylene group, and b) (meth)acrylic esters of a three hydroxyl groups containing compound.

2. Polymers or copolymers according to claim 1, wherein the (meth)acrylic esters are the reaction products of an equimolar reaction between (meth)acrylic acid and a three hydroxyl group containing compound.

3. Polymers or copolymers according to claim 1 wherein the diisocyanates used are aliphatic, alicyclic or aromatic.

4. Polymers or copolymers according to claim 1 wherein the comonomers for preparing the copolymer include moieties derived from vinylethers, vinylesters allyl esters, vinyl ketones, styrene, vinylamide, acrylamides, maleates, fumarates, acrylates and methacrylates.

5. Polymers or copolymers according to claim 1 wherein acrylates and methacrylates are used as comonomers.

6. Polymers or copolymers according to claim 1 wherein the fluoro compounds are perfluoro alkyl substituted compounds with a terminal hydroxyl group.

7. Polymers or copolymers according to claim 6 wherein the perfluoro alkyl substituted compounds are N-alkyl(perfluorooctane)sulphonamido alkyl alcohols or telomer alcohols.

8. Polymers or copolymers according to claim 1 wherein the three hydroxyl groups-containing compound is a alkanetriol or a nitrilotrialkanol.

9. Fluoroacrylate monomer obtainable by the reaction of a) diisocyanates with a perfluoro compound or an epichlorhydrinadduct thereof, said perfluoro compound having a terminal hydroxyl, thiol, primary or secondary amino group, attached to the perfluoroalkyl group directly via an alkylene bridge or indirectly via an alkylene bridge and a sulphonamido, carbonamide, ether, thioether, sulphonyl or carboxylic ester group between the perfluoroalkyl and the alkylene group, and b) (meth)acrylic esters of a three hydroxyl group-containing compound.

10. Fluoroacrylate monomer of claim 9 wherein the (meth)acrylic esters are the reaction products of an equimolar reaction between (meth)acrylic acid and a three hydroxyl group containing compound.

11. Fluoroacrylate monomer according to claim 9 wherein said diisocyanates are aliphatic, alicyclic or aromatic.

12. Fluoroacrylate monomer according to claim 9 wherein the three hydroxyl groups containing compound is a alkanetriol or a nitrilotrialkanol.

13. Fluoroacrylate monomer according to claim 9 wherein the fluoro compounds are perfluoro alkyl substituted compounds with a terminal hydroxyl group.

14. Fluoroacrylate monomers according to claim g wherein the perfluoro compounds are N-alkyl-(perfluorooctane)sulphoneamido alkyl alcohols or telomeralcohols.

15. A process for preparing the polymers or copolymers of claim 1 comprising the steps of a) forming a fluoroacrylate monomer prepared by reacting a1) a diisocyanate with a perfluoro compound or an epichlorhydrinadduct thereof, said perfluoro compound having a terminal hydroxyl, thiol, primary or econdary amino group, attachod to the perfluoro-alkyl group directly via an alkylene bridge or indirectly via an alkylene bridge and a 6ulphonamido, carbonamide, ether, thioether, sulphonyl or carboxylic ester group between the perfluoroalkyl and the alkylene group, and a2) (meth)acrylic esters of a three hydroxyl groups containing compound and b) polymerizing the monomer by homopolymerization or copolymerization in an organic solvent or in an aqueous emulsion.

16. Process according to claim 15, wherein the (meth)acrylic esters are the reaction products of an equimolar reaction between (meth)acrylic acid and a three hydroxyl group containing compound.

17. Process according to claim 15 wherein the temperature range for the polymerization reaction is from 50 to 110°C.

18. Process according to claim 15 wherein the total monomer concentration is from 5 to 60% by weight.

19. Process according to claim 15 wherein the reaction is conducted in the presence of a catalyst.

20. Treatment agent comprising the polymers or copolymers of claim 1 and a environmentally acceptable solvent.

21. Treatment agent according to claim 20, wherein the solvent is an alkanol, water, a ketone, ester or a mixture thereof.

22. Treatment agent according to claim 20 wherein the solvent is water or isopropanol or a mixture thereof.

23. Treated substrates having oil and water repellency comprising substrates selected from the group consisting of textiles, papers, non-woven articles, leather, plastic, wood, metal, glass, stone and cement having applied thereto the polymers and copolymers of

claim 1.