Process for the protection of stony or coating surfaces

A method of protecting objects from graffiti using fluorinated polymers based on fluoropolyethers in a dry formulation wherein the fluorinated polymer includes a fluorinated part R.sub.F and optionally an hydrogenated part R.sub.H not containing groups capable of linking to basic acceptors by means of hydrogen bonds, the bonds linking the fluorinated part, derived from (per)fluoropolyethers, to the hydrogenated part being of simple C--O ether type, the T' terminal groups being such as to render the structure bi- or polyfunctional thus making possible the curing reaction, and subsequent curing of the fluorinated polymer.

The present invention relates to a process for avoiding the decay effects 
on the usual building materials and coatings by the use of inks, spray or 
brush paints, coloured chalks, etc. 
The damage caused by the decay of said materials is relevant especially on 
buildings of great artistic interest: besides an aestetic degradation 
there is generally an irreversible damage. 
Methods used to clean surfaces from these graffiti are the following: a 
posteriori treatments and a priori treatments. 
The a posteriori treatments of the treated surfaces essentially involve: 
a) a coating thereof with paint; 
b) an abrasive treatment; 
c) washing attempts with solvents. 
In any case the final result of any of such treatments leads to new clearly 
heterogeneous surfaces, cleaned surfaces different from the original ones, 
not stained surfaces. In particular it happens that: 
a) the treatment by paint, which involves the application of a waterproof 
film, contravenes one of the main criteria to adopt for the 
preservation-protection of stone materials, that is, the maintenance 
thereon of the possibility to "breathe" with the result of possible 
medium-long term damages; 
b) the abrasive treatment results in a real attack of the material and, 
even if possible and suitable, cannot obviously be carried out for 
repeated cleanings; 
c) cleaning with solvent leads to soak the material with the solvent-paint 
mixture leaving clear and permanent stains. 
To these inconveniences, the economic cost of these cleaning treatments is 
obviously to be added. 
To obviate these drawbacks, a priori treatments are used by applying 
filming and not filming substances which hinder or make them more easily 
removable graffiti. 
In Applicant's earlier Italian patent application No. MI94A001584, the 
prior art in the antigraffiti field was described and a composition 
allowing to overcome the drawbacks of the prior art was described. 
In particular it was described that the use of organic polymeric products 
characterized by having a high number of carbon-hydrogen bonds, such as 
for instance silicone and acrylic resins, provided a partial solution to 
the problem. However, these polymers show some drawbacks due to their low 
stability to light and air pollution. See for silicone resins G. Biscontin 
et al work published in Atti del Convegno di Studi di Bressanone 
24-27/11/1986, pg. 597. 
Moreover the materials known in commerce have a further limitation: also 
those resulting more effective have not a high durability. In practice 
only one cleaning of the graffito is sufficient to remove also the 
protective treatment. For this reason there are too high costs which 
hinder an application thereof on industrial scale. 
Improvements have been obtained by using perfluoropolyethers (PFPE) with 
perfluoroalkylic terminal groups. These polymers are effective when the 
material porosity is lower than 10%. See for instance Italian patent No. 
1161595. 
When the porosity is higher, it is known the use of perfluoropolyethers 
with functional terminal groups alone or, optionally, in admixture with 
tetrafluoroethylene, homo or copolymers, under the form of fine powders 
from 0.05 to 0.5 micron in amounts from 2 to 30% by weight; see Italian 
patent No. 1233420. 
The advantage of PFPE-based protective agents resides in that they allow 
the absorbed water ato evaporate through capillarity from the underlying 
stone or coating material. However also these products cannot be 
industrially utilized since, although the graffito is easily removed from 
90% of the treated surface, there are halos or stains left which change 
the aesthetic aspect of the underlying material and which require 
therefore an additional treatment of abrasive type for their removal. 
Therefore the same disadvantages occur as in the "a posteriori" cleaning 
indicated above. 
In Applicant's Italian patent application No. MI94A001584 mentioned above, 
cured polymers based on (per)fluoropolyethers having hydroxilic 
polyfunctional terminal groups have been described. They make it possible 
to carry out an a priori treatment on the surface of the materials to be 
protected againt graffiti and have a high durability without leaving 
either halos or stains and without modifying the surface of the treated 
material. The treated surface was resistant also to 10 cleaning operations 
wherefore frequent protective treatments of the surface could be avoided. 
This has clear practical advantages, both economic and industrial, however 
it requires high amounts of solvent with the relevant drawbacks related to 
their use and elimination. The Applicant has unexpectedly and surprisingly 
found that it is possible to utilize high dry compositions, wherein the 
amount of solvent is lower than 20% by weight, preferably lower than 
5-10%, as described in the European patent application No. 95101145.1, as 
antigraffiti which give the same optimal results described in the above 
mentioned application MI94001548 but utilize lower amounts of solvents. 
Also the products obtained by said European patent application are moreover 
suitable as compositions for use utilizable as antigraffiti by further 
reaction of the functional terminal groups. High dry products are obtained 
which have superior compatibility with crosslinking agents and pigments 
and contemporaneously result in transparent films with superior gloss, 
adhesion, hardness and folding resistance. 
Object of the present invention is therefore the use as antigraffiti of 
cured fluorinated polymers based on fluoropolyethers in high dry 
formulation. The fluorinated polymer comprises a fluorinated part R.sub.F 
and optionally an hydrogenated part R.sub.H, the bonds linking the 
fluorinated part, derived from (per)fluoropolyethers, to the hydrogenated 
one being of simple C--O ether type, the T' terminal groups being such as 
to render bi- or polyfunctional the structure, thus making possible the 
curing reaction, the hydrogenated part R.sub.H not containing groups 
capable of linking to basic acceptors by hydrogen bonds and subsequent 
curing of the fluorinated polymer. 
More particularly are preferred the fluorinatd products according to the 
formula 
EQU T'--(R.sub.H).sub.x --R.sub.F --(R.sub.H).sub.x --T' (I) 
wherein 
R.sub.F is 
##STR1## 
wherein R.sub.f is a fluoropolyether chain, where Y and Y' are equal to or 
different from each other and are F or CF.sub.3 
x is an integer from 1 to 10, preferably from 1 to 3; 
R.sub.H is a linking bivalent radical of linear aliphatic 
--(CH.sub.2).sub.m -- type, wherein m is an integer from 1 to 20, or 
(alkylen)cycloaliphatic, (alkylen)aromatic optionally having also 
heteroatoms on the ring or in the chain, the number of carbon atoms of the 
cycloaliphatic compounds being from 3 to 20, for the aromatic compounds 
from 5 to 30; the R.sub.H group can be a combination of the indicated 
types; 
T'=--(CH.sub.2 CH.sub.2 O).sub.n --(R.sub.H).sub.x' --T, wherein n is an 
integer from 0 to 6, preferably from 1 to 2; 
x' is an integer from 0 to 10, preferably from 1 to 3, x' being equal to or 
different from x; and 
T being hydrogen or a terminal group capable of making bi- or 
polyfunctional the structure as to render it reactive towards the curing 
agents both of ionic and radical type. 
In particular the preferred end groups of T type are of the type: 
##STR2## 
In particular groups which must be absent from the hydrogenated part 
R.sub.H are, for instance, --COOH, --NH--COO--; --NH--CO--NH--; --OH; 
--NH.sub.2 ; --NH--; --CO--NH--. 
The radical R.sub.f having molecular weight preferably comprised from 500 
to 5000, more preferably from 700 to 1500, represents a fluoropolyether 
chain bifunctional radical comprising as repeating units sequences of one 
or more oxyfluoroalkylenic units of the --CF.sub.2 CF.sub.2 O--, 
--CR.sub.4 R.sub.5 CF.sub.2 CF.sub.2 O--, 
##STR3## 
type. wherein R.sub.4, R.sub.5, equal to or different from each other, are 
selected from H and Cl. 
The fluorinated polymers of the present invention lead by addition of small 
amounts of solvent lead to the formation of solutions having a very low 
viscosity, generally of the order of 50-300 cPoise at room temperature. 
Amounts of solvents of the order of 2-3% by weight, selected from those 
generally utilized in the paints field, are sufficient to obtain solutions 
having extremely low viscosity as to make them easily utilizable. 
The preferred compounds of the formula I are the following: 
##STR4## 
These products and the process for the preparation thereof are described in 
European patent application No. 95101145.1, incorporated herein by 
reference. 
Also the products obtained from these fluorinated polymers before curing, 
as indicated above, are an object of the present patent application. 
A further object of the present invention is the use as antigrafiti of 
cured fluorinated polymers based on fluoropolyethers in high dry curable 
formulations comprising a fluorinated part R.sub.F and optionally an 
hydrogenated part R.sub.H, not containing groups capable of linking to 
basic acceptors by hydrogen bonds an hydrogenated part Rh.sub.1 and 
Rh.sub.2 wherein Rh.sub.1 is equal to or different from Rh.sub.2, and 
Rh.sub.1 and/or Rh.sub.2 being linking bonds containing at least a 
functional group capable of linking to basic acceptors by means of 
hydrogen bonds, the bonds linking the fluorinated part to the hydrogenated 
part being of simple C--O ether type, the terminal groups T'.sub.a and T" 
being such as to render mono-, bi- or polyfunctional the structure, and 
subsequent curing of the fluorinated polymer, the monofunctional products 
always being in admixture with a resin having a higher functionality also 
of the type described. 
The preferred fluorinated products, pure or in admixture have the formula 
EQU T"--(Rh.sub.2).sub.y (R.sub.H).sub.x --R.sub.F --(R.sub.H).sub.x 
--(Rh.sub.1).sub.y' T'.sub.a (II) 
wherein 
Rh.sub.1 and Rh.sub.2, equal to or different from each other, are linking 
bonds as R.sub.H but containing at least a functional group capable of 
linking to basic aceptors by hydrogen bonds; 
y and y' equal to or different from each other, are integers from 0 to 1, 
at least one of the two being different from 0. 
T'.sub.a =--(CH.sub.2 CH.sub.2 O).sub.n --(R.sub.H).sub.x' --T.sub.a 
wherein n is an integer from 0 to 6, preferably from 1 to 2; 
T"=--(CH.sub.2 CH.sub.2 O).sub.n --(R.sub.H).sub.x' --T.sub.b T.sub.a and 
T.sub.b being hydrogen or a reactive terminal group, capable of rendering 
the structure mono or polyfunctional such as to make the resin reactive 
towards the curing agents both of ionic and radical type, and T.sub.a 
being equal to or different from T.sub.b such that the T.sub.a and T.sub.b 
terminal groups are not all contemporaneously H. 
The meaning of the other groups has already been reported. 
In particular the preferred T.sub.a and T.sub.b terminal groups are: 
##STR5## 
The preferred Rh.sub.1 e Rh.sub.2 groups are: 
##STR6## 
In particular, groups which must be absent from the hydrogenated part 
R.sub.H are, for instance, --COOH, --NH--COO--; --NH--CO--NH--; --OH; 
--NH.sub.2 ; --NH--; --CO--NH--. 
The fluorinated polymers described above are described in a previous patent 
application of the Applicant, Italian patent application No. MI94A000474, 
incorporated herein by reference. These fluorinated polymers by addition 
of amount of solvent lower than 30% by weight on the formulation, lead to 
the formation of solutions having extremely low viscosities, generally of 
the order of 100-150 cPoise at room temperature. In practice the high dry 
fluorinated polymers of the former European patent application No. 
95101145.1 in the name of the Applicant, modified as indicated above, show 
a slight increase of the viscosity which is reduced by adding small 
amounts of solvent, generally lower than 10% by weight with respect to the 
formulations of the cited European application. 
The preferred compound of formula II are the following: 
##STR7## 
wherein: 
R.sub.H =--CH.sub.2 --, x=1, y=0 
Rh.sub.1 = 
##STR8## 
y'=1 T.sub.b = 
##STR9## 
n=0 and x'=0; T.sub.a =--COOH; 
##STR10## 
wherein: 
R.sub.H =--CH.sub.2 --, x=1, y=0 
Rh.sub.1 = 
##STR11## 
T.sub.a =H, n=0 and x'=0 T.sub.b = 
##STR12## 
wherein: 
R.sub.H =--CH.sub.2 --, x=1 
Rh.sub.1 = 
##STR13## 
y'=1, y=0, 
n=0 and x'=0 
T.sub.b = 
##STR14## 
T.sub.a =--N(CH.sub.2 CH.sub.2 OH).sub.2 
Other preferred structures: 
##STR15## 
R.sub.H =--CH.sub.2 --, x integer from 1 to 10, T.sub.b 
=(HOCH.sub.2).sub.2 --CH-- 
y=0 
y.sub.1 =1 
Rh.sub.1 = 
##STR16## 
T.sub.a =--COOH; 
##STR17## 
wherein the meaning is equal to the above structure with the difference 
that: 
Rh.sub.1 = 
##STR18## 
T.sub.a =H--; 
##STR19## 
wherein 
R.sub.H =--CH.sub.2 --, x=1; 
T.sub.b = 
##STR20## 
y'=1 Rh.sub.1 = 
##STR21## 
T.sub.a =H--; 
##STR22## 
as the above formula wherein Rh.sub.1 = 
##STR23## 
The solvents and crosslinking agents utilized with the fluorinated polymers 
of the present invention are indicated hereinafter. 
The generally utilizable solvents are those widely employed in the paints 
field, they are, for instance: ketones, esters, heteroalcohols esters, 
alcohols, aromatics. Methylethylethylketone (MEK), methylisobutylketone 
(MIBK), ethyl or butyl acetate (ButAc), cellosolve acetate, 
propylenglycolmethylether acetate (PMA), xylene, halogen compounds 
containing hydrogen such as fluorocarbons HCFC, HFC and having 
fluoropolyether structure, are preferred. Chlorofluorocarbons not 
containing hydrogen are excluded as solvents. 
The utilized crosslinking agents are the commercial ones and those anyway 
well known for curing curable functional groups. For instance 
polyhydroxylated products are curable with melaminic resins, with weight 
ratios comprised between 70:30 and 90:10, preferabaly 8:20, between 
polyhydroxylated compound and melamine; the curing temperature is around 
130-150.degree. C. 
The obtained films are homogeneous, transparent and hydrolysis resistant. 
Alternatively and preferably the polyhydroxylated polymers are curable with 
polyisocyanates containing isocyanurates rings, or utilizing suitable 
polyisocyanic prepolymers based on isoforondisocyanate (IPDI), 
toluendiisocyanate (TDI), hexamethylendiisocyanate (HDI), etc. in the 
presence of metal or aminic catalysts, at room temperature or higher, by 
using a NCO/OH ratio for instance from 1/1 to 1.5/1. 
Also blocked polyisocyanates, obtainable from the polyisocyanates indicated 
above by reaction, for instance, with phenols or ketoxime, can be used. 
If the resin is radically curable peroxidic curing can be performed by 
using conventional organic peroxides, for instance di-ter-butylperoxide, 
lauroylperoxide, benzoylperoxide. Also other radical initiators not of 
peroxidic type can be used, such as AIBN (aza bisisobutyronitrile). 
For the applications of the present invention as anti-graffiti, curings 
occurring at room temperature are preferred. This is in particular true 
when protection of buildings is involved, in which case it is unadvisable 
to cure at high temperature considering the obvious practical 
difficulties. On the contray in case of handmade articles of limited sizes 
or of plates which can be treated in factory, curing can also be performed 
at high temperature. 
In particular the fluoropolyethers of the R.sub.f type for use according to 
the present invention, generally of number average molecular weight Mn 
between 500 and 7000, can be of the type, by indicating the repeating 
units of the chain: 
a) --(C.sub.3 F.sub.6 O).sub.m' --, --(CFYO).sub.n' -- wherein the (C.sub.3 
F.sub.6 O) and (CFYO) units are perfluorooxyalkylenic units statistically 
distributed along the chain; m' and n' are integers such as to give the 
above indicated molecular weight and, when n' is different from 0, m'/n' 
is comprised between 5 and 40; X is equal to F or CF.sub.3 ; n' can also 
be 0; 
##STR24## 
wherein p' and q' are integers such that p'/q' ranges between 5 and 0.3, 
preferably 2.7-0.5 and such that the molecular weight Mn is in the range 
indicated above; t' is an integer with the meaning of m' and can also be 
0; Y=F or CF.sub.3 ; q'/q'+p'+t' is lower than or equal to 1/10 and the 
t'/p' ratio is from 0.2 to 6; 
c) --CR.sub.4 R.sub.5 --CF.sub.2 CF.sub.2 --O-- wherein R.sub.4 and R.sub.5 
are equal to or different from each other and selected from H, Cl, the 
molecular weight is in the range indicated above, a fluorine atom of the 
perfluoromethylene unit can be substituted by H, Cl or perfluoroalkyl 
having, for instance, 1-4 C atoms. 
The indicated (R.sub.f) fluoropolyethers are obtainable by the processes 
well known in the art, for instance, U.S. Pat. Nos. 3,665,041, 2,242,218, 
3,715,378 and European patent EP 0239,123. The functionalized 
fluoropolyethers with R.sub.f chain are obtained for instance according to 
EP patent 148,482, U.S. Pat. No. 3,810.874, or according to EP patent 
application 95101145.1. 
The functionalized fluoropolyethers of formulae I or II can be mixed among 
each other in various proportions or with other products of formulae I or 
II and/or with bi- or polyfunctional hydrogenated monomers or resins. 
Among the latter polyols are preferred, e.g. butandiol, 
trimethylolpropane, pentaerythrol, polycaprolactones, polyester or acrylic 
resins having low molecular weight. The ratio in equivalents between the 
monomer/hydrogenated resin with the fluorinated polymer of the invention 
ranges, generally, from 0.1 to 5, with the proviso that the formulation is 
an homogeneous solution. In this way blends are obtained having specific 
properties depending on the desired particular coating type. 
The molar ratio between fluorinated resins of formula II and those of 
formula I is, for instance, from 10:1 to 1:10. 
The process for preparing the fluorinated polymers of formula II consists 
in reacting the products of formula I with reactants capable of reacting 
with at least a reactive functional group of the terminal group T of the 
compound of formula I and with the stoichiometry such as to leave at least 
one of the reactive groups contained in the terminal groups T of formula 
I. 
Particularly suitable reactants belong to the following classes: 
anhydrides: aliphatic from 2 to 18 C atoms, for instance butyric anhydride, 
cycloaliphatic from 4 to 12 C atoms, hexahydrophthalic anhydride being 
preferred; aromatic from 8 to 12 C atoms, preferably phthalic anhydride; 
acylic chlorides: from 2 to 18 carbon atoms; for instance butyryl chloride; 
isocyanates: aliphatic having from 4 to 12 C atoms; preferably butyl 
isocyanate; cycloaliphatic having from 7 to 12 C atoms, preferably 
cyclohexyl isocyanate; aromatic having from 7 to 12 C atoms, preferably 
phenyl isocyanate; 
halohydrins having from 3 to 12 C atoms, preferably epychlorohydrin, 
secondary amines NHR.sub.1 R.sub.2, wherein R.sub.1 and R.sub.2 contain 
alcoholic functions, R.sub.1 and R.sub.2, equal to or different from each 
other, are aliphatic from 2 to 12 C atoms, preferably diethanol amine; 
amino silanes NH.sub.2 --R--Si(OR.sub.1).sub.3 with R and R.sub.1, equal to 
or different from each other, aliphatic groups having from 1 to 10 C 
atoms, preferably .gamma.-aminopropyltrimethoxysilane. 
The process for preparing fluorinated polymers based on fluoropolyethers of 
formula I comprises: 
etherification of the hydroxy-terminated fluoropolyether by its 
salification and nucleophilic reaction with alkylic or arylic dihalides or 
pseudohalides; a fluorinated polymer A') is obtained, whose formula 
corresponds to (I) wherein T' is replaced by X), in which the X end group 
is susceptible of further nucleophilic attack; subsequent 
functionalization by nucleophilic attack of A' with carboanion containing 
compounds to obtain the compound of formula corresponding to (I) 
containing the T terminal group, then optionally transformation of the 
functional T groups curable by reduction reaction or extension of chains 
with polyols, or ammonolysis or hydrolysis depending on the end group of 
the compound (I). 
The hydroxy-terminated perfluoropolyethers, for instance of the z.sup.2, 
p.sup.2 and A.sup.2 type, are obtainable according to known processes. 
(A.sup.2) HO(CH.sub.2 CH.sub.2 O).sub.n CH.sub.2 CF.sub.2 O(CF.sub.2 
CF.sub.2 O).sub.p (CF.sub.2 O).sub.q CF.sub.2 CH.sub.2 (OCH.sub.2 
CH.sub.2).sub.n OH, wherein for instance p/q=1, and n=1.8 and having a 
number average molecular weight Mn 1250 and functionality 1.95; 
(Z.sup.2) HOCH.sub.2 CF.sub.2 O(CF.sub.2 CF.sub.2 O).sub.p (CF.sub.2 
O).sub.q CF.sub.2 CH.sub.2 OH having for instance p/q=0.77, Mn 1000 and 
functionality 1.96; 
##STR25## 
(see just as an indication example 1). 
Z.sup.2 is obtained for instance by reducing the corresponding diester 
according to U.S. Pat. No. 3,810,874; A.sup.2 is obtainable by 
salification of Z.sup.2 and reaction with ethylene oxide. Analogously the 
compounds with fluorooxyalkylenic units specified above are obtained for 
all the products of Z.sup.2, P.sup.2 an A.sup.2 type. 
The process for preparing products of formula (I) is reported in European 
patent application 95101145.1, those of formula (II) in Italian patent 
application MI 95A000474, both applications are herein incorporated by 
reference. 
From the products of formula I thus obtained, as already said, the products 
of formula II are obtained by a partial transformation of the reactive 
functional groups of the T terminal groups to obtain T.sub.a and T.sub.b 
defined above. 
For instance if T contains reactive groups of --OH type it is possible to 
carry out the reaction by condensation with anhydrides, acids, esters, 
acylic chlorides. 
Depending on the stoichiometric ratio utilized between the compounds of 
formula I and the selected reactant, the resins of formula II can be 
directly obtained in admixture with the resins of formula I or mixtures of 
products of formula II. If the pure product of formula II is desired, this 
can be obtained directly by synthesis with the reactant, or by 
chemical/physical separation, for instance distillation or column 
chromatography or fractional precipitation. 
If the T groups contain reactive groups of epoxydic type it is possible to 
obtain T.sub.a and T.sub.b for instance by reaction with nucleophiles, 
such as for instance primary or secondary amines, carboxylic acids in the 
presence of basic catalysts. 
In Table IA are reported for illustrative but not limitative purposes some 
products of formula II starting from the resins of formula I to give 
T.sub.a and T.sub.b. 
__________________________________________________________________________ 
FLUORIN- 
ATED RESIN 
REACTANT PRODUCT 
__________________________________________________________________________ 
Z DOL (A.sup.2) 
1 #STR26## 
2 #STR27## 
Z DOL (A.sup.2) 
3 #STR28## 
4 #STR29## 
X = Cl, Br, OTs, OMs 
(XI) HN(CH.sub.2 CH.sub.2 OH).sub.2 
7 #STR30## 
(XII) 
1 #STR31## 
5 #STR32## 
(XII) 
6 #STR33## 
7 #STR34## 
Z TETRAOL (P.sup.2) 
1 #STR35## 
8 #STR36## 
Z TETRAOL (P.sup.2) 
9 #STR37## 
0 #STR38## 
Z EPOX (VI) 
NH(CH.sub.2 CH.sub.2 OH).sub.2 
1 #STR39## 
(VII) 
6 #STR40## 
2 #STR41## 
Z EPOX (VI) 
H.sub.2 N(CH.sub.2).sub.4 --Si(OCH.sub.3).sub.3 
3 #STR42## 
Z TETRAOL (P.sup.2) 
4 #STR43## 
##STR44## 
Z TETRAOL (P.sup.2) 
6 #STR45## 
8 #STR46## 
__________________________________________________________________________ 
To the obtained paint the usual additives such as pigments and fillers can 
be added; the latter must be produced inert, that is they must not contain 
groups reactive towards the terminal groups of the product of formula (I) 
or (II). 
The pigments and the fillers serve to improve the surface characteristics, 
such as consistency, hardness and moisture resistance, colour stability, 
etc., of the paint after spreading and drying on the treated surface. 
The pigments can be selected from the natural, synthetic inorganic and 
synthetic organic pigments. As example of inorganic pigments it can be 
mentioned: metal oxides: titanium dioxide, iron oxides, mixed oxides of 
Ni, Co, Zn, Ti or Cu, Cr or Fe, Ni, Cr, Mn, cobalt aluminates; organic 
pigments; derivatives from anthraquinone, quinacridone, 
tetrachloroisoindolinone, diketo-perylene, phthalocyanines, etc. 
The fluorinated products utilized for preparing the paints object of the 
present invention are sufficiently fluorinated to be compatible with 
fillers such as polytetrafluoroethylene, polyfluoroethylene-propylene, 
etc.. These fillers can be added in high amounts such as, for instance, up 
to 50% by weight. The fillers, as well as inert pigments and any other 
type of additive, are added to the dispersion in very fine form, generally 
with sizes lower than 100 microns. Other examples of fillers are: 
colloidal silica, polyamides having sizes 20-100 .mu.m, glass spheres such 
as zeolites, etc; other additives are for instance: thixotropic agents, 
acrylic, silicone, polyurethane, polyaminic dispersants or with carboxylic 
or non ionic functionality; stretching, anticissing, antistatic, antifoam 
additives, etc.; additives to reduce photooxidation; UV adsorber (for ex. 
hydroxybenzophenones, hydroxybenzotriazol derivatives, etc.) and HALS 
(hindered amines such as tetramethyl-piperidine derivatives, etc.). 
The paints object of the present invention are characterized by high 
water-repellence, low surface critical tension and low friction 
coefficient. 
The amount of fluorinated products of the invention to be applied on the 
surfaces to be protected ranges depending on the material to be treated, 
in particular depending on its porosity. Higher amounts are obviously used 
for porous materials. Amounts comprised between 10 and 50 g/m.sup.2 of 
surface to be treated are usually used. 
The application of the paints to the surfaces of the material or 
manufactured article to be protected can be carried out with any technique 
usually employed for such purpose: by brush, or by a compressed air gun 
and by a spray method. 
The curing of the paints of the present invention is carried out preferably 
at room temperature for a sufficient time to obtain curing. 
The following examples are given only for illustrative purposes but are not 
limitative of the scope of the present invention.

EXAMPLE 1A 
Preparation of the Products of Formula I 
100 g of a fluoropolyether of formula: 
EQU HO(CH.sub.2 CH.sub.2 O).sub.n CH.sub.2 CF.sub.2 O(CF.sub.2 CF.sub.2 
O).sub.p (CF.sub.2 O).sub.q CF.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2).sub.n 
OH (A.sup.2) (ZDOL) 
having p/q=0.84, n=O, Mn 950 (number average molecular weight) and 
functionality 1.93 are loaded in a 4 necks glass flask equipped with 
dropping funnel, thermometer, refrigerant and mechanical stirrer; the 
internal temperature is brought to 70.degree. C. 
1.14 g of potassium diterbutylate are added under nitrogen, a solution is 
obtained. 
After 15 minutes 15.82 g of glycidol 
##STR47## 
are dropped, the reaction mixture is maintained at 70.degree. C. for other 
4 hours. 
It is cooled and acidified with aqueous HCl, the salts are removed by 
filtering and water is eliminated by distillation at 100.degree. C. under 
vacuum. 
102 g of a product are obtained which on the basis of the analysis results 
to be: 
##STR48## 
In accordance with the structure reported above the hydroxylic equivalent 
weight, determined by .sup.19 F NMR analysis results to be 280. The 
viscosity results to be at 20.degree. C. of 2500 cPs. 
EXAMPLE 1B 
Preparation of Epoxy-Terminated Products of Formula (II) 
100 g of fluoropolyether diol of formula A.sup.2 (of Example 1A) are added 
to a solution containing 23.95 g of potassium terbutylate in 150 ml of 
terbutanol under nitrogen. 
The resulting solution is then added in 4 hours, by means of the dropping 
funnel, to an epibromidrine solution (100 g) in 20 ml of terbutanol at 
70.degree. C. When the pH of the solution becomes neutral, it is cooled, 
the salt is removed by filtering and the reaction solvent is distilled, 
then the excess of epibromidrine is eliminated under vacuum at 80.degree. 
C. 
102 g of a product of formula (VI): 
##STR49## 
are thus recovered, containing oligomeric products in amounts lower than 
5% by weight; the epoxy equivalent weight is 550 and the viscosity is 120 
cPs at 20.degree. C. 
The fluorinated resin of formula (VI) is formulated with the polyamine, for 
instance DETA (diethylentriamine) NH.sub.2 CH.sub.2 CH.sub.2 NH--CH.sub.2 
CH.sub.2 NH.sub.2 and cured. 
A transparent film of good adhesion and hardness is obtained. 
100 g of the product of formula (VI) are mixed to 30 ml of anhydrous 
isopropanol and to 10.1 g of diethanolamine previously anhydrified under 
vacuum at 90.degree. C. for 2 hours. 
Such mixture is heated to 80.degree. C. for 6 hours in a 3 necks reactor 
equipped with thermometer, refrigerant and mechanical stirrer. 
The reaction product results to be formed by the starting product (VI) 
(22%), by the ammine mono adduct (VII) (56%) and by the bisadduct (VIII) 
(22%), by column chromatographic separation the two addition products of 
formula: 
##STR50## 
are isolated. 
The product (VII) has an epoxy equivalent weight of 1150, an hydroxylic 
equivalent weight of 350 and a viscosity of 1100 cPs at 20.degree. C. 
The product of formula (VIII) has an hydroxylic equivalent weight of 285 
and a viscosity at 25.degree. C. of 8000 cPs. 
EXAMPLE 1 
The formulation based on fluorinated polymers of the class of type I, 
formula I, ZDOL of example 1A having average molecular weight 950 and 
hydroxyl functionality 1.93, described in table 1, was spray applied 
(nozzle 1.2 mm, 3 atm) on cement samples polypropylene loaded Cembonit of 
the company SIL (density 1.4 kg/dm.sup.3, max absorption of water 30% by 
weight) in amounts corresponding to about 100 g/m.sup.2. 
TABLE 1 
______________________________________ 
g dry component g 
______________________________________ 
ZDOL 45.2 45.2 
Polurene MC (Sapici) 
49.3 29.6 
(60% in PMA/ButAc 30/70)