FR2755695A1 - Compositions containing functionalised silicon fluids - Google Patents

Abstract

Cross-linkable composition comprises 20-50 wt.% polyisocyanate; 50-80 wt.% acrylic oligomer containing hydroxyl groups whose content in weight relative to oligomer is 2.5-4%; and 1-10 wt.% silicone oil of formula (I) R<1>(R<2>)2Si-O\2lR<2>R<3>Si-OmR<2>R<4>Si-OnR<2>R<5>Si-Oo(R<2>)2Si-OpR <6>Si-O3/2q (I), where o and p = 1-100, preferably 1-50; l = 2+q; q = 0-10; m = 1-60, preferably 1-30, most preferably 1-10; n is number such that 20<(100\*m)\/(m+n)<60, preferably 25<(100\*m)\/(m+n)<55; R<1>,R<2> = 1-4 C alkyl or alkoxy, or aryl, e.g. methyl, phenyl or methoxy; R<3>,R<4> are selected from monovalent radicals of type -(CH2)h-Si-(R<1>)3, where h = 1-10, preferably 1-3, and monovalent 1-4 C alkylaryl radicals; R<5>,R<6> = monovalent functional group selected from -R<7>-NH2, where R<7> =1-6 C alkyl, -R<8>-NH-R<9>, where R<8>,R<9> = 1-6 C alkyl; -(CH2)a(NHCH2CH2)bNH2 where a = preferably 1-3 and b = preferably 0-1; -(CH2)c(OCH2CH2)d(OCH2CHCH3)e-OH, where c = preferably 1-10, d = preferably 0-12, and e = preferably 0-15; -(CH2)f-SH where f = preferably 1-3; and -(CH2)g-C(R')2-OH, where g = preferably 1-3 and R' = 1-4 C alkyl, alkylaryl or aryl. Also claimed are: method for preparation of polyurethane film using said composition; polyurethane film obtained by thermal hardening of said composition; use of composition in making polyurethane films for protective covering; and article covered with said polyurethane film.

Description

CROSS-LINKABLE COMPOSITIONS CONTAINING SILICON OILS
FUNCTIONALIZATION AND USE OF THESE COMPOSITIONS
TO PREPARE POLYURETHANIC FILMS
The subject of the present invention is novel crosslinkable compositions for forming new polyurethane films containing functionalized silicone oils, and the use of new polyurethane films as a protective coating, in particular for automobile bodies, boat hulls; the bodies of household articles and appliances or any other surface.

Protective coatings must have many qualities combining aesthetic and visual aspects as well as properties of resistance to external influences. A first fundamental criterion of effectiveness for protective coatings is the ability to resist acids, in particular in the case of automotive paints or lacquers; these must be resistant to the action of acid rain. A second fundamental criterion of effectiveness lies in the level of the hydrophobic qualities which must of course be high. A third fundamental criterion is resistance to mechanical stresses such as scratch resistance.

Many coating or paint compositions containing silicone oils have been proposed. Note in particular the compositions of the patent
US N "5,268,215 or those of patent EP 531 463; however, these do not have all the qualities required to obtain stable and durable protections over time. In addition, these compositions sometimes require rigorous and complex implementation. for an application which does not guarantee minimum efficiency.

The object of the present invention is to provide novel crosslinkable compositions for forming polyurethane films. These new crosslinkable compositions which contain functionalized silicone oils have qualities, evaluated according to the above criteria, improved compared to the known compositions of the prior art. In addition, the new crosslinkable compositions are relatively quick to prepare and easy to use.

For the new polyurethane films resulting from the crosslinkable compositions of the invention, a marked improvement in the quality and stability of the properties of resistance to acids, properties of resistance to mechanical stresses such as resistance to scratching, and of hydrophobic properties is observed.

dans laquelle: (1) o et p sont des nombres entiers identiques ou différents compris entre 1 à
100, et de préférence de 1 à 50, (2) I représente un nombre entier tel que 1=2 + q, (3) q représente un nombre entier compris entre 0 et 10, (4) m représente un nombre entier compris entre 1 et 60, de préférence entre
1 et 30, particulièrement de préférence de 1 à 10, (5) n est un nombre entier tel que 20 < (100 x m)/(m + n) < 60, de préférence 25 < (100 x m)/(m + n) < 55, (6) les symboles R1 et R2 sont identiques et/ou différents et représentent un
radical hydrocarboné choisi parmi les radicaux alkyles linéaires ou ramifiés
ayant de 1 à 4 atomes de carbone, les radicaux alkoxylinéaires ou ramifiés
ayant de 1 à 4 atomes de carbone, les radicaux aryles, les radicaux
alkylaryles, et de préférence, un radical méthyle, un radical phényle, un
radical méthoxy ou un radical éthoxy, (7) les symboles R3 et R4 sont identiques et/ou différents et sont choisis
parmi:
- les radicaux monovalents -(CH2)h-Si-(R1)3 où h est compris entre 1 et
10, de préférence de 1 à 3,
- les radicaux monovalents alkylaryles aromatiques, la partie alkyle
linéaire ou ramifiée contenant 1 à 4 atomes de carbone, de préférence
le symbole R3 représentant le radical monovalent -CH(CH3)C6H5 et le
symbole R4 représentant le radical monovalent -CH2CH2C6H5,
(8) les symboles R5 et R6 sont identiques et/ou différents et représentent un
groupe fonctionnel monovalent choisi parmi
- une amine primaire monovalente de type -R7-NH2 où R7 est un radical
alkyle linéaire, ramifié ou cyclique ayant de 1 à 6 atomes de carbone,
- une amine secondaire monovalente de type -R8-NH-R9 où R8 et R9,
identiques et/ou différents, sont des chaînes alkyles linéaires, ramifiées
ou cycliques, ayant de 1 à 6 atomes de carbone,
- un radical monovalent -(CH2)a(NHCH2CH2)bNH2 où c et d sont des
nombres entiers indépendants:
a est compris entre 1 et 10, de préférence 1 à 3,
b est compris entre 0 et 10, de préférence 0 à 1,
- un radical monovalent-(CH2)c(OCH2CH2)d(OCH2CHCH3)eOH où c, d
et e sont des nombres entiers indépendants
c est compris entre 1 et 20, de préférence 1 à 10,
d est compris entre 0 et 70, de préférence 0 à 12,
e est compris entre 0 et 70, de préférence 0 à 15,
- un radical monovalent -(CH2)fSH où f est un nombre entier pouvant
aller de 1 à 10, de préférence 1 à 3,
- un radical monovalent -(CH2)S-C(R')2-OH où g est un nombre entier
pouvant aller de 1 à 10 et de préférence 1 à 3, et R' représente un
radical hydrocarboné choisi parmi un radical alkyle linéaire ou ramifié
ayant de 1 à 4 atomes de carbone, les radicaux aryles et les radicaux
alkylaryles.The new crosslinkable compositions according to the invention comprise: (a) 20 to 50% by weight of polyisocyanate, (b) 50 to 80% by weight of acrylic oligomer containing groups
hydroxyls, the content of which by weight relative to the acrylic oligomer is
between 2.5 and 4.5%, (c) 1 to 10% by weight of a silicone oil of formula (I)

in which: (1) o and p are identical or different integers between 1 to
100, and preferably from 1 to 50, (2) I represents an integer such that 1 = 2 + q, (3) q represents an integer between 0 and 10, (4) m represents an integer between 1 and 60, preferably between
1 and 30, particularly preferably 1 to 10, (5) n is an integer such that 20 <(100 xm) / (m + n) <60, preferably 25 <(100 xm) / (m + n ) <55, (6) the symbols R1 and R2 are the same and / or different and represent a
hydrocarbon radical chosen from linear or branched alkyl radicals
having 1 to 4 carbon atoms, alkoxylinear or branched radicals
having 1 to 4 carbon atoms, aryl radicals, radicals
alkylaryl, and preferably a methyl radical, a phenyl radical, a
methoxy radical or an ethoxy radical, (7) the symbols R3 and R4 are identical and / or different and are chosen
among:
- monovalent radicals - (CH2) h-Si- (R1) 3 where h is between 1 and
10, preferably 1 to 3,
- monovalent aromatic alkylaryl radicals, the alkyl part
linear or branched containing 1 to 4 carbon atoms, preferably
the symbol R3 representing the monovalent radical -CH (CH3) C6H5 and the
symbol R4 representing the monovalent radical -CH2CH2C6H5,
(8) the symbols R5 and R6 are the same and / or different and represent a
monovalent functional group chosen from
- a monovalent primary amine of the -R7-NH2 type where R7 is a radical
linear, branched or cyclic alkyl having from 1 to 6 carbon atoms,
- a monovalent secondary amine of the -R8-NH-R9 type where R8 and R9,
identical and / or different, are linear, branched alkyl chains
or cyclic, having 1 to 6 carbon atoms,
- a monovalent radical - (CH2) a (NHCH2CH2) bNH2 where c and d are
independent integers:
a is between 1 and 10, preferably 1 to 3,
b is between 0 and 10, preferably 0 to 1,
- a monovalent radical- (CH2) c (OCH2CH2) d (OCH2CHCH3) eOH where c, d
and e are independent integers
c is between 1 and 20, preferably 1 to 10,
d is between 0 and 70, preferably 0 to 12,
e is between 0 and 70, preferably 0 to 15,
- a monovalent radical - (CH2) fSH where f is an integer which can
go from 1 to 10, preferably 1 to 3,
- a monovalent radical - (CH2) SC (R ') 2-OH where g is an integer
which can range from 1 to 10 and preferably 1 to 3, and R 'represents a
hydrocarbon radical chosen from a linear or branched alkyl radical
having 1 to 4 carbon atoms, the aryl radicals and the radicals
alkylaryls.

The values of weight percentages relating to compounds (a), (b) and (c) relate to the total solid matter content of the crosslinkable composition, ie the solid matter of the three compounds (a), (b) and (c) ).

According to an advantageous embodiment in accordance with the invention, the scratch resistance properties are optimized with a crosslinkable composition comprising (a) 20 to 40% by weight of polyisocyanate, (b) 60 to 80% by weight of acrylic oligomer hydroxylated, and (c) 1 to 4% by weight of a silicone oil of formula (I), such that the NCO / XH molar ratio of the polyurethane films is between 0.5 and 1.5 and preferably between 0, 95 and 1.1. NCO is the isocyanate function of the polyisocyanate and XH represents OH, NH and SH which are the reactive functions of the acrylic polymer and those of the functionalized silicone oil. In addition, the acrylic oligomer advantageously contains between 2.5 and 4.5% by weight of hydroxyl groups.

The crosslinkable composition generally contains a solvent such that the percentage by weight of compounds (a), (b) and (c) relative to the crosslinkable composition containing a solvent is between 50 and 80%, and preferably of the order by 60%. Different types of solvents can be used, for example, methyl amyl ketone, butyl acetate or the Solvesso 100 product (obtained from a petroleum cut).

The structure of the silicone oil contained in the composition according to the invention is chosen such that said oil is poorly miscible with the system consisting mainly of the mixture of acrylic oligomer and polyisocyanate. In this regard, the 2-phenylethyl and 1 -phenylethyl groups present within the structure of the silicone oil improve the miscibility of the chain of the silicone oil in the acrylic oligomer and polyisocyanate system. The content of Si units modified in the silicone oil by these groups varies from 20 to 40%.

In addition, according to another advantageous embodiment of the invention, the crosslinkable composition comprises silicone oils functionalized with units of HALS type.

dans laquelle: (1) les radicaux monovalents R11 sont identiques et/ou différents, choisis parmi
les radicaux alkyles linéaires ou ramifiés ayant 1 à 3 atomes de carbone et le
radical phényle, (2) le radical monovalent R12 représente un radical hydrogène, (3) le radical R10 est un radical hydrocarboné divalent choisi parmi
* les radicaux alkylènes linéaires ou ramifiés, ayant 2 à 18 atomes de
carbone,
+ les radicaux alkylènes-carbonyles dont la partie alkylène linéaire ou
ramifiée, comporte 2 à 20 atomes de carbone,
les radicaux alkylènes-cyclohexylènes dont la partie alkylène linéaire ou
ramifiée, comporte 2 à 12 atomes de carbone et la partie cyclohexylène
comporte un groupement OH et éventuellement 1 ou 2 radicaux alkyles
ayant 1 à 4 atomes de carbone,
les radicaux de formule-R13-O-R13 dans laquelle les radicaux R13
identiques ou différents représentent des radicaux alkylènes ayant 1 à
12 atomes de carbone, * les radicaux de formule -R13 - O - R13 dans laquelle les radicaux R13 ont les
significations indiquées précédemment et l'un d'entre eux ou les deux sont
substitués par un ou deux groupement(s) -OH;
les radicaux de formule -R13 - COO - R13 dans laquelle les radicaux R13 ont
les significations indiquées précédemment,
les radicaux de formule -R14 -O-R15 - o-Co-R14 dans laquelle les radicaux
R14 et R15 identiques et/ou différents, représentent des radicaux alkylènes
ayant 2 à 12 atomes de carbone et le radical R9 est éventuellement
substitué par un radical hydroxyle, * U représente -O- ou -NR16-, R16 étant un radical choisi parmi un atome
d'hydrogène, un radical alkyle linéaire ou ramifié comportant 1 à 6 atomes
de carbone et un radical divalent de formule:

In this case, at least part of the symbols R5 and R6, similar and / or different from silicone oil, represent a monovalent functional group chosen from a residue of formula (II) defined below and such that the number ratio of functional groups of formula (II) / number of Si units of the silicone oil is between 5 and 15%

in which: (1) the monovalent radicals R11 are identical and / or different, chosen from
linear or branched alkyl radicals having 1 to 3 carbon atoms and the
phenyl radical, (2) the monovalent radical R12 represents a hydrogen radical, (3) the radical R10 is a divalent hydrocarbon radical chosen from
* linear or branched alkylene radicals having 2 to 18 atoms of
carbon,
+ alkylene-carbonyl radicals including the linear alkylene part or
branched, has 2 to 20 carbon atoms,
alkylene-cyclohexylene radicals including the linear alkylene part or
branched, has 2 to 12 carbon atoms and the cyclohexylene part
contains an OH group and optionally 1 or 2 alkyl radicals
having 1 to 4 carbon atoms,
the radicals of formula-R13-O-R13 in which the radicals R13
identical or different represent alkylene radicals having 1 to
12 carbon atoms, * the radicals of formula -R13 - O - R13 in which the radicals R13 have the
meanings given above and one or both of them are
substituted with one or two -OH group (s);
the radicals of formula -R13 - COO - R13 in which the radicals R13 have
the meanings indicated above,
radicals of formula -R14 -O-R15 - o-Co-R14 in which the radicals
R14 and R15, which are identical and / or different, represent alkylene radicals
having 2 to 12 carbon atoms and the radical R9 is optionally
substituted by a hydroxyl radical, * U represents -O- or -NR16-, R16 being a radical chosen from an atom
of hydrogen, a linear or branched alkyl radical containing 1 to 6 atoms
of carbon and a divalent radical of formula:

in which R10 has the meaning indicated above, R11 and R12 have
the meanings indicated above and R17 represents a radical
divalent alkylene, linear or branched, having 1 to 12 carbon atoms,
One of the valential bonds (that of R17) being linked to the atom of -NR16-, the other
(that of R1o) being connected to a silicon atom.

According to a preferred embodiment of the invention, the ratio of the number of functional units of type (II) / number of Si units of the silicone oil is of the order of 6%.

On the other hand, the R12 radical of formula (II) may represent, in addition to a hydrogen radical, an R11 or O radical; which also gives the polyurethane films improved properties of protection against U.V. radiation.

Advantageously, the silicone oil can also contain hydroxyaryl units within its structure. These units have antioxidant properties and properties of protection against UV radiation and the ratio of the number of these hydroxyaryl units / number of Si units of the silicone oil being between 1 and 15%. In this case, at least part of the symbols R5 and R6, similar or different, represents a functional group - (CH2) n (V) (Ar) where
- n is between 1 and 10,
- the V radicals are identical and / or different and represent a divalent radical
selected from -NH-, NHR'-, -CHN-, -O-, -CHN-, -COO-,
- R 'is a linear or branched alkyl radical having 1 to 4 carbon atoms, and
- Ar is an aromatic group substituted by at least one OH radical and which can
be substituted by at least one hydrocarbon radical containing from 1 to 4 atoms
of carbon and possibly comprising a heteroatom, preferably Ar being a
phenol group.

As examples of hydroxyaryl units, reference will be made to those described in US Patents 4,430,235 and US. 4,879,378.

The polyisocyanate used in the context of the invention can be prepared according to different procedures and from different compounds. The characteristics of the polyisocyanate used can vary from one composition to another while remaining within the scope of the invention. For example, the polyisocyanate can be in the form of a trimer, a dimer, a biuret or a mixture thereof.

The viscosity of the polyisocyanates obtained and used in the context of the invention is between 2000 and 9000 mPa.s, and preferably is of the order of 2500 mPa.s. In addition, the NCO content of the polyisocyanates used is between 15 and 25% by weight relative to the dry extract of the polyisocyanate.

The preferred diisocyanates for the preparation of the polyisocyanates of the compositions according to the invention are those of formula R (NCO) 2 in which R is a divalent aliphatic hydrocarbon group having from 4 to 18 carbon atoms, a heterocycloaliphatic group whose ring contains 3 with 15 carbon atoms.

By way of examples, the following diisocyanates are suitable for the preparation of the polyisocyanates used in the compositions of the invention: 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1, 6-hexamethylene diisocyanate, 1, 1 2-dodecamethylenedi isocyan ate, cycloh exane- 1, 3-diisocyanate, cyclohexane 1, 4-diisocyanate, 1 -isocyanato-2-i socyanatomethylcyclopentane, 1 -isocyanato-3isocyanatomethyl 3,5,5- trimethylcycloh exane, bis- (4-isocyanatocyclohexyl) -methane, 1, 3bis (isocyanatomethyl) -cyclohexane, 1,4-bis (i socyanatomethyl) -cyclohexane, bis- (4-isocyanato-3-methyl-cyclohexyl) -meth ane , a, a, a ', a'-tetramethyl- 1, 3- and / or-1, 4-xylylene diisocyanate, 1 -isocyanato-1 -methyl-4 (3) -isocyanatomethyl cyclohexane, and 2,4- and / or 2,6-hexahydrotoluyl diisocyanate.

Preferably, the polyisocyanate is prepared by oligocondensation or polycondensation of polymethylene diisocyanate derivatives and in particular tetramethylene diisocyanate and hexamethylene diisocyanate.

Among these polycondensates or oligocondensates, it is possible to cite those prepared from mixing the diisocyanates mentioned above with monoisocyanates or polyisocyanates having at least 3 isocyanate groups. More particularly, mention should be made of derivatives with an isocyanuric ring (s) [designated under the term trimer], and derivatives having a biuret function.

The aliphatic or aromatic isocyanates, and preferably aromatic, are dimerizable at room temperature, more particularly in the presence of a dimerization catalyst such as triethylphosphine, pyridine, triethylamine or alkoxymetallic complexes.

The aliphatic or aromatic isocyanates are trimerisable at high temperature, in the presence of a trimerization catalyst such as calcium acetate, sodium formate, triethylamine or triphenyl phosphine. The trimers obtained form structures which are extremely stable to heat and to hydrolytic attack, and are characterized by a molecular weight of between 100 and 5000.

As examples of commercial products, the products marketed by
Rhône-Poulenc and Bayer AG are suitable for their use as a polyisocyanate in the compositions of the invention. On this subject, we will mention the products of the range
Desmodur from Bayer AG, including Desmodur N 3390 and Desmodur N 3300, products from the Tolonate HDT range from Rhône-Poulenc (Tolonate HDT LV and Tolonate HDT 90).

The hydroxylated acrylic oligomer, used in the crosslinkable compositions of the invention, has a hydroxyl group content by mass of 3.1 to 5.2% (relative to the dry extract) and a viscosity of 4000 to 6000 mPa.s. At least part of the OH groups contained in the acrylic oligomer are reactive with respect to isocyanate groups during the formation of the polyurethane films from the crosslinkable compositions of the invention.

By way of examples, the acrylic oligomers containing hydroxyl groups which can be used in the context of the invention are chosen from: 2hydroxyethylacrylate, 2-hydroxypropylacrylate, 2-hydroxyethylmethacrylate and 3hydroxypropylmethacrylate.

In general, acrylic oligomers are used as a solution in solvents and have a viscosity of 4000 to 10,000 mPa.s. Different types of solvents can be used, for example, methyl amyl ketone, butyl acetate, etc. Preferably, the solvent used is methyl amyl ketone. In general, the concentration by weight of acrylic oligomer in the solution of said oligomer is between 40 and 80%. In the case where methyl amyl ketone is used as solvent, the concentration by weight of acrylic oligomer is between 50 and 80%. However, it is possible to use acrylic oligomers without solvent within the scope of the invention.

As examples of commercial products, the products marketed by the companies Rhône-Poulenc, Dupont de Nemours, Johnson, Akzo, Hoechst, Cray Valley,
Croda are suitable for their use as a hydroxylated acrylic oligomer in the compositions of the invention. These include the products of the Johnson SCX range, in particular 910 and 920, the products of the Setalux range (1753 SS 60, etc.), the products of the Macrynal range (SM 510, etc.), the products of the range Synocure and the products of the Crodaplast range.

The preparation of polyurethane films from the crosslinkable compositions can be carried out according to various techniques such as by chemical curing, thermal curing, U.V. radiation or the use of an electron beam.

According to a preferred variant of preparation, the polyurethane films are obtained by heat treatment at a temperature between 50 and 200 "C and advantageously between 80 and 150 C. In addition, the best results are obtained in the presence of a catalyst such as as dibutyltin dilaureate, tin octanate, dibutyltin diacetate, thus promoting the reactions between the silicone oil, the polyol and the polyisocyanate. Advantageously, the catalyst used is dibutyltin dilaureate. Other catalysts can also be used for preparing polyurethane films, in this connection reference will be made in particular to document EP 524 501 A1. Preferably, the catalyst is added just before the addition of the polyisocyanate.

By way of example, the method of preparation by heat treatment of a polyurethane film comprises the steps consisting in
(1) mix the solvent, the hydroxylated oligomer and the silicone oil,
(2) add and mix the polyisocyanate to the mixture obtained in (1),
(4) spread the mixture on a perfectly clean and even surface, and
(5) dry the spread mixture and then cook it at a temperature between 50 "C
and 200 ° C, for 20 minutes to 1 hour.

As a variant of the preparation of polyurethane films from crosslinkable compositions according to the invention, silicone oil is mixed with the acrylic oligomer.

The polyisocyanate, the solvent and, optionally, the catalyst are then added to this mixture. It is also possible to bring a portion of the polyisocyanate into contact with the silicone oil beforehand. These two compounds having reacted with each other, they are then mixed with the acrylic oligomer, the polyisocyanate if necessary, the solvent and, optionally, the catalyst.

In accordance with the invention, the operating conditions for preparing polyurethane films and the compounds of the crosslinkable compositions, ie qualities and quantities, are chosen so that the NCO / XH molar ratio of the polyurethane films is between 0.5 and 1.5. and preferably between 0.95 and 1.1; NCO being the isocyanate function of the polyisocyanate and XH representing OH, NH and SH which are the reactive functions of the acrylic polymer and those of the functionalized silicone oil.

In particular, the controlled miscibility of silicone oil within the acrylic oligomer and polyisocyanate system allows it to migrate at a relatively low speed towards the surface of said film at the time of its formation, this low speed allowing, moreover, to silicone oil groups carrying active hydrogens react with the polyisocyanate. Thus, the major part of the silicone oil is found in the surface layer of the film and is fixed by chemical bond in the polyurethane matrix, which provides permanent anti-scratch properties even after several washes of the film, confirmed by the examples.

The improvement in the anti-scratch properties is observed in particular by a better sliding of the surface of the film which prevents the formation of scratches. If however the scratch does occur, the silicone oil present in the surface layer of the film fills the scratch (obtaining a state of minimum energy), which allows the occlusion of the scratch (healing effect).

The field of use of the polyurethane films obtained from the crosslinkable compositions of the invention is very varied. The films obtained from the crosslinkable compositions according to the invention can be used equally well for a series coating, a protective coating or for a repair coating (for example, clear coat, top coat, varnish, paint). In addition, the films can contain all the usual pigments and additives such as light protection agents or leveling agents. As regards the agents for protection against light, it was specified previously that the silicone oils used can be advantageously functionalized with functional groups of formula (II) which are HALS type radical scavengers, ie vis stabilizers. -with respect to light to sterically hindered amines, and / or hydroxyaryl functional groups. In this case, the films can contain on the one hand silicone oils functionalized with HALS functions and / or hydroxyaryl functions and on the other hand, if necessary, agents for protection against light, including those with HALS type functions. .

The examples below illustrate the preparation of particular silicone oils suitable for crosslinkable compositions in accordance with the invention, and the formulation of said crosslinkable compositions. In addition, the qualities of the polyurethane films obtained from the crosslinkable compositions are illustrated by the tests below.

EXAMPLES 1. Preparation of functionalized oils
The new silicone oils for crosslinkable compositions in accordance with the
present invention were prepared by double or triple hydrosilylation of an oil
silicone containing SiH units.

Example 1: preparation of Compound A
In a 250 ml reactor, equipped with a stirring system, a
temperature, of a refrigerant and the interior volume of which has been previously dried
thermally under a stream of nitrogen, is introduced by means of a syringe,
30 g of toluene (dried over activated molecular sieve). The solvent is stirred and the
temperature of the medium is brought to 90 "C. At this temperature, 60 mg of 4
methoxyphenol and 23 μl of a solution in divinyltetramethyldisiloxane of a
platinum catalyst (so-called Karstedt catalyst) containing 11% by weight of platinum
metal are introduced.

One then flows simultaneously, in a progressive manner, by means of two
syringes, over a period of 1 hour 30 minutes
- 15.77 g of styrene (or 151.64 mmoles) on the one hand
- and on the other hand 50.00 g (i.e. 240.7 meq of SiH functions) of a poly oil
methylhydrogenosiloxane, the characteristics of which are Mn = 1331 g.mol1 and
4814 meq of SiH functions for 1 Kg of oil.

At the end of the casting, the degree of conversion of the SiH functions is 62 mol%.

Are then introduced, through a syringe and over a period of 2
hours, 15 g of allyl alcohol (258 mmol).

The reaction mass is stirred at this temperature for 15 hours. The rate
transformation of the SiH functions is then 100 mol%.

The solvent and residual monomers are then removed by devolatilization which
takes place at 12000 under a vacuum of 4.102 Pa for 1 hour.

59 g of a slightly colored oil are recovered, the characteristics of which are defined.
by NMR are as follows

Example 2: preparation of Compound B
In a 500 ml reactor, previously thermally dried under a stream of nitrogen, equipped with a mechanical stirring system, a temperature probe, a condenser, 54.75 g are introduced via a syringe. of toluene (stored on a molecular sieve). The solvent is stirred and the temperature of the medium is brought to 90 ° C. At this temperature, 93 mg of 4-methoxyphenol and 41% of a solution in divinyltetramethyldisiloxane of a platinum catalyst (called Karstedt catalyst) containing 11 % by weight of platinum metal is introduced. A mixture consisting of - 47.42 g of styrene (ie 456 mmol), - and 90 g is then poured in a progressive manner, by means of a peristaltic pump over a period of 1 hour 30 minutes. (i.e. 617.7 meq of SiH functions) of a polymethylhydrogenosiloxane oil
whose characteristics are Mn = 1267 g.mole1 and 6864 meq of SiH functions
for 1 kg of oil.

At the end of casting, the degree of conversion of the SiH functions is 70 mol%.

Then, 30 μl of the same so-called Karstedt catalyst are introduced into the reaction mass. The operating conditions for stirring and heating are maintained for 18 hours. The degree of conversion of the SiH functions is then 73 mol%.

36.04 g of allyloxyethanol (ie 352.9 mmoles) and 10 1l of the same so-called Karstedt catalyst are then introduced by means of a dropping funnel and over a period of 3 hours.

At the end of casting, the degree of conversion of the SiH functions is then 91 mol%. The reaction mass is stirred at this temperature for 17 hours. The degree of conversion of the SiH functions is then 100 mol%.

The solvent and the residual monomers are removed by devolatilization which takes place at 13000 under 6.5 102 Pa for 2 h 30 min. 150 g of a slightly colored oil are recovered, the characteristics of which defined by nuclear magnetic resonance are as follows:

Example 3: preparation of compound C
Into a 500 ml reactor, previously thermally dried under nitrogen, fitted with a mechanical stirring system, a temperature probe, a condenser, is introduced via a syringe 56.61 g of toluene ( stored on molecular sieve). The solvent is stirred and the temperature of the medium is brought to 90 ° C. At this temperature, 140 mg of 4-methoxyphenol and 80 μl of a solution in divinyltetramethyldisiloxane of a platinum catalyst (called Karstedt catalyst) containing 11 % by weight of platinum metal is introduced. A mixture consisting of: - 76.44 g of styrene (ie 735 mmoles) of peristaltic pump is then poured in a progressive manner, over a period of 1 hour 30 minutes. one part, and - 150 g (i.e. 1029 meq of SiH functions) of a polymethylhydrogenosiloxane oil
on the other hand, whose characteristics are Mn = 1267 g.mole ~ 1 and 6864 meq of
SiH functions for 1 kg of oil.

At the end of the casting, the degree of conversion of the SiH functions is 66 mol%.

50 μl of the same so-called Karstedt catalyst are introduced into the reaction mass. The operating conditions for stirring and heating are maintained for 17 hours. The degree of conversion of the SiH functions is then 71.5 mol%. The solvent and the residual monomers are removed by devolatilization which takes place at 110 ° C. under a vacuum of 6.5 102 Pa for 2 hours.

221 g of a slightly colored oil are recovered, the general formula of which is (1220 meq of SiH functions per 1 kg of oil):

Example 4: preparation of compound D
In a 250 ml reactor, thermally dried under nitrogen, equipped with a mechanical stirring system, a temperature probe, a condenser and an isobaric pouring funnel, is introduced via a 25.10 g syringe of toluene (stored on a molecular sieve) on the one hand, and 17.82 g of allyloxytetramethylpiperidine (ie 90.4 mmol). The mixture is stirred and the temperature of the medium is brought to 90 ° C. At this temperature, 40% of a solution in divinyltetramethyldisiloxane of a platinum catalyst (called Karstedt catalyst) containing 11% by weight of platinum metal are 70 g of compound C prepared in Example 3 are then poured in gradually, via the dropping funnel, over a period of 1 hour 30 minutes.

At the end of casting, the degree of conversion of the SiH functions is 83%. 30 μl of the same so-called Karstedt catalyst are introduced into the reaction mass. These stirring and heating operating conditions are maintained for 19 hours. The degree of conversion of the SiH functions is then 100 mol%.

The solvent and the residual monomers are removed by devolatilization at 13000 under 1.4 102 Pa for 1 h 30 min. 80 g of a slightly colored oil are recovered, the characteristics of which are as follows - 981 meq of SiH functions per 1 kg of oil - Average structure (determined by NMR)

Example 5: Preparation of Compound E
In a 250 ml reactor, previously thermally dried under nitrogen, equipped with a mechanical stirring system, a temperature probe, a condenser and an isobaric pouring funnel, is introduced successively via the intermediary with a syringe 22.57 g of toluene (stored on a molecular sieve) on the one hand, and 20.30 g of 1-octa-2,7-diene oxytrimethylsilane (ie 103 mmol). The mixture is stirred and the temperature of the medium is brought to 90 ° C. At this temperature, 35 μl of a solution in divinyltetramethyldisiloxane of a platinum catalyst (called Karstedt catalyst) containing 11% by weight of platinum metal are 70 g of polymethylhydrogenostyrenylsiloxane C oil obtained in Example 3 are then poured in gradually, via a dropping funnel, over a period of 1 hour 30 minutes.

At the end of casting, the degree of conversion of the SiH functions is 93%. 20 Cil of the same so-called Karstedt catalyst are introduced into the reaction mass. These stirring and heating operating conditions are maintained for 18 hours. The degree of conversion of the SiH functions is then 100 mol%.

The solvent and the residual monomers are removed by devolatilization which takes place at 13,000 under 1.33.102 Pa for 3 hours. 85 g of a slightly colored oil are recovered, the average structure of which (determined by NMR) is as follows:

Example 6: preparation of compound F
67 g of the bifunctionalized oil E obtained in Example 5, ie 78 mmoles of OSi (Me) 3 units, are introduced into a 1 liter reactor, fitted with a mechanical stirring system. This oil is dispersed in 715 ml of a mixture consisting of acetic acid, tetrahydrofuran and water, the volume proportions of which are respectively 4, 2 and 1. Vigorous stirring is maintained for 24 hours at room temperature.

At the end of the reaction, the solvents are removed by several entrainments with toluene which take place at 80 ° C. under a vacuum of 2.5 102 Pa for 30 minutes. 61 g of a slightly colored oil are recovered, the average structure of which is as follows. (NMR):

Example 7: preparation of compound G
In a 500 ml reactor, previously thermally dried under nitrogen, equipped with a mechanical stirring system, a temperature probe, and a condenser, 54.15 g of toluene are introduced via a syringe. (preserved on molecular sieve). The solvent is stirred and the temperature of the medium is brought to 90 ° C. At this temperature, 410 mg of 4-methoxyphenol and 110 μl of a solution in divinyltetramethyldisiloxane of a platinum catalyst (called Karstedt catalyst) containing 11 % by weight of platinum metal is introduced. A mixture consisting of 54.15 g of styrene (ie 520.8 mmoles) and 128 g is then poured in gradually, by means of a peristaltic pump, over a period of 1 hour 30 minutes. (ie 911.4 meq of SiH functions) of a polymethylhydrogenosiloxane oil whose characteristics are as follows Mn = 1267 g.mole1 and 7120 meq of SiH functions per 1 kg of oil.

At the end of casting, the degree of conversion of the SiH functions is 51.5% by mole.

The operating conditions for stirring and heating are maintained for 9 hours. The degree of conversion of the SiH functions is then 56 mol%. Are then introduced, by means of a syringe pump and over a period of 3 hours, 36.04 g of allyloxypentamethylpiperidine (ie 130.2 mmoles). At the end of the casting, the degree of conversion of the SiH functions is 70.1% by mole. Into the reaction medium are introduced such as the same so-called Karstedt catalyst. The operating conditions for stirring and heating are maintained for 12 hours. The degree of conversion of the SiH functions is then 71 mol%. Then poured, gradually, by means of a syringe pump, over a period of 3 hours 45.27 g of allyl alcohol (or 780.5 mmoles) and 20 μl of the same catalyst known as Karstedt.
At the end of casting, the degree of conversion of SiH functions is then 97%. The operating conditions for stirring and heating are maintained for 20 hours. The degree of conversion of the SiH functions is then 100%.

The solvent and the residual monomers are removed by devolatilization which takes place at 1300C under 6.5102 Pa for 3:30. 215 g of a slightly colored oil are recovered, the characteristics of which are as follows - 543 meq of SiH functions per 1 kg of oil - Average structure (determined by NMR)

Example 8: preparation of compound H
Into a 500 ml reactor, thermally dried under nitrogen, fitted with a mechanical stirring system, a temperature probe, and a condenser, 66.0 g of toluene are introduced via a syringe ( stored on molecular sieve). The solvent is stirred and the temperature of the medium is brought to 90 ° C. At this temperature, 410 mg of 4-methoxyphenol and 90 μl of a solution in divinyltetramethyldisiloxane of a platinum catalyst (called Karstedt catalyst) containing 11 % by weight of platinum metal is introduced. A mixture consisting of: 62.45 g of styrene (i.e. 600.5 mmoles) and 200 g (ie 1401.2 meq of SiH functions) of a polymethylhydrogenosiloxane oil whose characteristics are Mn = 1267 g.mole1 and 7006 meq of SiH functions per 1 kg of oil.

At the end of casting, the degree of conversion of the SiH functions is 31.5% by mole.

The operating conditions for stirring and heating are maintained for 10 hours.

The degree of conversion of the SiH functions is then 42.5 mol%. Are then introduced, by means of a syringe pump and over a period of 3 hours, 59.35 g of vinyltrimethoxysilane (ie 400.4 mmoles). The operating conditions of stirring and heating are maintained for 11 hours. The degree of conversion of the SiH functions is then 72 mol%. Then poured, gradually, by means of a syringe pump, over a period of 3 hours, 34.83 g of allyl alcohol (ie 600.5 mmoles) and 30 IF of the same so-called catalyst.
Karstedt.

At the end of casting, the degree of transformation of SiH functions is then 91.5%. The operating conditions for stirring and heating are maintained for 20 hours. The degree of conversion of the SiH functions is then 100%.

2. Préparations de films polyuréthannes à partir des compositions réticulables selon
l'invention
A. Les compositions réticulables testées contiennent le composé A et sont
préparées par mélange des composants identifiés. La quantité des composants
est indiquée dans le Tableau 1; toutes les indications relatives aux parts et aux
pourcentages sont des indications pondérales, les pourcentages étant entre
parenthèses.The solvent and the residual monomers are removed by devolatilization which takes place at 13000 under a vacuum of 6.5 102 Pa for 3 h 30 min. 341.5 g of a slightly colored oil are recovered, the average structure of which (determined by NMR) is as follows:

2. Polyurethane film preparations from crosslinkable compositions according to
the invention
A. The crosslinkable compositions tested contain compound A and are
prepared by mixing the identified components. The quantity of components
is shown in Table 1; all information relating to units and
percentages are weight indications, the percentages being between
parentheses.

Table 1

<tb><SEP> COMPOSITIONS <SEP> Col <SEP> Co2 <SEP> Co3 <SEP> Co4
<tb><SEP> (witness) <SEP>
<tb><SEP> Polyisocyanate1) <SEP> 19.3 <SEP> 3.26 <SEP> 19.3
<tb><SEP> SCX <SEP> 9202) <SEP> 50.9 <SEP> 8.05 <SEP> 50.9 <SEP> 50.9
<tb><SEP> Dilaureate <SEP> of <SEP> dibutyltin <SEP> 0.01
<tb><SEP> Compound <SEP> A <SEP> (% <SEP> compound <SEP> A <SEP> / <SEP> extract <SEP> sec) <SEP> 0.29 <SEP> (1.5) <SEP> 0.6 <SEP> (1.0)
<tb><SEP> Acetate <SEP> of <SEP> but <SEP> I <SEP> 29.8 <SEP> 8.39 <SEP> 29.2 <SEP> 29.2
<tb><SEP> containing <SEP>% <SEP> of the composed <SEP>
<tb> Polyisocyanate1) <SEP> containing <SEP> 1 <SEP> of the <SEP> compound <SEP> A3) <SEP> 19.9
<tb><SEP> Nô / <SEP> OH <SEP> (molar) <SEP> 1.05 <SEP> 1.1 <SEP> 1 <SEP> 1.05 <SEP> 1.05
<tb><SEP> Extract <SEP> sec <SEP> (% <SEP>) <SEP> 60 <SEP> 50 <SEP> 60 <SEP> 60
<tb>
1) Low viscosity liquid trimer type aliphatic polyisocyanate without
solvent with 23% NCO functions and 100% dry extract (tolonate HDT-LV
marketed by Rhône-Poulenc).

2) Acrylic oligomer containing hydroxyl groups with an OH index of 140 and
at a rate of 80% in methyl n-amyl ketone (product marketed by
Johnson Polymer).

3) Compound A pre-reacts with the polyisocyanate for 16 hours at 40 ° C.

The Col to Co4 compositions thus obtained are applied to a glass plate
(350 x 105 x 2 mm) using a speed regulated Ericksen bench giving a
100 m thick wet film. The crosslinking of the films is done by treatment
thermal in an oven or evolution at ambient temperature in a conditioned room
during many days.

B. The crosslinkable compositions according to the invention, containing the compounds B, D, F,
G and H, are prepared by mixing the components identified and whose quantity
is shown in Table 2. All information relating to the units and
percentages are weight indications, the percentages being between
parentheses.

Table 2

<tb><SEP> COMPOSITIONS <SEP> CoS <SEP><SEP> Co6 <SEP><SEP> Co7 <SEP> Co8 <SEP> Co9 <SEP> ColO
<tb><SEP> (Witness) <SEP>
<tb><SEP> Polyisocyanate <SEP> 1) <SEP> 16.67 <SEP> 16.67 <SEP> 16.67 <SEP> 16.67 <SEP> 16.67 <SEP> 16.67
<tb><SEP> SCX <SEP> 920 <SEP> 2) <SEP> 43.25 <SEP> 42.37 <SEP> 42.42 <SEP> 42.37 <SEP> 42.34 <SEP> 42.34
<tb> Dilaureate <SEP> of <SEP> dibutyl <SEP> tin <SEP> 0.01 <SEP> 0.01 <SEP> 0.01 <SEP> 0.01 <SEP> 0.01 <SEP> 0.01
<tb><SEP> B <SEP> D <SEP> F <SEP> G <SEP> H
<tb><SEP> Compound <SEP> / <SEP><SEP> 1.56 <SEP> 1.56 <SEP> 1.56 <SEP> 1.56 <SEP> 1.56
<tb><SEP> (% <SEP> compound <SEP> / <SEP> extract <SEP> sec) <SEP> (3.08) <SEP> (3.08) <SEP> (3.08) <SEP> (3.07) <SEP> (3.08)
<tb><SEP> Butyl <SEP> acetate <SEP><SEP> 25.53 <SEP> 26.24 <SEP> 26.26 <SEP> 26.24 <SEP> 26.24 <SEP> 26.24
<tb><SEP> NCO / OH <SEP> (molar) <SEP> 1.05 <SEP> 1.05 <SEP> 1.05 <SEP> 1.05 <SEP> 1.05 <SEP> 1.05
<tb><SEP> Extract <SEP> sec <SEP> (%) <SEP> 60 <SEP> 60 <SEP> 60 <SEP> 60 <SEP> 60 <SEP> 60
<tb>
1) Low viscosity liquid trimer type aliphatic polyisocyanate without
solvent with 23% NCO functions and 100% dry extract (tolonate HDT-LV
marketed by Rhône-Poulenc).

2) Acrylic oligomer containing hydroxyl groups with an OH index of 140 and
at a rate of 80% in methyl n-amyl ketone (product marketed by
Johnson Polymer).

3. Application tests of the compositions according to the invention
The tests for evaluating the properties of films or coatings described below
make it possible to highlight the improved properties and in particular a
better resistance to scratching of the Rel to Re19 coatings obtained
from crosslinkable compositions Col to Col 0.

at. Appearance of the plates after cooking
It is observed that the quality of the coating, judged by the external appearance of
plates, is perfect in appearance. Tables 3 and 4 describe the conditions for
cooking as well as the appearance of the plates containing the silicone oils A, B, D, F, G
or H.

Table 3 ~~~~~~~~~~~~~~~

<tb><SEP> Coating <SEP> Rel * <SEP> Re2 <SEP> Re3 <SEP> Re4 <SEP> Re5 * <SEP> Re6 <SEP> Re7 <SEP> Re8 <SEP> Re9 <SEP> RelO
<tb> Composition <SEP> Col <SEP> Co2 <SEP> Co3 <SEP> Co4 <SEP> Col <SEP> Co3 <SEP> Co4 <SEP> Col <SEP> Co3 <SEP> Co4
<tb> Appearance <SEP>##########
<tb><SEP> 8000 <SEP> 80 C <SEP> 15000 <SEP> 80 C <SEP> 80 C <SEP> 23 C <SEP> 23 C <SEP> 23 C <SEP> 23 C <SEP> 23 C <SEP> 23 C <SEP>
<tb> Cooking <SEP> 30 <SEP> min <SEP> 10 <SEP> min <SEP> 30 <SEP> min <SEP> 30 <SEP> min <SEP> 7 <SEP> days <SEP> 7 <SEP > days <SEP> 7 <SEP> days <SEP> 15 <SEP> bear <SEP> 15 <SEP> days <SEP> 15 <SEP> days
<tb>> transparent film, perfect appearance Re1 * Re5 *: control coating
Table 4

<tb><SEP> Coating <SEP> Re112 <SEP> Re12 <SEP> Re13 <SEP> Re14 <SEP> Re15 <SEP> Rel6 <SEP> Re17 <SEP> Re18 <SEP> Rel9
<tb> Composition <SEP> Co5 <SEP> Co6 <SEP> Co7 <SEP> Co8 <SEP> Co8 <SEP> Co8 <SEP> Co8 <SEP> Co9 <SEP> ColO
<tb> Appearance <SEP>##########
<tb><SEP> 800C <SEP> 800C <SEP> 800C <SEP> 800C <SEP> 1 <SEP> 1 <SEP> 00C <SEP> 1 <SEP> 300C <SEP> 1 <SEP> 500C <SEP> 800C <SEP> 800C
<tb> Cooking <SEP> 30 <SEP> 30 <SEP> 30 <SEP> 30 <SEP> 30 <SEP> 30 <SEP> 30 <SEP> 30 <SEP> 30
<tb><SEP> min <SEP> min <SEP> min <SEP> min <SEP> min <SEP> min <SEP> min <SEP> min <SEP> min
<tb>
transparent film, perfect appearance.

Rel 1 *: control coating.

b. Scratch resistance
i) The transparent coatings Rel, Re3 to RelO have been subjected to the tests of
scratch resistance.

The glass plates are fixed and then subjected to scratches under pressure
weighing 500 g at the rate of 5 passages at regular and moderate speed
in one direction and 5 passages in the other direction of:
+ a dry pad of dimension (150 x 38.4 mm) of Scotch-Brite brand () ultra
end of Du pont.

+ a wet pad of dimension (150 x 38.4 mm) of type Scotch-Britee ultra
end of Du pont.

+ a tracing paper (reference NFE 04502 from Photogay, Lyon, France).

The Scotch-Brite brand pad or tracing paper is renewed to
each type of coating.

The evaluation of the more or less significant presence of scratches is done by the
measurement of loss of gloss of the coating. These measurements are carried out using
an Ericksen glossmeter with an incident radius of 20 "C. For each plate,
5 measurements are taken at defined locations.

The measurements are carried out on
- plates that have not undergone the scratch test,
- plaques that have undergone the scratch test, one hour later (see
Table 5).

- plates having undergone the scratch test, 1 month later (see Table 6).

The results are expressed as a percentage of loss of gloss of the
coating before and after carrying out the scratch test.

Table 5

<tb><SEP> Coating <SEP> Re2 <SEP> Re3 <SEP> Re4 <SEP> Re5 <SEP> Re6 <SEP> Re7 <SEP> Re8 <SEP> Re9 <SEP> RelO
<tb> Scotch-Brite <SEP> sec <SEP> 26 <SEP> 5 <SEP> 5 <SEP> 21 <SEP> 20 <SEP> 17 <SEP> 24 <SEP> 21 <SEP> 20
<tb> Scotch-Brite <SEP> wet <SEP> 7 <SEP> 5 <SEP> 4 <SEP> 16 <SEP> 15 <SEP> 16 <SEP> 19 <SEP> 16 <SEP> 17
<tb> Tracing paper <SEP><SEP> ue <SEP> 4 <SEP> 2 <SEP> 2 <SEP> 14 <SEP> 7 <SEP> 4 <SEP> 12 <SEP> 4 <SEP> 7
<tb>
Table 6

<tb><SEP> Coating <SEP> Re2 <SEP> Re3 <SEP> Re4 <SEP> Re5 <SEP> Re6 <SEP> Re7 <SEP> Re8 <SEP> Re9 <SEP> RelO <SEP>
<tb> Scotch-Brite <SEP> sec <SEP> 29 <SEP> 7 <SEP> 6 <SEP> 7 <SEP> 7 <SEP> 6 <SEP> 3 <SEP> 3 <SEP> 5
<tb> Scotch-Brite <SEP> wet <SEP> 8 <SEP> 5 <SEP> 2 <SEP> 4 <SEP> 4 <SEP> 3 <SEP> 3 <SEP> 1 <SEP> 1
<tb> Layer paper <SEP><SEP> ue <SEP> 6 <SEP> 5 <SEP> 1 <SEP> 5 <SEP> 3 <SEP> 4 <SEP> 1 <SEP> 0 <SEP><SEP> i <SEP>
<tb> ii) Other scratch tests were carried out on the Re 11 to Re 19 coatings.

The glass plates are fixed and then subjected to scratches under pressure
weighing 600g with 15 back and forth movements at regular speed and
moderate.

Equipment used:
- a cotton fabric measuring 150 x 150 mm VERATEC () (Graphic Arts
Cheesecloth),
- a BON-AM | # abrasive powder (Bon Ami Co, Kansas City, MO 64101),
- an abrasimeter.

The friction between the weight and the abrasive powder results in the formation of
scratches. Cotton fabric and abrasive powder are renewed for each
type of coating. The assessment of the presence of more or less
scratching is done by measuring the loss of gloss of the coating. These measures
are carried out using an Ericksen glossmeter with an incident radius of 20.

For each plate, 3 measurements at well-defined places are carried out.

The measurements are carried out on plates
- not having undergone the scratch test
- having undergone the scratch test 1 hour later
- having undergone the scratch test 7 days later.

The results (Table 7) are expressed as a percentage of loss of gloss
of the coating before and after carrying out the scratch test.

Table 7

<tb><SEP> Re11 <SEP> Re12 <SEP> Rel3 <SEP> Rel4 <SEP> Re15 <SEP> | <SEP> Rel6 <SEP> | <SEP> Rel7 <SEP> | <SEP> Rel8 <SEP> ReI9 <SEP>
<tb> Loss <SEP> brightness (%) <SEP> 35.2 <SEP> 28.7 <SEP> 1a.4 <SEP> 27.9 <SEP> 29.4 <SEP> 28.3 <SEP> 22.8 <SEP> 25.7 <SEP> 28.6 <SEP>
<tb> (1h <SEP> after <SEP> scratch) <SEP> 3. <SEP> 28.7 <SEP> 18.4 <SEP> 27.9 <SEP> 29.4 <SEP> 28.3 <SEP> 22.6 <SEP> 25.7 <SEP> 28.6 <SEP>
<tb> Loss <SEP> of <SEP> brightness <SEP> 20.3 <SEP> 14.9 <SEP> 3.3 <SEP> 14.3 <SEP> 15.3 <SEP> 16.1 <SEP> 14.3 <SEP> 10.6 <SEP> 14.9 <SEP >
<tb> (7d. <SEP> after <SEP> scratch)
<tb> c. Surface energy measurements.

The surface energy measurement was carried out under the following conditions:
on each plate coated with polyurethane films obtained from
crosslinkable compositions according to the invention and other compositions not containing
no silicone, a drop of double-distilled water and a drop of diiodomethane are available; during the deposition of the drop, the contact angle between the latter and the surface of the plate is measured; taking into account the values of the surface tensions of water and diiodomethane, the surface energy (yS) and these polar components yP and dispersive yD are calculated.

Table 8

<tb> Coating <SEP> Rel <SEP> Re3 <SEP> Re4 <SEP> Reli <SEP> Rez <SEP> 2 <SEP> Rel4 <SEP> Rez <SEP> 8 <SEP> Rel9
<tb><SEP> 2.2 <SEP> 2.0 <SEP> 1.9 <SEP> 1.8 <SEP> 2.4 <SEP> 3.4 <SEP> 3.8 <SEP> 3.4
<tb><SEP>&gamma; D <SEP> 33.3 <SEP><SEP> 23.4 <SEP> 24.3 <SEP> 36.4 <SEP> 24.1 <SEP> 23.2 <SEP> 22.1 <SEP> 22.2
<tb><SEP> VL <SEP> 35.5 <SEP> 25.4 <SEP> 26.0 <SEP> 38.2 <SEP> 26.5 <SEP> 26.9 <SEP> 25.8 <SEP> 25.6
<tb>
The results of Table 8 show that the coatings consisting of polyurethane films according to the invention have a lower surface energy than that of the coatings obtained from compositions without silicone (Re1 and Rel 1); this reflects in particular that the coatings made up of polyurethane films contain silicone oil on the surface.

In addition, surface energy measurements were also carried out on coatings after they had undergone a washing operation. In this case, the washing consists of wiping the coating three times with fleece paper soaked in isopropanol, at the rate of 4 round trips and change of paper by wiping. The results of Table 9 show that the surface energy is always lower for the coatings according to the invention compared to that of the silicone-free coatings, which therefore reflects the lasting and constant presence of silicone oil within the coating. polyurethane matrix after washing (no elimination of silicone oil on the surface of said film).

Table 9

<tb> Coating <SEP> Re1 <SEP> (indicator) <SEP> Re3 <SEP> Re4 <SEP> Re12 <SEP> Rel <SEP> 3 <SEP> Re14 <SEP> Re18 <SEP> Re19
<tb><SEP> 1tP <SEP> 2.2 <SEP> 2.0 <SEP> 1.9 <SEP> 3.6 <SEP> 2.6 <SEP> 3.8 <SEP> 2.6 <SEP> j <SEP> 4.3
<tb><SEP> yD <SEP> 33.3 <SEP> 23.4 <SEP> 24.3 <SEP> 22.8 <SEP> 27.5 <SEP> 24.7 <SEP> 22.6 <SEP> 21.5
<tb><SEP> rL <SEP> 35.5 <SEP> 25.4 <SEP> 26.0 <SEP> 26.5 <SEP> 30.1 <SEP> 28.6 <SEP> 25.2 <SEP> 25.8
<tb>

Claims (22)

(c) 1 to 10% by weight of a silicone oil of formula (I): between 2.5 and 4.5%, hydroxyls whose content by weight relative to the acrylic oligomer is (b) 50 to 80% by weight of acrylic oligomer containing groups (a) 20 to 50% by weight of polyisocyanate, CLAIMS 1. Crosslinkable composition comprising the following compounds (1) o and p are identical or different integers ranging between in which: 1 to 100, and preferably 1 to 50, (2) I represents an integer such that 1 = 2 + q, (3) q represents an integer between 0 and 10, (4) m represents an integer between 1 and 60, preferably between 1 and 30, particularly preferably 1 to 10, (5) n is an integer such that 20 <(100 x m) / (m + n) <60, of preferably 25 <(100 x m) / (m + n) <55, (6) the symbols R1 and R2 are the same and / or different and represent a hydrocarbon radical chosen from linear alkyl radicals or branched having 1 to 4 carbon atoms, the alkoxy radicals linear or branched having 1 to 4 carbon atoms, the radicals aryls, alkylaryl radicals, and preferably a methyl radical, a phenyl radical, a methoxy radical or an ethoxy radical, (7) the symbols R3 and R4 are identical and / or different and are chosen among: - monovalent radicals - (CH2) h-Si- (R1) 3 where h is between 1 and 10, preferably 1 to 3, - monovalent aromatic alkylaryl radicals, the alkyl part linear or branched containing 1 to 4 carbon atoms, from preferably the symbol R3 representing the monovalent radical -CH (CH3) C6H5 and the symbol R4 representing the monovalent radical -CH2CH2C6H5 (8) the symbols R5 and R6 are the same and / or different and represent a monovalent functional group chosen from - a monovalent primary amine of the -R7-NH2 type where R7 and a linear, branched or cyclic alkyl radical having from 1 to 6 atoms of carbon, - a monovalent secondary amine of the -R8-NH-R9 type where R8 and R9, identical and / or different are linear alkyl chains, branched or cyclic, having 1 to 6 carbon atoms, - a monovalent radical - (CH2) a (NHCH2CH2) bNH2 where c and d are independent integers a is between 1 and 10, preferably 1 to 3, b is between 0 and 10, preferably 0 to 1, - a monovalent radical - (CH2) C (OCH2CH2) d (OCH2CHCH3) eOH where c, d and e are independent integers c is between 1 and 20, preferably 1 to 10, d is between 0 and 70, preferably 0 to 12, e is between 0 and 70, preferably 0 to 15, - a monovalent radical - (CH2) fSH where f is an integer which can go from 1 to 10, preferably 1 to 3, - a monovalent radical - (CH2) 9-C (R ') 2-OH where g is an integer which can range from 1 to 10 and preferably 1 to 3, and R 'represents a hydrocarbon radical chosen from a linear or branched alkyl radical having 1 to 4 carbon atoms, aryl radicals and alkylaryl radicals. acrylic and polyisocyanate. silicone is poorly miscible with the couple consisting of the oligomer mixture 2. Crosslinkable composition according to claim 1, characterized in that the oil - (C) 1 to 4% by weight of a silicone oil of formula (I), preferably 2 to 3%. - (b) 60 to 80% by weight of hydroxylated acrylic oligomer, preferably 70%, and - (a) 20 to 40% by weight of polyisocyanate, preferably 30%, 3. Crosslinkable composition according to claim 1 or 2 comprising: preferably of the order of 60%. crosslinkable composition containing a solvent is between 50 and 80%, and such as the percentage by weight of compounds (a), (b) and (c) relative to the hydroxyls characterized in that the crosslinkable composition comprises a solvent acrylic advantageously contains between 2.5 and 4.5% by weight of groups 4. Crosslinkable composition according to claim 3, characterized in that the oligomer identical or different represent alkylene radicals having 1 to * the radicals of formula-R13-O-R13 in which the radicals R13 having 1 to 4 carbon atoms; contains an OH group and optionally 1 or 2 alkyl radicals branched, has 2 to 12 carbon atoms and the cyclohexylene part alkylene-cyclohexylene radicals including the linear alkylene part or branched, has 2 to 20 carbon atoms; * alkylene-carbonyl radicals including the linear alkylene part or carbon; linear or branched alkylene radicals having 2 to 18 atoms of phenyl radical; (2) the monovalent radical R12 represents a hydrogen radical; (3) the R10 radical is a divalent hydrocarbon radical chosen from linear or branched alkyl radicals having 1 to 3 carbon atoms and the in which: (1) the monovalent radicals R11 are identical and / or different, chosen from

a remainder of formula (Il) that a fraction of the symbols R1 and R5, which are identical and / or different, represent 5. Crosslinkable composition according to one of claims 1 to 4, characterized in that

of carbon and a divalent radical of formula (lii) of hydrogen, a linear or branched alkyl radical containing 1 to 6 atoms U represents -O- or -NR16-, R16 being a radical chosen from an atom optionally substituted by a hydroxyl radical; alkylene having 2 to 12 carbon atoms and the radical R9 is identical and / or different R14 and R15 radicals represent radicals have the meanings indicated above; Ies radicals of formula -R14 -O -R15 - O-CO-R14 in which the * radicals of formula -R13 - COO - R13 in which the radicals R13 are substituted by one or two -OH group (s); meanings given above and one or both of them the radicals of formula -R13 - O - R13 in which the radicals R13 have 12 carbon atoms; The other (that of R10) being linked to a silicon atom. One of the valential bonds (that of R17) being linked to the atom of -NR16-, divalent alkylene, linear or branched, having 1 to 12 carbon atoms, the meanings indicated above and R17 represents a radical in which R10 has the meaning indicated above, R11 and R12 have silicone is between 5 and 15%, and preferably of the order of 6%. number of functional groups of formula (II) / number of Si units of the oil 6. Crosslinkable composition according to claim 5, characterized in that the ratio 7 Crosslinkable composition according to claim 5 or 6, characterized in that the monovalent radical R12 of formula (II) and / or (III) represents a radical hydrogen; the R5 or O radical; 8. Crosslinkable composition according to one of claims 1 to 7, characterized in that that a fraction of the symbols R1 and R5, which are identical and / or different, represent hydroxyaryl units - (CH2) n- (V) (Ar) where - n is between 1 and 10, - the V radicals are identical and / or different and represent a divalent radical selected from -NH-, NHR'-, -CHN-, -O-, -CHN-, -COO-, Ar is an aromatic group substituted by at least one OH radical and possibly be substituted by at least one hydrocarbon radical containing from 1 to 4 atoms of carbon and possibly comprising a heteroatom, preferably Ar being a phenol group, and - R 'is a linear or branched alkyl radical having 1 to 4 carbon atoms. that the polyisocyanate is prepared from polymethylene diisocyanate. 9. Crosslinkable composition according to one of claims 1 to 8, characterized in that diisocyanate. polymethylene diisocyanate is tetramethylene diisoicyanate or hexamethylene 10. Crosslinkable composition according to claim 9, characterized in that the and 200 ° C, for 20 minutes to 1 hour. (5) dry the spread mixture and then cook it at a temperature between 50 "C (4) spread the mixture over the surface to be coated, and (2) add and mix the polyisocyanate to the mixture obtained in (1), (1) mix the solvent, the hydroxylated oligomer and the silicone oil, that the method comprises the steps of: of a crosslinkable composition according to one of claims 1 to 10, characterized in 11. Process for preparing a polyurethane film by heat treatment from polyisocyanate before step (2). characterized in that at least a fraction of the silicone oil is added to the 12. A process for preparing a polyurethane film according to claim 11, a catalyst, preferably added before the addition of polyisocyanate. characterized in that the preparation of the polyurethane film is carried out in the presence 13. A process for preparing a polyurethane film according to claim 11 or 12, a catalyst, preferably added before the addition of polyisocyanate. characterized in that the preparation of the polyurethane film is carried out in the presence 14. A process for preparing a polyurethane film according to claim 13, characterized in that the catalyst is dibutyltin dilaureate. 15. A process for preparing a polyurethane film according to claim 14, according to one of claims 1 to 10. 16. Polyurethane film obtainable from the crosslinkable compositions crosslinkable. polyurethane is obtained by thermal curing of the composition 17. Polyurethane film according to claim 16, characterized in that the film the preparation of polyurethane films. 18. Use of the crosslinkable composition according to one of claims 1 to 10 for polyurethanes. crosslinkable is thermally cured during film preparation 19. Use according to claim 18, characterized in that the composition polyurethane is a protective coating. 20. Use according to claim 18 or 19, characterized in that the film according to claim 1 to 10. 21. Object covered with a polyurethane film obtained from a crosslinkable composition 22. Object covered with a polyurethane film according to claim 16 or 17.