FR2825368A1 - PRESSURE-SENSITIVE ADHESIVE SILICONE COMPOSITIONS, PREPARATION METHOD AND USES THEREOF - Google Patents

Abstract

The invention relates to a pressure-sensitive solvent-free composition which can be hardened radically based on: (a) at least one silicone resin Re, (b) at least one silicon rubber Go which has a viscosity of over 100 000 mPa.s and which is terminally functionalized with at least one hydroxy,acrylate, and/or vinyl group, (c) a diluent Di which has a viscosity of less than 100 mPa.s and (d) an effective amount of an initiator Am which can be activated by means of UV and/or electron beam treatment.

Description

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 Pressure-sensitive adhesive silicone compositions, process for their preparation and their uses

 The present invention relates to silicone-based and solvent-free pressure-sensitive adhesive compositions, as well as processes for preparing and using such compositions that are capable of radically curing under UV and / or electron beam treatment. .

 Silicone-based compositions are known to render adherent surfaces. In this regard, it is often necessary to apply these silicone coatings in the form of solutions in a solvent to reduce their viscosity and thus make these compositions usable in coating applications. The solvent effectively facilitates the spreading of the coating, however, this is not satisfactory because it is then necessary to evaporate the solvent in question, which requires a high energy consumption. In addition, its evaporation poses environmental problems and in particular problems related to releases to the atmosphere; this requires the removal and recovery of the solvent, thereby resulting in a considerable cost in equipment and energy.

 There is therefore a definite need for adhesive compositions without solvent and capable, however, of being spread easily on a support. The absence of solvent in these compositions lowers the amount of energy required to cure them and limits the need for pollution control equipment. This object is achieved by the invention which relates to new silicone compositions curable pressure sensitive adhesives, commonly called PSA.

 Another essential objective of the invention is to provide crosslinkable compositions and / or polymerizable by free radical under U.V treatment and / or electron beam and not requiring heat treatment.

 Another object of the invention is to provide compositions that can be used both in thin layer and in thick layer.

 These various objects are now achieved by the invention which relates to a curable, solvent-free, pressure-sensitive adhesive composition comprising: (a) at least one silicone resin Re containing: at least one RS / Of / x unit (1) )

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dans laquelle : - a=0, 1ou2,

3 - R3, identique ou différent, représente un radical alkyle, cycloalkyle, aryle, vinyle, alcoxy, de préférence un alkyle inférieur en C1-C6, - Z, identique ou différent, est un substituant organique comportant au moins une fonction réactive acrylate, acrylamide et/ou alcénylether, (d) et une quantité efficace d'amorceur Am activable par traitement sous U. V et/ou traitement sous faisceau d'électrons choisi parmi au moins un composé répondant à l'une des formules (III) à (VI) suivantes :

lez Ar---T'" 0 n formu) e ( !))) dans laquelle : - lorsque n = 1, Ar1 représente un radical aryle contenant de 6 à 18 atomes de carbone, un radical tétrahydronaphtyle, thiényle, pyridyle ou furyle ou un radical phényle porteur d'un ou plusieurs substituants choisis dans le # and at least one tetrafunctional SiO 2 unit and / or a trifunctional unit
R 2 SiO 3/2 in which: R and R, which may be identical or different, are monovalent radicals chosen from lower alkyl radicals, for example C 1 -C 6, alkenyl radicals and hydroxyl radicals; (b) at least one Go silicone gum having a viscosity greater than 100,000 mPa. s, and preferably greater than 200,000 mPa. s, and functionalized at the end (s) of chain (s) with at least one acrylate group and / or vinyl and preferably hydroxy, # (c) 1 to 50% by weight of a diluent of silicone nature of viscosity less than
100 mPa. s based on at least one silicone Di comprising: 0 at least one unit of formula e (II):

in which: - a = 0, 1 or 2,

R 3, which may be identical or different, represents an alkyl, cycloalkyl, aryl, vinyl or alkoxy radical, preferably a C 1 -C 6 lower alkyl, which may be identical or different, is an organic substituent comprising at least one acrylate reactive function, acrylamide and / or alkenyl ether, (d) and an effective amount of initiator Am activatable by treatment under U. V and / or electron beam treatment chosen from at least one compound corresponding to one of formulas (III) to (VI) following:

embedded image in which: when n = 1, Ar 1 represents an aryl radical containing from 6 to 18 carbon atoms, a tetrahydronaphthyl, thienyl, pyridyl or furyl radical; or a phenyl radical bearing one or more substituents chosen from

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groupe constitué de F, CI, Br, CN, OH, les alkyles linéaires ou ramifiés en C1-C12,-CF3,-OR6,-OPhényle,-SR6,-SPhényle,-SO2Phényle, - COOR6, -O- (CH2-CH=CH2), -0 (CH2H4-0) m-H, -0 (C3H60) m-H, m étant compris entre 1 et 100, - lorsque n = 2, Ar1 représente un radical arylène en C6-C12 ou un radical phénylène-T-phénylène, où T représente -O-, -S-, -SO2- ou -CH2-, - X représente un groupe-OR7 ou-OSiR8 (R9) 2 ou forme, avec R4, un groupe -0-CH (R1 0) ~, - ruz représente un radical alkyle linéaire ou ramifié en C1-C8 non substitué ou porteur d'un groupe -OH, -OR6, acyloxy en C2-C8, -COOR6, -CF3, ou

- CN, un radical alcényle en C3 ou C4, un radical aryle en C6 à Cl 8~, un radical phénylalkyle en C7 à Cg, - R5 a l'une des significations données pour R4 ou représente un radical -CH2CH2R11, ou encore forme avec R4, un radical alkylène en C2-C8 ou un radical oxa-alkylène ou aza-alkylène en C3-C9, - R6 représente un radical alkyle inférieur contenant de 1 à 12 atomes de carbone, - R7 représente un atome d'hydrogène, un radical alkyle en C1-C12, un radical alkyle en C2-C6 porteur d'un groupe-OH,-ORS ou-CN, un radical alcényle en C3-C6, un radical cyclohexyle ou benzyle, un radical phényle éventuellement substitué par un atome de chlore ou un radical alkyle linéaire ou ramifié en C1-C12, ou un radical tétrahydropyrannyle-2, -R8 et R9, identiques ou différents, représentent chacun un radical alkyle en C1-C4 ou un radical phényle, - R10 représente un atome d'hydrogène, un radical alkyle en C1-C8 ou un radical phényle,

- R11 représente un radical -CONH2, -CONHR6, -CON (R6) 2, -P (0) (OR6) 2 ou pyridyl-2 ;

A----fj----R15 formule (IV) 0 dans laquelle : - Ar2 a la même signification que Ar de la formule (III) dans le cas où

group consisting of F, Cl, Br, CN, OH, C1-C12 linear or branched alkyls, -CF3, -OR6, -OPhenyl, -SR6, -SPhenyl, -SO2Phenyl, -COOR6, -O- (CH2- CH = CH2), -O (CH2H4-O) mH, -O (C3H60) mH, m being between 1 and 100, when n = 2, Ar1 represents a C6-C12 arylene radical or a phenylene-T radical; -phenylene, where T represents -O-, -S-, -SO2- or -CH2-, -X represents a group -OR7 or -SOlR8 (R9) 2 or forms, with R4, a group -O-CH (R1 0) ~, - ruz represents a linear or branched C1-C8 alkyl radical unsubstituted or bearing a -OH group, -OR6, C2-C8 acyloxy, -COOR6, -CF3, or

- CN, a C3 or C4 alkenyl radical, a C6 to C18 aryl radical, a C7 to C8 phenylalkyl radical, - R5 has one of the meanings given for R4 or represents a radical -CH2CH2R11, or else form with R4, a C2-C8 alkylene radical or a C3-C9 oxa-alkylene or aza-alkylene radical, - R6 represents a lower alkyl radical containing from 1 to 12 carbon atoms, - R7 represents a hydrogen atom, a C1-C12 alkyl radical, a C2-C6 alkyl radical bearing an -OH, -ORS or-CN group, a C3-C6 alkenyl radical, a cyclohexyl or benzyl radical, a phenyl radical optionally substituted with a chlorine atom or a linear or branched C 1 -C 12 alkyl radical, or a tetrahydropyranyl-2 radical, R 8 and R 9, which may be identical or different, each represent a C 1 -C 4 alkyl radical or a phenyl radical, R 10 represents an atom hydrogen, a C1-C8 alkyl radical or a phenyl radical,

R11 represents a radical -CONH2, -CONHR6, -CON (R6) 2, -P (O) (OR6) 2 or pyridyl-2;

In which: Ar2 has the same meaning as Ar of the formula (III) in the case where

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radicaux alcényles linéaires ou ramifiés en C-j-Cg ;

R16 1 Arzt Ar3 11 g R16 formule (V) o o dans laquelle : - Ar3 a la même signification que Ar1 de la formule (III) dans le cas où n=1, - R16, identiques ou différents, représentent un radical choisi parmi le groupe constitué d'un radical Ar3, un radical -(C=O)-Ar3, un radical alkyle linéaire ou ramifié en Cl-Cl2, un radical cycloalkyle en Cg-C, ces radicaux pouvant être substitués par un ou plusieurs substituants choisis dans le groupe constitué de-F,-CI,-Br,-CN,-OH,-CF3,-OR6,-SR6,-
COOR6, les radicaux alkyles linéaires ou ramifiés en C1-C12 porteurs éventuellement d'un groupe -OH, -OR6 et/ou -CN, et les radicaux

alcényles linéaires ou ramifiés en C-j-Cg ;

y y Ar-- [ "-----Ar4 0 0 formule (VI) R5 R5 aans laquelle : - R5, identiques ou différents, ont les mêmes significations que dans la formule (III), - Y, identiques ou différents, représentent X et/ou R4, - Z représente : . une liaison directe, - un radical divalent alkylène en C1-C6, ou un radical phénylène, diphénylène ou phénylène-T-phénylène, ou encore forme, avec les deux R15 represents a radical chosen from the group consisting of a radical Ar2, a radical - (C = O) -Ar2, a linear or branched alkyl radical C1-C12, a cycloalkyl radical C6-C12, and a cycloalkyl radical forming a C6-C12 ring with the carbon of the ketone or a carbon of the radical Ar2, which radicals may be substituted with one or more substituents selected from the group consisting of -F, -CI, -Br, -CN, -OH, -
CF 3, -OR 6, -COOR 6, linear or branched C 1 -C 12 alkyl radicals optionally bearing an -OH, -OR 6 and / or -CN group, and

linear or branched C 1 -C 6 alkenyl radicals;

Wherein: Ar3 has the same meaning as Ar1 of formula (III) in the case where n = 1, - R16, identical or different, represent a radical selected from the group consisting of: a group consisting of a radical Ar3, a radical - (C = O) -Ar3, a linear or branched C1-Cl2 alkyl radical, a Cg-C cycloalkyl radical, these radicals being able to be substituted by one or more substituents chosen from the group consisting of -F, -CI, -Br, -CN, -OH, -CF3, -OR6, -SR6, -
COOR6, linear or branched C1-C12 alkyl radicals optionally bearing a -OH, -OR6 and / or -CN group, and radicals

linear or branched C 1 -C 6 alkenyls;

embedded image in which: R 5, which are identical or different, have the same meanings as in formula (III); Y, which are identical or different, represent X and / or R 4, - Z represents: a direct bond, a divalent C 1 -C 6 alkylene radical, or a phenylene, diphenylene or phenylene-T-phenylene radical, or alternatively forms with both

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substituents R5 and the two carbon atoms bearing these substituents, a cyclopentane or cyclohexane ring, a divalent group -O-RO -, -O-SiR8R9-o-SiR8R9-o-, or -O-SiR8R9 ~ 0 -, - R12 represents a C2-C8 alkylene radical, C4-C6 alkenylene or xylylene.

and Art has the same meaning as Ar1 of formula (III) in the case where n = 1.

 In the case where the composition to be crosslinked and / or polymerized contains absorbent pigments in the U.V. domain, a radical initiator Am having a maximum absorption in the visible range will be selected.

 In the case of use for the manufacture of transparent silicone adhesive under U.V. activation, a radical initiator Am will be chosen whose absorption maximum is superimposable with the emission lines of the U.V.

1, 5 dihydroxyanthraquinone ; 1, 3-diphényl-1, 3-propanedione ; 5, 7-dihydroxyflavone ; dibenzoylperoxyde ; acide 2-benzoylbenzoique ; 2-hydroxy-2méthylpropiophénone ; 2-phénylacétophénone ; 2,4, 6-triméthylbenzoyldiphénylphosphine oxyde ; anthrone ; bi (2,6 diméthylbenzoyl) -2, 4, 4-triméthylpentylphosphine oxyde ; poly [, 1, 4-benzènedicarbonyi- ait-bis (4-phénoxyphényl) méthanone] ;

"

As examples of initiator compounds, mention will be made in particular of the following products:
9-xanthenone; 1-4 dihydroxyanthraquinone; anthraquinone; 2-methylanthraquinone; 2,2'-bis (3-hydroxy-1,4-naphthoquinone);
2-6 dihydroxyanthraquinone; 1-hydroxycyclohexylphenylketone;

1,5-dihydroxyanthraquinone; 1,3-diphenyl-1,3-propanedione; 5,7-dihydroxyflavone; dibenzoylperoxide; 2-benzoylbenzoic acid; 2-hydroxy-2-methylpropiophenone; 2-phenylacetophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide; anthrone; bis (2,6-dimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide; poly [, 1,4-benzenedicarbonyl-bis (4-phenoxyphenyl) methanone];

"

4, 4'diméthoxybenzoïne ; phénanthrènequinone ; 2-éthylanthraquinone ; 2-méthylanthraquinone ; Preferably, the initiator compound (s) will be chosen from the group consisting of:

4,4'-dimethoxybenzoin;phenanthrenequinone;2-ethylanthraquinone;2-methylanthraquinone;

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2-hydroxy-2méthylpropiophénone ; benzaldéhyde ; 4- (2-hydroxyéthoxy) phényl- (2-hydroxy-2-méthylpropyl) cétone ;

TTT benzoylacétone ; < x/-rr-cH,-oc et et leur mélange.

1,8-dihydroxyanthraquinone; dibenzoylperoxide; 2,2-dimethoxy-2-phenylacetophenone; benzoin;

2-hydroxy-2-methylpropiophenone; benzaldehyde; 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-methylpropyl) ketone;

TT benzoylacetone; <x / -rr-cH, -oc and and their mixture.

As examples of commercial products of initiator compounds, mention may be made of the products marketed by CIBA-GEIGY: Irgacure 369, Irgacure 651, Irgacure 907, Darocure 1173, etc.

The initiator compounds used in the compositions of the invention may be used, as they are obtained at the end of their preparation process, for example in solid or liquid form or in solution in a suitable solvent or in a diluent Di and / or Do.

 According to a first variant concerning the diluent, the silicone Di is preferably of the oligomeric or polymeric type.

 According to a second variant, the silicone Di comprises at least two silicon atoms.

This silicone Di can be chosen from a large number of silicones bearing at least one reactive function Z. These functions Z can be chosen in particular from the following radicals:

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- avec R'représentant un radical alkyle linéaire ou ramifié en C1-C6.

with R.sub.1 being a linear or branched C.sub.1-C.sub.6 alkyl radical.

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By way of examples, the silicone Di may be based on species whose average formulas a) to f) are given below with R being a hydrocarbon radical of 1 to 15 carbon atoms, or an oxyalkyl group of 1 at 15 carbon atoms and at <100.

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 According to a third variant concerning the diluent, it may comprise a species of organic nature C which can be advantageously combined with the silicone Di. In this case, the amount by weight of silicone diluent is preferably higher than that of the organic diluent.

 Among these organic species Do having diluent properties include those bearing at least one acrylate function, alcohol and / or acid.

triméthylolpropane éthoxylate triacrylate, tétraéthylène glycol diacrylate (TTEGDA), tripropylène-glycoldiacrylate (TREGDA), triéthylène-glycol diacrylate (TREGDA), triméthylpropane triméthacrylate (TMPTMA), acrylo-uréthanes, acrylopolyéthers, acrylopolyesters, polyesters insaturés, et acryloacryliques, l'éthylhexyl acrylate, le 2-éthoxyethyl acrylate, le lauryl acrylate, le stéaryl acrylate, l'isobornyl acrylate, les acrylates d'huile de soja époxydée, 1,4 butanedioldiacrylate, le néopentylglycoldiacrylate, l'isododécylacrylate, l'hydroxyéthylacrylate, l'hydroxyéthylméthacrylate, et le composé de formule ci-après :

For organic acrylate diluents, there may be mentioned, for example, the following compounds: bisphenol-A-epoxydiacrylate; acryloglycero-polyester obtained from glycerol and polyester, pentaerythritoltriacrylate (PETA), trimethylol propane triacrylate (TMPTA), 1,6-hexanediol diacrylate (HDODA),

trimethylolpropane ethoxylate triacrylate, tetraethylene glycol diacrylate (TTEGDA), tripropyleneglycoldiacrylate (TREGDA), triethylene glycol diacrylate (TREGDA), trimethylpropane trimethacrylate (TMPTMA), acrylourethanes, acrylopolyethers, acrylopolyesters, unsaturated polyesters, and acryloacrylics, ethylhexyl acrylate , 2-ethoxyethyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, epoxidized soybean oil acrylates, 1,4 butanedioldiacrylate, neopentylglycoldiacrylate, isododecylacrylate, hydroxyethylacrylate, hydroxyethylmethacrylate, and the compound of formula below:

For organic diluents alcohols, mention may be made in particular of polyols; and by way of example the following compound:

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Examples of organic diluents for alkenyl ethers are: dodecylvinyl ether (DDVE), cyclohexylvinyl ether (CVE), butanedioldivinyl ether (BDVE), butanediolmonovinyl ether (HBVE), cyclohexanedimethanol divinyl ether (CHDVE) and cyclohexane dimethanol monovinyl ether (CHMVE), triethylene glycol divinyl ether (DVE-3), and 1,4-cyclohexane dimethanol divinylether (CHVE).

The composition according to the invention may also contain a stabilizing additive based on primary, secondary or tertiary amine; this amine is preferably chosen from the derivatives described in the patent application WO98 / 07798
In general, the adhesive composition according to the invention is prepared by mixing (i) the resin Re, (ii) the silicone gum Go in solution, (iii) diluent Di, and (iv) optionally of the initiator Am. After this first step, the solvent is removed by devolatilization. The initiator Am is then added if it is not present in the initial mixture.

 The silicone adhesive composition can be applied to various types of carriers by any of the known methods of spreading, for example scraping, etching, brushing, spraying and indirect roll coating. As a support, there may be mentioned, for example, paper, glass, metals, plastics or any other support based on synthetic and / or fibrous material.

 Once the support selected and coated with the desired thickness of the composition according to the invention, the crosslinking and / or polymerization is carried out by U.V. treatment and / or electron beam. Advantageously, the curing of the adhesive silicone composition can be carried out in the presence of oxygen if the duration of the treatment under U.V. and / or electron beam is greater than 1/10 of a second.

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 In general, the desired coating thickness is on the order of 0.1 μm to 100 μm in a thin layer and in the order of 100 μm to 10 cm in a thick layer.

 After crosslinking and / or polymerization of the compositions according to the invention on a support, the adhesives obtained which are sensitive to pressure can be associated with non-adherent supports with respect to said adhesive and thus form so-called adhesive complexes. Adhesive protective papers such as labels, decorative papers, adhesive tapes are in particular made from this type of complex. Other types of PSA adhesives can be developed; for example, adhesive tapes for electrical insulation, for electronic circuits, adhesive tapes for protecting electrical cable ends, or adhesive tapes for masking areas exposed to plasma spraying of metals or carbides at high temperatures.

Examples.

The examples below illustrate some advantages of the compositions according to the invention.

1. Preparation of the crosslinkable PSA1 composition

 A pressure sensitive adhesive composition for micaceous tape is obtained by preparing a resin in a reactive diluent medium.

An MQ-type silicone resin with a molar ratio M / Q = 60/40 in 60% toluene is mixed with a patterned silicone rubber D with a viscosity of 1 million mPa. s and hydroxylated end of chain with a ratio gum / resin of 0,89 (or 65% of resin in solution for 35% of gum)
100 parts by weight of this mixture are added to 24 parts by weight of silicone diluent b) where a = 13. The toluene is removed under vacuum from 20 mm / Hg at 70 ° C. with stirring for one hour.

The resin obtained contains from 28 to 30% of diluent b) and has a viscosity at 20 C of about 20000 mPa. s. After devolatilization, 2.5 parts by weight of an initiator Am1 composed of 50% by weight of 1-hydroxycyclohexyl phenyl ketone and 50% by weight of benzophenone (= Irgacure 500 from CIBA) are added.
The PSA composition 1 is thus obtained.

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He. Preparation of the crosslinkable PSA2 composition

 To the PS1 composition is added 10% by weight of cyclohexanedimethanoldivinyl ether diluent. The viscosity measured is 2000 mPa. s.

 After devolatilization, 2.5 parts by weight of initiator Am1 are added. The PSA2 composition is thus obtained.

III. Tests on micaceous paper or polyester film.

 1. Application of these formulations on micaceous paper and polyester film.

 The compositions are applied to the Meyer 2 bar on micaceous paper or on polyester film to obtain a coating 10 microns thick.

 The compositions coated on the supports are then cross-linked and / or polymerized under different irradiation conditions from a scroll of the coated support on a conveyor whose carpet runs under two mercury vapor lamps (UV bench with arc lamp IST of 2 Hg - 80W / cm, marketed by the company IST).

 2. Evaluation of adhesiveness.

 Adhesiveness or tack is measured by characterizing the force required to separate the support coated with a crosslinked adhesive composition and / or polymerized and a support vis-à-vis, such as a steel plate or glass.

After the crosslinking polymerization, the tack is measured for each of the coatings obtained at different speeds of travel of the support under the UV lamp. Coatings having a low, medium or high tack are thus obtained.

<Tb>
<Tb>

Tests <SEP> Compositions <SEP> Support <SEP> Speed <SEP> Tack
<tb> m / min <SEP> On <SEP> steel
<tb> polite
<tb> 1 <SEP> PSA1 <SEP> PET / Mylar <SEP> 10 <SEP> Medium
<tb> 2 <SEP> PSA2 <SEP> PET / Mylar <SEP> 10 <SEP> Low
<tb> 3 <SEP> PSA1 <SEP> PET / Mylar <SEP> 100 <SEP> Strong
<tb> 4 <SEP> PSA2 <SEP> PET / Mylar <SEP> 100 <SEP> medium
<tb> 5 <SEP> PSA1 <SEP> Paper <SEP> Mica <SEP> 10 <SEP> Medium
<tb> 6 <SEP> PSA2 <SEP> Paper <SEP> Mica <SEP> 10 <SEP> Low
<tb> 7 <SEP> PSA1 <SEP> Paper <SEP> Mica <SEP> 100 <SEP> Strong
<tb> 8 <SEP> PSA2 <SEP> Paper <SEP> Mica <SEP> 100 <SEP> Medium
<Tb>

Claims (1)

Claims 1. A pressure-sensitive, solvent-free, cationically curable adhesive composition comprising: (a) at least one Re silicone resin containing at least one R13SiO1 / 2 unit, and at least one Sitz tetrafunctional unit and / or a trifunctional unit OFHN. where R1 and R2, which are identical or different, are monovalent radicals chosen from alkyl radicals, alkenyl radicals and hydroxyl radicals, # (b) at least one Go silicone gum having a viscosity greater than 100,000 mPa. s, and preferably greater than 200,000 mPa. s, and functionalized at the end (s) of chain (s) with at least one acrylate group and / or vinyl and preferably hydroxy, # (c) 1 to 50% by weight of a diluent of silicone nature of viscosity less than 100 mPa. s based on at least one silicone Di comprising: it has at least one unit of formula (11):

 in which: a = 0, 1 or 2, - R 3, which is identical or different, represents an alkyl, kyl, cycloalkyl, aryl, vinyl or alkoxy radical, preferably a lower C 1 -C 6 alkyl, the same or different, is an organic substituent comprising at least one acrylate, acrylamide and / or alkenyl ether reactive functional group, # (d) and an effective amount of U activatable activator Am and / or electron beam selected from at least one compound corresponding to one of the following formulas (III) to (VI):

 Wherein: n = 1, Ar represents an aryl radical containing from 6 to 18 carbon atoms, a tetrahydronaphthyl, thienyl, pyridyl or furyl radical or an aryl radical; <Desc / Clms Page number 14>  phenyl radical bearing one or more substituents selected from the group consisting of F, Cl, Br, CN, OH, linear or branched alkyls;

 C1-C12, -CF3, -OR6, -OPhenyl, -SR6, -SPhenyl, -SO2Phenyl, -COOR6, -O- (CH2-CH = CH2), -O (CH2H4-O) mH, -O (C3H60) mH, m being from 1 to 100, when n = 2, Ar1 represents a C6-C12 arylene radical or a phenylene-T-phenylene radical, where T represents -O-, -S-, -SO2- or - CH2-, X represents a group -OR7 or -OSiR8 (R9) 2 or forms, with R4, a group -O-CH (R10) ~, -R4 represents an unsubstituted C1-C8 linear or branched alkyl radical;

 or bearing a group -OH, -OR6, acyloxy C-Cg, -COOR, -CF, or - CN, a C3 or C4 alkenyl radical, a C6 to C18 aryl radical, a phenylalkyl radical; R5 has one of the meanings given for R4 or represents a -CH2CH2R11 radical, or else forms with R4, a C2-C8 alkylene radical or a C3-C9 oxa-alkylene or aza-alkylene radical, R 6 represents a lower alkyl radical containing from 1 to 12 carbon atoms, R 7 represents a hydrogen atom, a C 1 -C 12 alkyl radical, a C 2 -C 6 alkyl radical carrying an -OH group, -OR or-CN, a C3-C6 alkenyl radical, a cyclohexyl or benzyl radical, a phenyl radical optionally substituted by a chlorine atom or a linear or branched C1-C12 alkyl radical, or a tetrahydropyranyl-2, -R8 radical and R9 are the same or different and each represents a C1-C4 alkyl radical or a phenyl radical, - R10 represents a hydrogen atom, a C1-C8 alkyl radical; or a phenyl radical; R11 represents a radical -CONH2, -CONHR6, -CON (R6) 2, -P (O) (OR6) 2 or pyridyl-2;

 A 2 1 R 15 A (2 n R 15 formula (IV) 0

 in which: Ar2 has the same meaning as Ar1 of formula (III) in the case where <Desc / Clms Page number 15>  R15 represents a radical chosen from the group consisting of a radical Ar2, a radical - (C = O) -Ar2, a linear or branched alkyl radical in C1-C12, a C6-C12 cycloalkyl radical, and a cycloalkyl radical forming a C6-C12 ring with the carbon of the ketone or a carbon of the radical Ar2, these radicals being able to be substituted by one or more substituents chosen from the group consisting of -F, -CI, -Br, -CN, -OH, - CF 3, -OR 6, -SR 6, -COOR 6, linear or branched C 1 -C 12 alkyl radicals optionally bearing an -OH, -OR 6 and / or -CN group, and

 linear or branched alkenyl radicals C 1 -C 8;

 In which: Ar3 has the same meaning as Ar1 of formula (III) in the case where n = 1, R16, identical or different, represent a radical chosen from the group consisting of a radical Ar3, a radical - (C = O) -Ar3, a linear or branched alkyl radical C1-C12, a cycloalkyl radical C6-C12, these radicals being able to be substituted by one or more substituents selected from the group consisting of -F, -Cl, -Br, -CN, -OH, -CF3, -OR6, -SR6, - COOR6, linear or branched C1-C12 alkyl radicals optionally bearing an -OH, -OR6 and / or -CN group, and linear or branched C1-C8 alkenyl radicals;

 in which: RS, which are identical or different, have the same meanings as in formula (III); Y, which are identical or different, represent X and / or R4; Z represents: ## STR5 ## a direct bond, a divalent C 1 -C 6 alkylene radical, or a phenylene, diphenylene or phenylene-T-phenylene radical, or else forms with both <Desc / Clms Page number 16>  substituents R5 and the two carbon atoms bearing these substituents, a cyclopentane or cyclohexane ring, a divalent group -O-R-O-, -O-SiR8R9-0-SiR8R9-O-, or -O- SiR8R9-o-, - R12 represents a C2-C8 alkylene, C4-C6 alkenylene or xylylene radical.  and Ar4 has the same meaning as Ar1 of formula (III) in the case where n = 1. 2. Composition according to the preceding claim characterized in that the silicone of the diluent Di comprises at least two silicon atoms. 3. Composition according to the preceding claim characterized in that the eraser Go is functionalized at the end (s) of chain (s) with at least one hydroxyl group. 4. Composition according to any one of the preceding claims, characterized in that the initiator compound Am is chosen from at least compounds of the group consisting of: 4,4'-dimethoxybenzoin; phenanthrenequinone;

 2-ethylanthraquinone; 2-methylanthraquinone; 1,8-dihydroxyanthraquinone; dibenzoylperoxide; 2,2-dimethoxy-2-phenylacetophenone; benzoin; 2-hydroxy-2-methylpropiophenone; benzaldehyde; 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-methylpropyl) ketone,

 benzoy) acetone; - "-" -, (\ /) - r'2- [r '' 5 OC2Hs

 5. Composition according to any one of the preceding claims, characterized in that the silicone diluent Di is chosen from silicone species comprising at least one reactive function Z chosen from the following radicals: <Desc / Clms Page number 17>

 6. Composition according to any one of the preceding claims, characterized in that said composition comprises, in addition to a silicone diluent Di, an organic diluent Do. 7. Composition according to the preceding claim characterized in that the organic diluent Do is selected from organic species bearing at least one function an acrylate function, alcohol and / or acid. 8. The coating obtained from a composition according to any one of the preceding claims. 9. Coating according to the preceding claim characterized in that the coating is a pressure-sensitive adhesive. <Desc / Clms Page number 18> 10. A process for preparing a pressure-sensitive and solvent-free silicone adhesive coating comprising: an initial step of mixing the resin Re and the silicone gum Go in solution, the diluent Di, and optionally the initiator Am as defined in claims 1 to 7, a step of devolatilization to remove the solvent, a step of adding the initiator Am if it is not present in the mixture of the initial step, - a step of spreading on a support, and a step of crosslinking and / or polymerization by treatment under UV and / or electron beam. 11. A process for preparing a pressure-sensitive adhesive coating from a composition according to any one of claims 1 to 7 of the product obtained according to the process of claim 10. 12. Method according to the preceding claim characterized in that the composition is applied to a support selected from paper, plastic, metal and / or glass; and exposed to U.V. and / or electron beam processing.