EP1401975A1

EP1401975A1 - Compositions based on radiation-curable functionalised silicones and anti-adhesive coatings obtained from same

Info

Publication number: EP1401975A1
Application number: EP02740851A
Authority: EP
Inventors: Jean-Marc Frances; Véronique HANTIN; Gérard Mignani; Michel Sciolla; Lucile Gambut-Garel
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 2001-06-01
Filing date: 2002-05-31
Publication date: 2004-03-31
Also published as: US20040214018A1; FR2825367A1; WO2002096998A1; FR2825367B1; US7109251B2

Abstract

The invention concerns a radiation-curable silicone coating based on silicones having a viscosity not more than 1500 mPa's, radiation-curable, comprising: (a) at least a liquid polyorganopolysiloxane polymer Pa with viscosity higher than 500 mPa's and having at least a terminal unit of formula [Z-Si (R1)(R2) -O-] (I), and (b) at least a polyorganopolysiloxane polymer Pb, with viscosity less than 150 mPa's and having at least a unit of formula (I) defined above and/or at least a unit of type D of formula -[-(Si(R1)(Z)-O-]- (ii), Z being a crosslinkable and/or polymerisable group; (c) at least an efficient amount of at least an initiator consisting of onium borate.

Description

Compositions based on functionalized silicones curable under irradiation and non-stick coatings obtained from these compositions.

The present invention relates to new silicone compositions curable under UV irradiation and / or electron beam. More specifically, the subject of the invention is new compositions for coatings based on a mixture of polyorganosiloxanes with a viscosity of less than 1500 mPa.s comprising at least one polyorganosiloxane Pa with at least one unit M carrying at least one reactive function and at least one polyorganosiloxane Pb carrying at least one reactive function on at least one M or D unit; these functions being crosslinkable and / or polymerizable under UV irradiation or electron beam. These mixtures are effectively crosslinked and / or polymerized under irradiation in the presence of compatible cationic initiators and are particularly suitable for their use in the field of non-stick paper supports.

It is known to use curable silicone compositions to make surfaces non-adherent to materials which would normally adhere to them. To date, it is known to use cationic crosslinkable and / or photopolymerizable compositions to obtain coatings with non-stick properties consisting of silicone oils or resins functionalized with epoxide (s), alkenylether (s), oxetane ( s), etc.

Non-stick coatings are useful for many applications where it is necessary to make a surface or a material which would normally adhere to them non-stick to other materials.

For example, the silicone compositions are used as coatings for release papers and can therefore be combined with adhesive elements which can be easily released without losing their adhesive properties, these elements being pressure-sensitive adhesives for labels, decorative laminates, transfer tape, etc. Silicone-based non-stick coatings applied to paper, polyethylene, polypropylene, polyester and the like are also useful as non-stick surfaces for food handling and industrial packaging applications. For example, when a label is coated with an adhesive and associated with a non-adherent support, it is desirable that the latter be easily separated during use, without its quality of adhesion being reduced by the fact that it was separated from the support. The same principle applies to certain ribbons with a non-stick side and a stick side and which are supplied in reels. In fact, it is necessary for the tape to unroll easily and retain its adhesion characteristics on the adherent side after a long period of storage and possibly a high pressure between the adhesive side and the non-stick side, in particular insofar as these coils can sometimes reach more than a meter in diameter. We try to obtain these results by coating the non-stick support or the non-stick side of the tape with a silicone-based non-stick composition which will subsequently come into contact in a reversible manner with the adhesive.

It therefore appears necessary that the silicone-based non-stick coatings, when combined with adhesives, give these associations called silicone / adhesive complexes a weak release force, stable over time, and stable whatever the pressure exerted. between the non-stick coating and the adhesive, while also ensuring constant adhesion properties for the latter.

On the other hand, the non-stick coatings must fulfill other conditions at best, and in particular, they must harden quickly and the initiator must be selected to be miscible with the silicones of the composition.

These objectives are precisely achieved and optimized according to the present invention. Indeed, the silicone compositions developed are specifically adapted for the preparation of non-stick coatings and give the silicone / adhesive complexes a low release force; this detachment force being stable during storage over time and stable regardless of the pressure exerted between the non-stick coating and the adhesive. Other advantages, and in particular the improvement of the properties of instant adhesiveness, of exfoliation and of slippery-tacky, will become apparent on reading the description.

Thus, the subject of the present invention is a crosslinkable and / or polymerizable composition for non-stick coating based on silicone based on silicones of viscosity less than or equal to 1500 mPa.s, curable under irradiation, characterized in that it comprises :

(a) from 50 to 99% by weight, preferably 70 to 99%, of at least one linear, branched and / or cyclic liquid polyorganopolysiloxane polymer Pa with a viscosity greater than 500 mPa.s and having at least one terminal unit of type M of formula (I):

[Z-Si (R ¹ ) (R ² ) -O -] - (I) in which: - the symbols R ¹ and R ² , identical and / or different, represent: (i) a linear or branched alkyl radical containing 1 to 8 carbon atoms, optionally substituted with at least one halogen, preferably fluorine, the alkyl radicals preferably being methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl,

(ii) a cycloalkyl radical containing between 5 and 8 cyclic carbon atoms, optionally substituted,

(iii) an aryl radical containing between 6 and 12 carbon atoms which can be substituted, preferably phenyl or dichlorophenyl,

(iv) an aralkyl part having an alkyl part containing between 5 and 14 carbon atoms and an aryl part containing between 6 and

12 carbon atoms, possibly substituted on the part aryl with halogens, alkyls and / or alkoxyls containing 1 to 3 carbon atoms,

(v) an OH hydroxyl group or an alkoxyl group containing from 1 to 8 carbon atoms (vi) a hydrogen radical,

the symbols Z, which are identical and / or different, represent: a crosslinkable and / or polymerizable organofunctional group, preferably epoxy, acrylate, alkenyloxy and / or oxetane, the organofunctional group being linked to the silicon of the polyorganosiloxane by means of a divalent radical containing from two to twenty carbon atoms and which may contain at least one heteroatom, preferably oxygen.

(b) from 1 to 50% by weight, preferably 1 to 30%, of at least one liquid polyorganopolysiloxane polymer Pb, linear, branched and / or cyclic, of viscosity less than 150 mPa.s and having at least one unit type M terminal of formula (I) defined above and / or at least one type D unit of formula (II):

- [- (Si (R ¹ ) (Z) -O -] - (II) in which the symbols R ¹ and Z, identical or different, have definitions identical to those given above,

(c) and an effective amount of at least one initiator consisting of an onium borate.

In general, the irradiation is carried out under UV radiation and / or under an electron beam.

For UV radiation, a wavelength between 200 and 400 nanometers is preferably used between 230 and 360 nanometers. The irradiation time can be short, that is to say less than 1 second and, on the order of a few hundredths of a second for small thicknesses of coatings. The curing time is regulated (a) by the number of UV lamps used, (b) by the duration of exposure to UV and / or (c) by the distance between the composition and the UV lamp Examples of usable devices for the electron beam are those with a pulsed electron beam ("Scanned Electron Beam Acceleratot") and those with a curtain electron beam ("Electron Curtain Accelerator") .

The reactive functions Z can be of very varied structures. As examples of divalent radicals linking a functional group Z of the epoxy and / or oxetane type, mention may be made of those included in the following formulas:

(CH ₂ ) ₃ O— CH ₂ - CH- -CH ₂ ; (CH ₂ ) ₃ O— CH- -CH

\ _{_0/0}

As regards the functional groups Z of the alkenyloxy type, mention may be made of those contained in the following formulas:

(0) _n (CH ₂ ) - O-CH = CH ₂

(O) n '(CH ₂ ) - R ³ - O-CH = CH ₂ ;

⁽⁰⁾ n '(CH ₂ ) - O-CH = CH -R ⁴

in which :

• n 'represents 0 or 1 and n "an integer between 1 and 5

R ³ represents: a linear, branched or cyclic C1-C1 ₂ alkylene radical, optionally substituted, - or a C5-C12 arylene radical, preferably phenylene, optionally substituted, preferably by one to three C1-Cβ alkyl groups,

• R ⁴ represents a linear or branched Cι-C ₆ alkyl radical. As regards the functional groups Z of dioxolane type, mention may be made of those contained in the following formulas:

According to a first preferred mode, for the silicone Pa, the latter only comprises groups Z at the end of the chain.

According to a second preferred mode, the polyorganosiloxane Pa also comprises type D groups of formula (II).

According to a third preferred mode for the silicone Pa, the Z functions of the polymer Pa are polymerizable and / or crosslinkable functions of the epoxy type.

According to a preferred embodiment for the silicone Pb, the Z functions of the polymer Pb are polymerizable and / or crosslinkable functions of the epoxy type. More particularly, the polyorganosiloxanes Pb used comprise 4 to 6 organofunctional Z groups per macromolecular chain.

The onium borate used in the context of the present invention is judiciously chosen; in fact, it must be miscible with the mixture of silicone constituents Pa and Pb and therefore it must be capable of dissolving well or dispersing in the composition according to the invention. This onium borate is chosen from onium borates of an element of groups 15 to 17 of the periodic table [Chem. & Eng. News, vol. 63, No. 5, 26 of February 4, 1985] of which: m the cationic entity of borate is selected from: (1 ") the onium salts of formula (I): [(R5) _n - A - (R6) _m ] ⁺ (I) formula in which:

• A represents an element from groups 15 to 17 such as for example: I, S, Se, P or N,

R5 represents a CQ-C20 carbocyclic or heterocyclic aryl radical, said heterocyclic radical possibly containing nitrogen or sulfur as heteroelements,

• R6 represents R ^ OR a linear or branched C1-C30 alkyl or alkenyl radical; said radicals R§ and R being optionally substituted by a C1-C25 alkoxy, C1-C25 alkyl, nitro, chloro, bromo, cyano, carboxy, ester or mercapto group,

• n is an integer ranging from 1 to v + 1, v being the valence of the element A,

• m is an integer ranging from 0 to v - 1 with n + m = v + 1,

(2 ") the oxoisothiochromanium salts described in patent application WO 90/11303, in particular the sulfonium salt of 2-ethyl-4-oxoisothiochromanium or of 2-dodecyl-4-oxoisothio-chromanium,

"and the anionic borate entity has the formula [BX ' _a R ^? b] ^" in which:

- a and b are integers ranging for a from 0 to 3 and for b from 1 to 4 with a + b = 4, - the symbols X 'represent:

* a halogen atom (chlorine, fluorine) with a = 0 to 3,

^* an OH function with a = 0 to 2,

- the symbols R ⁷ , identical or different, represent:

> a phenyl radical substituted by at least one electron-withdrawing group such as for example OCF3, CF3, NO2, CN, and / or by at least 2 halogen atoms (all fluorine particularly), and this when the cationic entity is an onium of an element from groups 15 to 17,

> a phenyl radical substituted by at least one element or an electron-withdrawing group, in particular a halogen atom (especially fluorine), CF3, OCF3, NO2,

CN, and this when the cationic entity is an organometallic complex of an element from groups 4 to 10

> an aryl radical containing at least two aromatic rings such as for example biphenyl, naphthyl, optionally substituted with at least one element or an electron-withdrawing group, in particular a halogen atom (fluorine in particular), OCF3, CF3, NO2, CN, whatever the cationic entity.

Without being limiting, more details are given below as to the subclasses of onium borate more particularly preferred in the context of the compositions according to the invention.

According to a first preferred variant of the invention, the species of the anionic borate entity which are very particularly suitable are the following:

V [B (C ₆ F ₅ ) ₄ ] - 5 ': [B (C ₆ H ₃ (CF ₃ ) 2) ₄ ]

2 '[(C ₆ F5) ₂ BF ₂ ] - 6': [B (C ₆ H ₃ F ₂ ) ₄ ] -

3 '[B (C ₆ H ₄ CF ₃ ) 4] - T: [C ₆ F ₅ BF ₃ ] -

4 '[B (C ₆ F ₄ OCF ₃ ) ₄ ] -.

According to a second preferred variant of the invention, onium salts

(1) which can be used are described in numerous documents, especially in patents US-A-4,026,705, US-A-4,032,673, US-A-4,069,056, US-A- 4,136,102, US-A- 4,173,476. Among these, the following cations will be particularly favored: [(Φ-CH ₃ ) ₂ I] ⁺ [(C ₈ H ₁₇ -0-Φ) ₂ l] ⁺

[(C ₁₂ H ₂ 5-) 2 '] ⁺ [(CH ₃ -Φ-I-Φ-C ₁₂ H ₂ 5] ⁺ [(HO-CH ₂ -CH ₂ ) ₂ S-CH ₂ -Φ] ⁺ [(C ₁₂ H ₂₅ -CH (OH) -CH ₂ -O-Φ) ₂ l] ⁺

[(HO-CH ₂ -CH ₂ -O Φ) ₃ S] ⁺ [(HO-CH ₂ -CH ₂ -OΦ) 2-S-Φ-OC ₈ Hi7] ⁺ and [(CH ₃ -Φ-I- Φ-CH (CH ₃ ) 2] ⁺ [(CH ₃ ) ₃ C-Φ-I-ΦC (CH ₃ ) ₃ ] ⁺

In agreement with these two preferred variants, mention may be made, as examples of initiators of the onium borate type, of the following products:

[(C ₁₂ H ₂ 5-CH (OH) -CH ₂ -O-Φ) ₂ l] ⁺ , [B (C ₆ F ₅ ) 4] ^" [(C8H ₁₇ -O-Φ) 2l] ⁺ , [ B (C ₆ F5) ₄ ] -

[(CH ₃ ) ₃ C-Φ-I-ΦC (CH ₃ ) ₃ ] ⁺ , [B (C ₆ F ₅ ) ₄ ] -

[(C ₁₂ H25-Φ) 2l] ⁺ _I [B (C ₆ F ₅ ) ₄ ] -

[(Φ-CH ₃ ) ₂ I] ⁺ , [B (C ₆ F ₅ ) ₄ ] -

[(Φ-CH ₃ ) ₂ l] ⁺ , [B (C ₆ F ₄ OCF ₃ ) ₄ ] - [CH ₃ -Φ-I-Φ-CH (CH ₃ ) ₂ ] ⁺ , [B (C ₆ F ₅ ) ₄ ] ^"

[(HO-CH ₂ -CH ₂ ) ₂ S-CH ₂ -Φ] ⁺ , [B (C ₆ F ₅ ) ₄ ] ^'

[CH3-Φ-I-Φ-CH (CH ₃ ) ₂ ] ⁺ , [B (C ₆ H ₃ (CF ₃ ) 2) ₄ r and [(C ₁₂ H ₂₅ Φ) ₂ I] ⁺ , [B ( C ₆ H ₃ (CF ₃ ) 2) 4] ^'

The composition according to the invention can also comprise additives such as for example stabilizers, bonding additives, (photo) sensitizers. The stabilization additive can be based on primary, secondary or tertiary amine; preferably, this amine is chosen from the derivatives described in patent application WO98 / 07798. The bonding additive is generally based on silanes and / or organic monomers. The sensitizer (photo) can for example be chosen from the compounds of the benzophenone type described in application WO 99/05181.

A second aspect of the present invention relates to a non-stick silicone / adhesive complex comprising at least one silicone coating applied to a first support and an adhesive coating applied or not to a second support, characterized in that said silicone coating is derived of a mixture of polyorganosiloxane (s) Pa and Pb in the presence of a miscible photocell as defined above.

According to a first variant, the two supports are made of two separate materials, arranged so that the silicone coating of the first support is in contact with the adhesive coating of the second support. This embodiment is in particular illustrated by systems known as self-adhesive labels associated with a non-adherent support. In this particular case, the release force of the silicone / adhesive interface is exerted during the separation of the two supports. In a second variant, the two supports are constituted respectively by each of the two faces of the same material. This second embodiment is in particular illustrated by the systems known as adhesive tapes. The non-stick coating, that is to say based on the silicone matrix and the adhesive coating are brought into contact during the winding of the support on itself. In this case, the release force is exerted at the silicone / adhesive interface under the effect of the separation of a lower face with an upper face of the material.

With regard to the adhesive coating, it can be very diverse in nature insofar as it is chemically compatible with the silicone coating.

In the context of the present invention, it can in particular be chosen from adhesives of the acrylic type, natural or synthetic gums and / or latex. In general, the adhesive coatings deposited on the surface of a wide variety of materials so as to obtain labels, tapes or any other self-adhesive material derive from emulsions called pressure-sensitive adhesive emulsions (PSA). They give the material the ability to adhere to the surface of a support, without requiring activation other than low pressure.

The monomers used to prepare the PSAs are selected according to their glass transition temperature, Tg, for give the polymers incorporating them the expected behavior in terms of adhesion and viscoelasticity. For this purpose, the monomers advantageously have a sufficiently low glass transition temperature, generally between -70 and -10 ° C and preferably is less than -30 ° C.

More specifically, these monomers are chosen from the group consisting

- (meth) acrylic esters such as the esters of acrylic acid and methacrylic acid with hydrogenated or fluorinated Cι-C ₁₂ alkanols, preferably Cι-C ₈ , in particular methyl acrylate, acrylate ethyl, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, tert-butyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, iso-octyl acrylate, decyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate , isobutyl methacrylate;

- vinyl nitriles including more particularly those having 3 to 12 carbon atoms, such as in particular acrylonitrile and methacrylonitrile;

- vinyl esters of carboxylic acid such as vinyl acetate, vinyl versatate, vinyl propionate,

- ethylenic unsaturated mono- and dicarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the mono- and di-alkyl esters of mono- and di acids -carboxylic of the type mentioned with the alkanols preferably having 1 to 8 carbon atoms and their N-substituted derivatives, the amides of unsaturated carboxylic acids such as acrylamide, methacrylamide, N-methylolacrylamide or methacrylamide, N-alkylacrylamides, ethylenic monomers comprising a sulfonic acid group and its alkali or ammonium salts, for example vinylsulfonic acid, vinylbenzenesulfonic acid, alpha-acrylamido methylpropane-sulfonic acid, 2-sulfoethylene-methacrylate, - the unsaturated ethylenic monomers comprising a secondary, tertiary or quaternary amino group, or a heterocyclic group containing nitrogen such as for example vinylpyridines, vinylimidazole, aminoalkyl (meth) acrylates and (meth) acrylamides) aminoalkyl such as dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate, ditertiobutylaminoethyl acrylate or ditertiobutylaminoethyl methacrylate, dimethylaminomethyl-acrylamide or dimethylaminomethyl-methacrylamide,

- zwitterionic monomers such as, for example, sulfopropyl (dimethyl) aminopropyl acrylate,

- ethylenic monomers carrying a sulfate group,

- ethylenic monomers carrying one or more phosphate and / or phosphonate function (s),

- and their mixtures.

Conventionally, PSAs are obtained by polymerization mainly of alkyl acrylate monomers which are generally present in an amount of 50 to about 99% and preferably in an amount of 80 to 99

% by weight and of copolymerizable polar monomers such as for example acrylic acid, in smaller proportions.

In the context of the present invention, a release force is generally obtained which is less than 20 g / cm, and more frequently a release force is less than 10 g / cm. In general, the force required to peel off the non-stick silicone coating from the adhesive changes at most by a factor of less than 4 and more frequently less than 2, at the end of the 7-day aging test at 70 ° C. , representative of an aging of 6 months.

This release force also does not change, and at most changes by a factor of less than 2, regardless of the pressure exerted between the adhesive and the non-stick silicone coating. EXAMPLES

1. Preparation of coating compositions.

The compositions according to the invention and by way of reference are prepared from the compounds below. These compositions are described in Table 1.

The silicones for the reference compositions are chosen from the silicones Re 1 and Re ₂ of formula (III) below:

in which :

- a = 80, b = 7 and the viscosity = 350 mPa.s for Re ^

- and a = 222, b = 3 and the viscosity = 1000 mPa.s for Re _2.

The Pb type silicones are chosen from Re1 silicone and Pbi silicone of formula (IV) below:

in which ,

- a = 11, b = 0 and the viscosity = 30 mPa.s. The Pa type silicones are chosen from the Pa 2 Pa ₂ and Pa ₃ silicones of formula (IV) in which:

- a = 450, b = 1, 5 and the viscosity≈ 4710 mPa.s ± 300 for Pa ^ -and a = 243, b = 0 and the viscosity = 1050 mPa.s ± 300 for Pa _2. ,

- and a = 400; b = 0 and the viscosity = 3500 mPa.s ± 300 for Pa ₃ .

The photoinitiator Am used is in 18% solution in isopropanol and corresponds to the formula:

2. Polymerization of the compositions.

(i) The compositions prepared are deposited at a rate of 0.8 g / m ² on a polyester film PET6001 from the company TORAY and then irradiated at a speed of 200 m / min under two mercury lamps [power 360W / cm (H ⁺ ), Fusion company]. After exposure to UV light, the coatings obtained are perfectly dry.

3. Tests.

(i) Non-stick silicone / adhesive complexes. The coatings obtained are then combined with the following adhesives:

- adhesive based on rubber compounds: TESA 4651 ® from the company Beïersdorf,

- adhesive based on acrylic compounds and formulated in solvent phase: TESA 4970 ® from the company Beïersdorf, - and adhesive based on acrylic compounds and formulated in the aqueous phase at 50% in water: Rhodotak 315P ® from the company Rhodia Chimie .

(ii) Measures. The detachment force of the different complexes obtained is measured after storage for 20 h at 20 ° C according to the standardized FINAT3 test under a force of 70 g / cm ² with a detachment speed of 300 mm / min

The release force is also measured after 7 days at 70 ° C simulating an aging of 6 months at 20 ° C under pressure conditions of 70 g / cm ² .

In addition, the adhesiveness (tack), exfoliation (rub off) and slip-stick (slip-stick) properties are evaluated.

Exfoliation characterizes the attachment of a silicone coating to a support. It is measured by a trade test which consists of passing the finger up to 10 round trips over the silicone coating by applying light pressure with the finger. If the finger does not catch the coating after 10 round trips, the score is 10. If the finger hangs (scrub) after 5 round trips, the score is 5. If the layer is torn off at the 1st round - return; the score is 0 or 1; the note 0 signifying that the coating does not hold on the support used.

Instant adhesiveness or "tack" characterizes the force necessary to separate at a speed of the order of 300 mm / min an adhesive tape brought into contact with the silicone coating of the invention according to the standardized FINAT 9 test.

The results of the tests are given in Table 2.

Table-1-:

Table 2.

Claims

CLAIMS.

1. A coating composition based on silicone of viscosity less than or equal to 1500 mPa.s, curable under irradiation, characterized in that it comprises:

(a) from 50 to 99% by weight, preferably 70 to 99%, of at least one linear, branched and / or cyclic liquid polyorganopolysiloxane polymer Pa with a viscosity greater than 500 mPa.s and having at least one terminal unit of type M of formula (I): [Z-Si (R ¹ ) (R ² ) -O -] - (I) in which: - the symbols R ¹ and R ² , identical and / or different, represent:

(i) a linear or branched alkyl radical containing 1 to 8 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl radicals being preferably methyl, ethyl, propyl, octyl and 3,3,3- trifluoropropyIe,

(iv) an aralkyl part having an alkyl part containing between 5 and

14 carbon atoms and an aryl part containing between 6 and

12 carbon atoms, optionally substituted on the aryl part by halogens, alkyls and / or alkoxyls containing 1 to 3 carbon atoms,

(v) an OH hydroxyl group or an alkoxyl group containing from 1 to 8 carbon atoms (vi) a hydrogen radical, - the symbols Z, which are identical and / or different, represent: a crosslinkable and / or polymerizable organofunctional group, preferably epoxy, acrylate, alkenyloxy and / or oxetane, the organofunctional group being linked to the silicon of the polyorganosiloxane via a divalent radical containing from two to twenty carbon atoms and which may contain at least one heteroatom, preferably oxygen.

2. Composition according to the preceding claim, characterized in that the polyorganosiloxane Pa only comprises Z groups at the end of the chain.

3. Composition according to any one of the preceding claims, characterized in that the polyorganosiloxane Pa also comprises type D groups of formula (II).

4. Composition according to any one of the preceding claims, characterized in that the Z function of the polymer Pa is a polymerizable and / or crosslinkable function of the epoxy type.

5. Composition according to any one of the preceding claims, characterized in that the Z function of the polymer Pb is a polymerizable and / or crosslinkable function of epoxy type.

6. Composition according to any one of the preceding claims, characterized in that the Fb function is chosen from the group consisting of epoxy, and / or alkenylether and / or oxetane and / or dioxolane functions.

7. Composition according to any one of the preceding claims, characterized in that the onium borate is chosen from onium borates of an element from groups 15 to 17 of the periodic table or of an organometallic complex of element from groups 4 to 10 of the periodic table, of which: the cationic entity of borate is selected from:

(1 ") the onium salts of formula (I):

[(R5) _n - A - (R6) _m ] ⁺ (I) formula in which: »A represents an element from groups 15 to 17 such as for example:

I, S, Se, P or N,

• R ⁵ represents a carbocyclic or heterocyclic CQ-C20 aryl radical, said heterocyclic radical possibly containing nitrogen or sulfur as heteroelements, • R6 represents R5 or a linear or branched C1 or C30 alkyl or alkenyl radical; said radicals R ⁵ and R ^ being optionally substituted by a C-1-C25 alkoxy, C1-C25 alkyl, nitro, chloro, bromo, cyano, carboxy, ester or mercapto group,

• m is an integer ranging from 0 to v - 1 with n + m = v + 1,

a and the anionic borate entity has the formula [BX ' _a R ⁷ fc)] ^~ in which:

* a halogen atom (chlorine, fluorine) with a = 0 to 3,

* an OH function with a = 0 to 2,

- the symbols R, which are identical or different, represent:> a phenyl radical substituted by at least one electron-withdrawing group such as, for example, OCF3, CF3, NO2, CN, and / or by at least 2 halogen atoms (especially fluorine) , and this when the cationic entity is an onium of an element from groups 15 to 17,> a phenyl radical substituted by at least one element or an electron-withdrawing group, in particular halogen atom (fluorine in particular), CF3, OCF3, NO2, CN, and this when the cationic entity is an organometallic complex of an element from groups 4 to 10> an aryl radical containing at least two aromatic rings such as for example biphenyl, naphthyl, optionally substituted by at least one element or an electron-withdrawing group, in particular a halogen atom (especially fluorine), OCF3, CF3, NO2, CN, whatever the cationic entity.

8. Non-stick coating capable of being obtained by crosslinking and / or polymerization from compositions according to any one of the preceding claims.

9. Non-stick silicone / adhesive complex comprising at least one silicone coating applied to a first support and an adhesive coating applied to a second support, characterized in that said silicone coating is derived from a composition according to any one of claims 1 to 7.