WO2001036512A1

WO2001036512A1 - Radiation polymerisable and/or crosslinkable adhesive for plastic based on matrix with reactive functions

Info

Publication number: WO2001036512A1
Application number: PCT/FR2000/003186
Authority: WO
Inventors: Jean-Marc Frances
Original assignee: Rhodia Chimie
Priority date: 1999-11-19
Filing date: 2000-11-16
Publication date: 2001-05-25
Also published as: EP1237982A1; FR2801315A1; AU1867301A

Abstract

The invention concerns a radiation and/or electron beam polymerisable and/or crosslinkable adhesive for bonding two opposite plastic surfaces comprising: 1 to 99 wt. % of at least an organic and/or polymerisable silicone and/or at least partly polymerised matrix A, comprising (co)monomers, (co)oligomers and/or (co) polymers selected among those having oxetane reactive functions (frA); 99 to 1 wt. % of at least an organic and/or polymerisable silicone and/or at least partly polymerised matrix B, comprising (co)monomers, (co)oligomers and/or (co)polymers selected among those having reactive epoxy (α1) and/or acrylate (α2) and/or alkenyl-ether (α3) and/or hydroxy (α4) functions (frB); an efficient amount of at least a cationic and/or radical photoinitiator C, and optionally at least a photosensitizer D.

Description

ADHESIVE FOR POLYMERIZABLE AND / OR CROSSLINKABLE UNDER IRRADIATION MATRIX BASED ON REACTIVE FUNCTIONS.

The field of the invention is that of adhesives for crosslinkable plastics and / or polyméπsables under irradiation, in particular under UV irradiation and / or by electron beam, usable, in particular, to durably assemble two surfaces in vis-

Plastics are increasingly used as packaging materials such as cases and pouches These plastics can be transparent, translucent, colored or opaque and are generally based on polyethylene or polypropylene The nature of the plastics and the shape of the packaging generally require the use of various technologies based on the use of adhesives or the thermofusion technique to secure the different parts of said packaging

To date, however, the technologies proposed are not always suitable for effectively assembling two facing plastic surfaces and for creating an assembly which is stable to handling and / or durable over time.

The present invention proposes to overcome the existing shortcomings in the field of the assembly of two facing plastic surfaces, in particular to improve the solidarity between said surfaces in contact. One of the essential objectives of the present invention is therefore to provide new adhesives based on photopolymerizable and / or photoreticulable compositions by cationic and / or radical route which meet these expectations

Another objective of the present invention is to provide new adhesives for easy implementation using irradiation technologies, in particular UV, and or electron beam

The present invention therefore relates to the use of a polymerizable and / or crosslinkable adhesive under irradiation and / or under electron beam (s), by cationic and / or radical route, to assemble two plastic surfaces facing each other. comprising

- 1 to 99% by weight, and preferably 1 to 60% by weight, of at least one organic matrix A and or polymerizable and / or at least partially polymerized silicone, comprising (co) monomers, (co) oligomers and / or (co) polymers chosen from those having reactive oxetane functions (frA)

- 99 to 1% by weight, and preferably 99 to 40% by weight, of at least one organic matrix B and / or polymerizable silicone and / or at least partially polymerized, comprising (co) monomers, (co) olιgomers and / or (co) polymers chosen from those having reactive functions (frB) epoxy (α- _| ) and or acrylate (_) and or alkenyl ether ( 0: 3) and / or hydroxy (0: 4),

an effective amount of at least one cationic and / or radical photoinitiator C,

- and possibly at least one photosensitizer D

These new adhesives are particularly suitable for effectively joining two plastic surfaces facing each other. The assembly obtained is particularly stable in handling and durable over time.

The matrix A with reactive oxetane functions (frA) used within the composition according to the invention can be based on (co) monomers, (co) olιgomers and / or (co) polymers of very varied natures On this subject , are suitable in particular the (co) monomers, the (co) olιgomers and / or the following (co) polymers consisting of at least one of the following species.

A1) the monomers with oxetane and alkoxy functions, oxetane and hydroxy functions, or oxetane and alkoxysilyl functions of formula

o in which

- Ri is (i) a hydrogen atom, (n) a linear or branched alkyl radical comprising from 1 to 30 carbon atoms, (m) an aryl radical comprising from 6 to 30 carbon atoms optionally substituted by at least one fluorine atom, a carboxy radical, a hydroxy radical, an ester radical or a radical with a ketone function, (iv) a cycloalkyl radical comprising from 5 to 6 carbon atoms optionally substituted by at least one fluorine atom, a hydroxy radical , a carboxy radical, an ester radical or a radical with a ketone function, (v) an OR 'radical where R' is a linear or branched alkyl radical comprising from 1 to 30 carbon atoms, or (vi) an alkenyl radical comprising from 2 to 12 carbon atoms

R ₂ is (i) a hydrogen atom; (n) an alkenyl radical comprising from 2 to 12 carbon atoms (for example a vinyl radical, a propenyl radical), (m) a linear or branched alkyl radical comprising from 1 to 30 carbon atoms optionally substituted, for example, by a group oxirane, (ιv) an aryl radical comprising from 6 to 30 carbon atoms optionally substituted, for example, by at least one alkyl radical comprising from 1 to 30 carbon atoms, a benzyl radical, a CF ₃ radical, a halogen atom, a hydroxy radical, a carboxy radical, an alkoxy radical, (v) a silyl group (CH2) n-SιR ₃ R ₄ R ₅ or n is between 0 and 12, and R ₃ , R ^ and R ₅ , identical or different, represent a hydrogen atom, a hydroxy radical, an alkoxy radical OR 'where R' is a linear or branched alkyl radical comprising from 1 to 30 carbon atoms, (vi) a linear or branched alkyl radical comprising from 1 to 30 carbon atoms, (seen) an aryl radical comprising from 6 to 30 optionally substituted carbon atoms, (wine) an alkenyl radical comprising from 2 to 12 carbon atoms, (ix) an acrylate radical, (x) a methacrylate radical (for example -CO-CH = CH ₂ ), or (xi) a urethane radical -CO-NH-R _T in which R- has the same definition as that given previously

A2) the monomers with carboxy and oxetane functions, or with oxetane and alkoxysilyl functions of formula

in which

- R ^ has the same definition as that given in A1),

- R ₂ has the same definition as that given in A1), A3) the difunctional oxetane monomers of formula

in which

- m, identical or different, is equal to 0 or 1, - R-i is of definition identical to that given in A1)

- R ₆ , a divalent radical, is (i) a linear or branched alkyl radical comprising from 1 to 30 carbon atoms, (n) an aryl radical comprising from 6 to 30 carbon atoms optionally substituted (by at least one alkyl radical comprising from 1 to 30 carbon atoms, (ni) an aryl radical comprising from 6 to 30 carbon atoms (for example a benzyl radical), (iv) a cycloalkyl radical comprising from 5 to 30 carbon atoms (ex cyclohexyl), ( v) a radical -CH ₂ -C ₆ H ₁₀ -CH ₂ -, (vi) a radical -CH ₂ -C ₆ H ₄ -CH ₂ -, (seen) a radical CF ₃ , (wine) an atom of halogen; (ix) a hydroxy radical, (x) a carboxy radical, (xi) an alkoxy radical OR 'where R' has the same definition as that given in A1), (xn) a silylated group = SιR ₃ R where n is between 0 and 12, and R ₃ , R ₄ , identical or different, represent a hydrogen atom, a hydroxy radical, an alkoxy radical OR 'where R' is identical definition to that given in A1), a linear or branched alkyl radical comprising from 1 to 30 carbon atoms, an aryl radical comprising from 6 to 30 carbon atoms optionally substituted, a radical -C ₆ H ₄ -C (CH ₃ ) ₂ -C ₆ H ₄ -, or an alkenyl radical comprising from 2 to 12 carbon atoms.

A4) and the polyorganosiloxanes, consisting of units of formula (II) and terminated by units of formula (III) or cyclic units consisting of units of formula (II) shown below

- 6 R ⁶

(Si-O) - (II) Z - (Si-O) (III

in which the symbols R ⁶ and R ⁷ , similar or different, represent

^• 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-tπfluoropropyle, a cycloalkyl radical containing between 5 and 8 cyclic carbon atoms, optionally substituted, ^• an aryl radical containing between 6 and 12 carbon atoms which can be substituted, preferably phenyl or dichlorophenyl,

^• an aralkyl radical 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,

- the symbols Z, similar or different, represent

^• an R ⁶ and / or R ^{7 group} ,

^• a hydrogen radical,

^• and / or a crosslinkable oxetane-functional group linked to the silicon of the polyorganosiloxane via a divalent radical containing

2 to 20 carbon atoms and which can contain at least one heteroatom, preferably oxygen, which can be directly linked to silicon by forming a ≡Si-OC≡ bond ^• with at least one of the symbols Z representing a crosslinkable oxetane-functional group.

Examples of species A1 include those of the following formulas

Examples of A2 species include those of the following formulas

As A3 species, we will mention those of the following formulas

According to a preferred variant of the invention, the polyorganosiloxaπes A4 used comprise from 1 to 10 organofunctional groups per macromolecular chain

These linear polyorganosiloxanes can be oils of dynamic viscosity at 25 ° C, of the order of 10 to 10,000 mPa.s at 25 ° C, generally of the order of 20 to 5,000 mPa.s at 25 ° C and , more preferably still, from 20 to 600 mPa s at 25 ° C, or gums having a molecular mass of the order of 1,000,000

When cyclic polyorganosiloxanes are involved, these consist of units (II) which can be, for example, of the dialkylsiloxy or alkylarylsiloxy type. These cyclic polyorganosiloxanes have a viscosity of the order of 1 to 5000 mPa s As examples of an organofunctional radical of the oxetane type linked to the backbone of the polyorganosiloxane A4, the group of formula below may be mentioned

The functional polyorganosiloxane oxetanes can be prepared by hydrosilylation of unsaturated oxetanes or condensation of oxetanes containing a hydroxy function.

The polyorganosiloxanes A4 which best meet the object of the invention are described in the formulas below. X can represent an alkyl or cyclohexyl group; trifluoropropyl; perfiuoroalkyle; alkoxy or hydroxypropyl, and R may represent an alkyl radical -C _10, cyclohexyl, trifluoropropyl or perfluoroalkyl in d to C ₁₀ (0≤a <1000); (1 <b <1000):

S8

S9

Regarding matrix B, this can in particular comprise at least one of the following organic species B1 α _η | \ cycloaliphatic epoxides and in particular epoxides of the 3,4-epoxycyclohexylmethyl-3 ', 4'- epoxycyclohexane carboxylate type

or Bιs (3,4-epoxycyclohexyl) adιpate, ^α 1.2) ^{non-cycloaliphatic} epoxides, and in particular

• epoxides of the type of those resulting from the condensation of Bis-phenol A and of epichlorhydπne and of the di and triglyαdylethers of Bisphenol A alkoxylated of 1, 6 hexane diol, of glycerol, of neopentylglycol and of propane tπmethylol, or diglycidyl ethers of Bisphenol A,

• alpha-olefin epoxides, NOVOLAC epoxides, epoxy soybean oil, epoxidized linseed oil, and epoxidized polybutadiene, _Λ acrylates, and in particular

• epoxidized acrylates, preferably the oisomer of Bisphenol A- epoxydiacrylate (EBECRYL 600), • acryloglycero-polyester, preferably a mixture of trifunctional acrylate oligomer obtained from glycerol and polyester (EBECRYL 810),

• multifunctional acrylates, preferably pentaerythritol triacrylate (PETA), trimethylol propane triacrylate (TMPTA), 1, 6-hexanediol diacrylate (HDODA), trimethylolpropane ethoxylate triacrylate, thiodiethylene glycol diacrylate, tetraacrylethylene tetraethylene glycol, tetraethylethylene glycol diethylacrylate diacrylate diacrylate TRPGDA), thethylene glycol diacrylate (TREGDA), thmethylpropane trimethacrylate (TMPTMA),

• acrylo-urethanes,

• acrylo-polyethers,

• acrylo-polyesters,

• unsaturated polyesters,

• acrylo-acrylics,

03) alkenyl ethers, linear or cyclic, and in particular:

• vinyl ethers, in particular dodecylvinylether (DDVE), cyclohexylvinylether (CVE), butanediol divinylether (BDVE), butanediol monovinylether (HBVE), cyclohexane dimethanol divinylether (CHDVE), cyclohexane dimethanol monovinyl) triethyleneglycol divinylether (DVE-3) and the vinyl ethers of formula:

• propenyl ethers,

• and butenyl ethers;

Gt4) polyols, and preferably the compound of formula

In addition to organic species B1, the matrix B may also contain or be based on monomer (s), (co) olιgomer (s) and / or (co) polymer (s), of polyorganosiloxane B2 nature, consisting of units of formula (IV) and terminated with units of formula (V) or cyclic units consisting of units of formula (IV) represented below

R ⁶

- (Si-O) - (IV) Z- - (Si-O) (V)

Z 'in which the symbols R ⁶ and R ⁷ , similar or different, have definitions identical to those given for A4, - the symbols Z', similar or different, represent

^• a group R ⁶ and or R ⁷ ,

^• a hydrogen radical,

^• and / or a crosslinkable organofunctional group, preferably an epoxyfunctional, dioxolanefunctional and / or alkenyl etherfunctional group, linked to the silicon of the polyorganosiloxane via a divalent radical containing from 2 to 20 carbon atoms and which may contain at least one heteroatom , preferably oxygen,

^• with at least one of the symbols Z ′ representing a crosslinkable functional organic group

According to a preferred variant of the invention, the polyorganosiloxanes B2 used comprise from 1 to 10 organofunctional groups (frB) per macromolecular chain For an epoxyfunctional group this corresponds to epoxide levels varying from 20 to 2000 meq mol / 100 g of polyorganosiloxane The linear polyorganosiloxanes B2 can be oils of dynamic viscosity at 25 ° C, of the order of 10 to 10,000 mPa s at 25 ° C, generally of the order of 20 to 5,000 mPa.s at 25 ° C and , more preferably still, from 20 to 600 mPa at 25 ° C. or gums having a molecular mass of the order of 1,000,000

When cyclic polyorganosiloxanes B2 are concerned, these consist of units (IV) which can be, for example, of the dialkylsiloxy or alkylarylsiloxy type. These cyclic polyorganosiloxanes have a viscosity of the order of 1 to 5000 mPa s As examples of organofunctional groups (frB) of the epoxy type linked to the polyorganosiloxane B2 backbone, mention may be made of those of the following formulas:

(CH ₂ ) ₃ O CH ₂ C H- -CH ₂ , (CH ₂ ) ₃ OC H- -CH ₂

With regard to organofunctional groups (frB) of the alkenylether type, mention may be made of those contained in the following formulas:

0) n- (CH ₂ ) n "-0-CH = CH ₂

- (0) _n - (CH ₂ ) n "-R ⁸ -0-CH = CH ₂

- (CV (CH ₂ ) _n. -0-CH = CH-R ⁹ in which:

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

• R ⁸ represents:

- a linear, branched or cyclic CC ₁₂ alkylene radical, optionally substituted, - or a C ₅ -C arylene radical | ₂ , preferably phenylene, optionally substituted, preferably with one to three CC ₆ alkyl groups,

• R ⁹ represents a linear or branched alkyl radical in CC ₆ .

With regard to organofunctional dioxolane groups (frB), mention may be made of those contained in the following formulas:

Polyorganosiloxanes B2 with epoxy, dioxolane or alkenylether (frB) functions are generally in the form of fluids having a viscosity at 25 ° C of 10 to 10,000 mm ² / s and preferably from 20 to 600 mm ² / s

The dynamic viscosity at 25 ° C of all the silicones considered in this description can be measured using a BROOKFIELD viscometer, according to AFNOR NFT 76 102 of February 1972

The alkenyl ether functional polyorganosiloxanes B2 can be prepared by hydrosilylation reaction between oils with Si-H units and vinyloxy functional compounds such as allylvinylether, allylvinyloxyethoxybenzene The functional epoxy polyorganosiloxanes B2 can be prepared by hydrosilylation reaction between oils with Si-H units and epoxyfunctional compounds such as vιnyl-4 cyclohexeneoxide, allylglycidylether

The functional dioxolane B2 polyorganosiloxanes can be prepared by hydrosilylation of unsaturated dioxolanes. The polyorganosiloxanes B2 which best meet the object of the invention are described in the formulas below and have at least one epoxy, alkenylether or oxetane group X can represent an alkyl, cyclohexyl, trifluoropropyl, perfiuoroalkyl, alkoxy or hydroxypropyl group. , and R can represent a C 1 to C ₁₀ alkyl, cyclohexyl, trifluoropropyl or C 1 to C ₁₀ perfiuoroalkyl radical and (0≤a <1000), (1 <b <1000)

CH ₃ CH,

I

(CH ₃ ) ₃ Sι - C <- Sι-0 -Si-O- -Sι (CH ₃ ), CH,

1

O

/ \

CH ₂ CHCH.

0

The initiation of the photopolymerization and / or crosslinking of the adhesive composition according to the invention is carried out thanks to the presence of at least one cationic and / or radical, and preferably cationic, photoinitiator C. These cationic photoinitiators can be chosen from onium borates

(taken alone or as a mixture between them) of an element from groups 15 to 17 of the periodic table [Chem. & Eng News, vol.63, N ° 5, 26 of February 4, 1985] or of an organometallic complex of an element from groups 4 to 10 of the periodic table [same reference],

Λ whose cationic entity is selected from

(1) onium salts of formula (VI)

[(R ¹⁰ ) n - A - (RH) _m ] ⁺ (VI) in which “A represents an element from groups 15 to 17 such as for example I, S, Se, P or N,

• R10 represents a C6-C2O1 carbocyclic or heterocyclic aryl radical, said heterocyclic radical possibly containing nitrogen or sulfur as heteroelements, • R ^{1 1} represents R ¹ 0 or a linear or branched alkyl or alkenyl radical in C- _j -

C30, said radicals R ¹ 0 and R 11 being optionally substituted by a C-1-C25 alkoxy, C-1-C25 alkyl, nitro, chloro, bromo, cyano, carboxy, ester or mercapto group,

• n is an integer going from 1 to v + 1, v being the valence of the element A, “m is an integer going 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-oxoιsothιochromanιum or 2-dodecyl-4-oxoιsothιo-chromanιum,

(3) sulfonium salts in which the cationic entity comprises ^* 3- | at least one polysulfonium species of formula VIII 1

Ar - S - Ar Ar - S - Ar (VIII.l)

Ar ^" Ar-

in which

- the symbols Ar ¹ , which may be identical or different from each other, each represent a monovalent phenyl or naphthyl radical, optionally substituted with one or more radicals chosen from a linear or branched C- alkyl radical | - C-12, preferably Ci-Cβ, a linear or branched C- alkoxy radical | - C-12, preferably C-1-C5, a halogen atom, an -OH group, a -COOH group, an ester group - COO-alkyl in which the alkyl part is a linear or branched residue at C- | - C-12- preferably at C1-C5, and a group of formula -Y ^ -Ar ^ where the symbols Y ^ and Ar ^ have the meanings given just below,

- The symbols Ar2, which may be identical or different from each other or with Ar each represent a monovalent phenyl or naphthyl radical, optionally substituted with one or more radicals chosen from a linear or branched C-1-C-12 alkyl radical. preferably at C- | -Cg, a linear or branched alkoxy radical at C- | -C- | 2, preferably at C-1-C5, a halogen atom, an -OH group, a -COOH group, an ester group - COO-alkyl in which the alkyl part is a linear or branched C1-C-12 residue. preferably in C- -CQ,

the symbols Ar3, which may be identical or different from each other, each represent a divalent phenylene or naphthylene radical, optionally substituted with one or more radicals chosen from a linear or branched C- | -C- | 2_ alkyl radical, preferably in Ci-Cg, a linear or branched alkoxy radical at C- | -C- | 2, preferably at C1-C5, a halogen atom, an -OH group, a -COOH group, an ester group - COO-alkyl in which the alkyl part is a linear or branched residue at C-1-C12. preferably in C- | -C, - t is an integer equal to 0 or 1, with the additional conditions that:

+ when t = 0, the symbol Y is then a monovalent radical Y- representing the group of formula

Y '- S-Ar ¹

I, Ar ^" where the symbols Ar ^" and Ar2 have the meanings given above, + when t = 1

O on the one hand, the symbol Y is then a divalent radical having the meanings Y 2 to Y ^ below • Y ^ a group of formula

Ar ^" where the symbol Ar2 has the meanings given above,

• γ3: a simple valential link,

• Y ^{4 •} a divalent residue chosen from S ^{- •} ,. - C - 'oo a linear or branched alkylene residue in C- | -C- | 2, preferably in C- | -C6, and a residue of formula - Sι (CH3) 2θ -, O on the other hand, in the case only where the symbol Y represents γ3 or Y ⁴ , the radicals Ar ¹ and Ar2 (terminals) have, in addition to the meanings given above, the possibility of being linked together by the remainder Y 'consisting in Y'1 a simple valential link or in Y'2 a divalent remainder chosen from the rests cited in connection with the definition of Y ⁴ , which is installed between the carbon atoms, facing each other, located on each aromatic cycle in position ortho to the carbon atom directly linked to the S ⁺ cation,

^* 32 and / or at least one monosulfonium species having a single cationic center S ⁺ per mole of cation and consisting in most cases in species of formula

Ar ¹ - S - Ar '(VIII 2)

I, Ar ^" in which Ar ^" ! and Ar ² have the meanings given above with regard to the formula (III 1), including the possibility of directly linking together only one of the radicals Ar ¹ to Ar ² in the manner indicated above with regard to the definition of the additional condition in force when t = 1 in formula (II), calling on the remainder Y ',

(4) the organometallic salts of formula (IX)

(L ¹ L ² L ³ M) ⁺ q (IX) formula in which: “M represents a metal from group 4 to 10, in particular iron, manganese, chromium, cobalt,

• L ¹ represents 1 gand hey to the metal M by π electrons, ligand chosen from the ligands η ^ -alkyl, η5- cyclopendadiènyl and η ^ -cycloheptratnènyl and the η6-aromatic compounds chosen from ligands η ^ -benzene optionally substituted and compounds having from 2 to 4 condensed cycles, each cycle being capable of contributing to the valence layer of the metal M by 3 to 8 π electrons,

• L ² represents a gand linked to the metal M by π electrons, a gand chosen from the hgands η ⁷ -cycloheptatrιènyl and the compounds

chosen from the optionally substituted η6-benzene gands and the compounds having 2 with 4 condensed cycles, each cycle being capable of contributing to the valence layer of the metal M by 6 or 7 π electrons, • L3 represents from 0 to 3 identical or different hgands linked to the metal M by σ, hgand (s) electrons choιsι (s) among CO and Nθ2 ⁺ , the total electronic charge q of the complex to which L ¹ , L ² and L ^{3 contribute} and the ionic charge of the metal M being positive and equal to 1 or 2,

Δ and whose borate anionic entity has the formula (X)

[BX " _a R ^{1 2} _b ] - (X) in which

- a and b are whole numbers going 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 ¹² , 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 one electron-withdrawing group, in particular a halogen atom (especially fluorine), OCF3, CF3, NO2, CN, whatever the cationic entity

According to a first particularly advantageous variant of the invention relating to the photoinitiator used, the results obtained are particularly advantageous with photoinitiators whose cationic entity is chosen from onium salts of formula (VI). This family of cationic entities is described in numerous documents, in particular 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 More particularly, the borate anionic entity (VI) is chosen from the anions of formula [BX " _a R ¹² t,] ^" in which

- the symbols X represent a fluorine atom,

- the symbols R ¹² , identical or different, represent a phenyl radical substituted by at least one electro-attracting group chosen from OCF3, CF3, NO2 and CN, and / or by at least two fluorine atoms

Among these, particular preference will be given to the following cations of formula (VI)

[(Φ) ₂ I] ⁺ [C8H ₁₇ -0-Φ-l-Φ] ⁺ [(Φ-CH ₃ ) ₂ l] ⁺ [C _{1 2} H25-Φ-I-Φ] ⁺ [(C ₈ H ₁₇ -0-Φ) ₂ l] ⁺ [(C ₈ H ₁₇ -0-Φ- l-Φ)] ⁺

[(Φ) 3 Sf [(Φ) ₂ -S-Φ-0-C ₈ H _{1 7} ] ⁺ [(CH ₃ -Φ-I-Φ-CH (CH ₃ ) ₂ ] ⁺ [Φ-S-Φ -S- (Φ) 2] ⁺ [(C _{1 2} H ₂ 5-) 2 l] ⁺ [(CH3-Φ-l-Φ-OC ₂ H ₅ 3 ⁺

According to a second advantageous variant of the invention relating to the selected photoinitiator, the species which are particularly suitable for the anionic borate entity are the following [B (C ₆ F ₅ ) 4] - 5 "[B (C ₆ H ₃ (CF ₃ ) 2) 4] -

2 '[(C ₆ F5) 2BF ₂ ] - 6 ¹ [B (C ₆ H ₃ F ₂ ) ₄ ] -

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

In agreement with these two advantageous variants, the following products may be mentioned by way of examples.

[(Φ) ₂ l] ⁺ , [B (C ₆ F ₅ ) ₄ ] - [(C ₈ H ₁₇ ) -0-Φ-l-Φ)] ⁺ , [B (C ₆ F ₅ ) ₄ ] - [C _{1 2} H ₂₅ -Φ-I-Φ] ⁺ . [B (C ₆ F ₅ ) ₄ r [(C ₈ H ₁₇ -0-Φ) ₂ l] ⁺ , [B (C ₆ F ₅ ) ₄ ] -

[(C ₈ H ₁₇ ) -0-Φ-l-Φ)] ⁺ , [B (C ₆ F ₅ ) ₄ ] - [(Φ) ₃ S] ⁺ , [B (C ₆ F ₅ ) ₄ ] -

[(Φ) ₂ S-Φ-0-C ₈ H _{1 7} ] ⁺ , [B (C ₆ H ₄ CF ₃ ) ₄ ] - [(C ₁₂ H ₂₅ -Φ) 2l] ⁺ . [B (C ₆ F ₅ ) ₄ ] -

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

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

According to a third variant concerning the photoinitiator selected, the other cationic entities (2), (3) and (4) are also suitable in the context of the adhesives according to the invention. With regard to these other cationic entities preferably used, a distinction is made - the oxoisothiochromanium salts of formula (VII), - the oxoisothiochromanium salts of formula (VII),

- the mono and or polysylfonium salts of formula (VIII 1) and / or (VIII 2),

- and the organometal salts of formula (IX)

As regards the family of cationic entities of formula (VII) and of the oxoisothiochromanium type, it preferably comprises cations corresponding to the structure Dj which is defined on page 14 of application WO-A-90/1303 and has formula (VII)

where the radical R ¹³ has the meaning given in this application WO in connection with the symbol R ¹ , a cationic entity of this type which is more preferred is that where R ¹ represents an alkyl radical, linear or branched, in C1-C20 As salts oxoisothiochromanium which are particularly suitable, there may be mentioned in particular the sulfonium salt of 2-ethyl-4-oxoιsothιochromanιum or 2-dodecyl-4-oxoisothiochromanium

As regards the cationic polysulfonium entities (VIII 1), it will be specified that the cationic polysulfonium entity preferably comprises a species or a mixture of species of formula (VIII 1) in which - the radicals Ar ¹ , which are identical or different between them, each represent a phenyl radical, optionally substituted by a linear or branched C- | -C ₄ alkyl radical or by the group of formula

→ or ^{~ S ~} VJ

the radicals Ar ² , identical or different from each other and with Ar1, each represent a phenyl radical, optionally substituted by a linear or branched C1-C4 alkyl radical,

the Ar ³ radicals each represent an unsubstituted para-phenylene radical,

- t is equal to 0 or 1, with the additional conditions according to which ^• + when t = 0, Y = Y ¹ = - S'-Ar ¹

'2 Ar

where the radicals Ar ^{* 1} and Ar ² have the preferred meanings given just above in this paragraph; + when t = 1: O on the one hand, Y = Y ² to Y ⁴ with

. Y ² =

+

-

where the radical Ar ² has the preferred meaning given just above in this paragraph, • Y ³ = a valential link,

. Y ⁴ = - O— or —S—, and O on the other hand, when Y = Y ³ or Y ⁴ and when we then wish to implement radicals Ar ^ and Ar ² (terminals) linked together, we install a bond Y 'consisting in a valential bond or the rest - O - The mono-sulfonium species, when there are any, which fall within the framework of this preferential modality are the species of formula (IX) in which the symbols Ar ¹ and Ar ² have the preferred meanings indicated above in the preceding paragraph, including, when these radicals are directly linked together by a residue Y ', the installation of a valential bond or of the remainder - O - As examples of cationic sulfonium entities, there may be mentioned in particular

2 "

3 '

Knowing that the borate anionic entity of formula [BX " _a R> 12 \ _] ^~ is preferably chosen from the following anions 1 ', 2', 3 ', 4', 5 ', 6', 7 ' , the polysulfonium borates, which will be used very preferably, are the salts formed by the association of the following cations and anions

Cation Anion

2 »

21 21

£ 21

2 "+ 31 mixes!

2 "+ 31 2 mixes!

2 "+ 31 4 mixes!

These polysulfonium borates can be prepared by exchange reaction between a salt of the cationic entity (halide such as for example chloride, lodide) with an alkali metal salt (sodium, lithium, potassium) of the anionic entity

The operating conditions (respective quantities of reagents, choice of solvents, duration, temperature, stirring) are within the reach of those skilled in the art, these must make it possible to recover the polysulfonium borate sought in solid form by filtration of the precipitate formed or in oily form by extraction using an appropriate solvent

The procedures for synthesizing halides of cationic entities of formula (VIII 1) are described in particular in "Polymer Bulletin (Berlin)", vol 14. pages 279 - 286 (1985) and US-A-4,400,541 According to an alternative concerning the preparation of polysulfonium borates, the latter can be prepared directly by reaction between a diarylsulfoxide and a diarylsulfide according to the teaching described in "J Org Chem", Vol 55, pages 4222 - 4225 (1990) These borates of polysulfonium can 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, in adhesives according to the invention, which are intended to be polymerized and or crosslinked cationically and under activation, for example UV

The mono-sulfonium species (VIII 2) mentioned above may be in particular the co-products which are formed during the preparation of the polysulfonium cations and the presence of which can be more or less avoided

Up to 99%, more generally up to 90% and even more generally up to 50%, by mole (of cation) of the polysulfonium species of formula (VIII 1) can be replaced by monosulfonium species (VIII 2)

As regards the cationic entities of type (IX), they are described in US patent A-4,973,722, US-A-4,992,572, European patent applications EP-A-203,829, EP-A -323 584 and EP-A-354 181 The organometallic salts more readily used in practice are in particular (η5 - cyclopentadienyl) (η6 - toluene) Fe ⁺ - bis (η6 - benzene) Cr ⁺ le (η5 - cyclopentadienyl) ( η6 - cumene) Fe ⁺ - bis (η6 - mesitylene) Fe ⁺ - and (η ⁵ - cyclopentadienyl) (η6 - methyl-1-naphthalene) Fe ⁺

Mention may be made, as examples of boron onium photoinitiators of cationic entity (IX), of the following products

(η ⁵ - cyclopentadienyl) (η ⁶ - toluene) Fe ⁺ , [B (C6F5) 4] ^"

(η5 - cyclopentadienyl) (η6 - methyll-naphthalene) Fe ⁺ , [B (CsF5) 4] ^" and (η ⁵ - cyclopentadienyl) (η6 - cumene) Fe ⁺ , [B (C6F5) ₄ ] ^~

As another literary reference for defining the onium borates (1) and (2) and the borates of organometal salts (4), selected as photoinitiator in the context of the invention, mention may be made of the entire content of the patent applications EP 0 562 897 and EP 0 562 922 This content is fully incorporated by reference to the description As another example of onium salt usable as photoinitiator C, mention may be made of those disclosed in American patents US 4,138,255 and US 4,310,469 (CRIVELLO)

In the case of the use of radical photoinitiators, these α are based on benzophenones. By way of example, mention may be made of those sold by Ciba-Geigy Irgacure 184, Irgacure 500, Darocure 1173, Irgacure 1700, Darocure 4265, Irgacure 907, Irgacure 369, Irgacure 261, Irgacure 784 DO, Irgacure 2959 and Irgacure 651

Radical photoinitiators can contain one or more phosphorus atoms, like those sold by Ciba-Geigy (Irgacure 1700) or BASF (Luciπn TPO)

Advantageously, the photoinitiator C, in particular of cationic nature, is used in solution in an organic solvent (accelerator), preferably chosen from the proton donors and, more preferably still, from the following groups isopropyl alcohols, benzyl alcohols, diacetone alcohol , butyl lactate and mixtures thereof. The photoinitiator C can also be used directly by solubilization in the matrix A and / or B

The adhesive according to the invention can also comprise at least one photosensitizer D In fact, to overcome the possible drawbacks linked to the composition of certain adhesives according to the invention, to the type of activation used and / or to the intrinsic inhibiting properties of certain packaging. (thick packaging, packaging with pigments, etc.), the use of a photosensitizer D is very profitable. For example, photosensitizer D can be selected from (poly) aromatic products - possibly metallic - and heterocychic products and, preferably, chosen from the following list of products phenothiazine, tetracene, perylene, anthracene, dιphenyl-9-10-anthracene thioxanthone, 2-chlorothιoxanthen-9-one, 1-chloro 4 propoxy 9H-thιoxanthen-9- one, ιsopropyl-OH-thιoxanten-9-one, mixture of isomers 2 and 4, 2-ιsopropyl-9H -thioxanthen- 9-one, benzophenone, [4- (4-methylphenylthιo) phenyl] phenylmethanone, 4-benzyl -4'- methyldiphenylsulphide, acetophenone, xanthone, fluorenone, anthraquinone, 9,10- dimethylanthracene, 2-ethyl-9,10-dιmethyloxyanthracene, 2,6-dιmethyl-naphthalene, 2,5- dιphenyl-1-3-4- oxadιazole, xanthopinacol, 1, 2-benzanthracene, 9-nιtro-anthracene, and mixtures thereof By effective amount of initiator system is meant, within the meaning of the invention, the amount sufficient to initiate crosslinking Advantageously, this effective amount corresponds to 1 10 ~ 6 to 1, preferably from 1 10 "5 to 1 10 ^{~ 1} and, more preferably still from 1 10 " ⁴ to 1 10" ² moles of photoinitiator per 1 mole of frA and frB

In addition to the various components mentioned above, the adhesives according to the invention may contain a stabilization additive based on secondary or primary tertiary ahphatic amine, and preferably chosen from the derivatives described in patent application WO98 / 07798.

The invention also relates to an adhesive based on a polymerizable and or crosslinkable composition, under irradiation and / or under electron beam (s), cationically and / or free-radical, to assemble two plastic surfaces vis-à-vis screw, including

- 1 to 99% by weight of at least one matrix A according to the definition given above,

- 99 to 1% by weight of at least one matrix B according to the definition given above, - optionally at least one photosensitizer D

- And an effective amount of at least one cationic photoinitiator C chosen from onium borates of an element from groups 15 to 17 of the periodic table or from an organometallic complex of an element from groups 4 to 10 of the periodic classification Δ whose cationic entity is selected from onium salts of formula (VI) according to the definition given above and Δ whose borate anionic entity is of formula (X) according to the definition given above

EXAMPLES

The examples which follow will make it possible to better understand the invention and to highlight all of its advantages and to glimpse some of its variant embodiments.

Polypropylene sheets are secured by UV application of a layer of adhesive comprising the formulation of an oxetane monomer Example 1

A control formulation respectively comprises by mass

- 83.54% of Cyracure® 6105 from the company Union-Carbide stabilized with 10 ppm of Tinuvin 765,

- 14.56% of Cyracure ® TON201 from the company Union-Carbide,

- 1.17% of BYK 361 spreading agent from BYK Chemie,

- 0.73% of Rhodorsil ® Photoinitiator 2074 from the company Rhodia sihcones,

- and 0.04% of diethylthioxanthone from the company Lambson The viscosity of the control formulation is approximately 200 mPa s

Example 2

The adhesive formulated according to the invention comprises respectively by mass

- 67.23% of Cyracure® 6105 from the company Union-Carbide stabilized with 10 ppm of Tinuvin 765, - 11.65% of Cyracure® TON201 from the company Union-Carbide,

- 19.42% of 3-Ethyl-3 (hydroxymethyl) -oxetane,

- 0.93% BYK 361 spreading agent from BYK Chemie,

- 0.73% of Rhodorsil ® Photoinitiator 2074 from the company Rhodia sihcones,

- and 0.04% of diethylthioxanthone from the company Lambson The viscosity of the adhesive is approximately 200 mPa s

Example 3

- 77.73% of UVACURE® 1534 resin from the company UCB stabilizes with 10 ppm of Tinuvin 765

- 19.42% of 3-Ethyl-3 (hydroxymethyl) -oxetane

- 0.6% of Rhodorsil ® Photoinitiator 2074 from the company Rhodia Silicones,

- 2.25% methylethyl ketone

- and 0.04% of diethylthioxanthone from the company Lambson The viscosity of the adhesive is 700 +/- 200 mPa s depending on the rate of methylethylketone introduced

tests

Each formulation is applied at different grammages on bluish or transparent rough polypropylene plates. The plates are 500 μm thick and are laid horizontally. Each plate comprising the adhesive is assembled with an adhesive-free plate by simple pressure

It is irradiated using two lamps from the company IST Hg / Ga of 180W / cm at speeds between 25 and 100 m / min through the polypropylene plates. The release forces are measured by peeling at 180 ° at 1 using a dynamometer fitted with a 100 N cell on rectangular test pieces 2 cm wide and 10 cm long

Results The test results are reported in the table below

Polypropylene Deposition Test Speed Force g / m ² m / min N / mm

ExemplelA 60 Blue 100 0 2

Example B 60 Blue 50 0 29

Example C 60 Transparent 100 0.2

Example 2A 60 Blue 100 '0 22

Example 2B 60 Blue 50 0 35

Example 3A 60 Blue 100 0 3

Example 3B 60 Blue 50! 0 7

Example 3C 60 Blue 25 0 7

Example 3D 60 Transparent 50 1 7

Example 3E 60 Transparent 100

Claims

CLAIMS.

1. Use of a polymerizable and / or crosslinkable adhesive to assemble two facing plastic surfaces, comprising - 1 to 99% by weight of at least one organic matrix A and / or silicone polymerizable and / or at least partially polymerized, comprising (co) monomers, (co) olιgomers and / or (co) polymers chosen from those having reactive oxetane (frA) functions

- 99 to 1% by weight of at least one polymerizable and / or at least partially polymerized organic matrix B and / or silicone, comprising

(co) monomers, (co) olιgomers and or (co) polymers chosen from those having reactive functions (frB) epoxy (α- |) and / or acrylate (0: 2) and / or alkenyl ether (013 ) and / or hydroxy (α ₄ ),

an effective amount of at least one cationic and / or radical photoinitiator C,

- possibly at least one photosensitizer D

2. Use according to the preceding claim, characterized in that the bonding is carried out by polymerization / crosslinking of the adhesive under irradiation, and / or under electron beam (s), by cationic and / or radical route

3. Use according to any one of the preceding claims, characterized in that the polymeπsation / crosslinking is carried out cationically in the presence of at least one cationic photoinitiator chosen from onium borates of an element from groups 15 to 17 of the periodic table or an organometallic complex of an element from groups 4 to 10 of the periodic table,

Δ whose cationic entity is selected from 1) the onium salts of formula (VI)

[(Rl0) _n - A - (Rl 1) _m ] ⁺ (VI) in which

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

• R ^" " - ¹ represents a carbocyc aryl or heterocyclic C5-C20 radical. said heterocyc radical which may contain nitrogen or sulfur as heteroelements,

• RU represents R ^" O OR a linear or branched C- | - C30 alkyl or alkenyl radical, said radicals R ^{1 u"} and R ^{1 1} being optionally substituted with a C 1 -C 25 alkoxy group, C 1 -C 25 alkyl, nitro, chloro, bromo, cyano, carboxy, ester or mercapto,

• 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-oxoιsothιochromanιum or 2-dodecyl-4-oxoιsothιo-chromanium,

3) sulfonium salts in which the cationic entity comprises: ^* 3- | at least one polysulfonium species of formula VIII.1:

Ar - S - Ar Ar ^" - S - λr (VIII.1) I, l„ Ar ^" Ar ^"

in which :

- the symbols Ar ¹ , which may be identical or different from each other, each represent a monovalent phenyl or naphthyl radical, optionally substituted with one or more radicals chosen from ^• a linear or branched C- alkyl radical | - C-12, preferably C- | -Cs, a linear or branched C- | - CJ 2, preferably at C- \ -CQ, a halogen atom, a group -OH, a group -COOH, an ester group - COO-alkyl in which the alkyl part is a linear or branched residue at C- | - C-12. preferably in C- _| -Cs, and a group of formula -Y ⁴ -Ar ² where the symbols Y ⁴ and Ar ² have the meanings given just below,

- the symbols Ar ² , which may be identical or different between themselves or with Ar ¹ , each represent a monovalent phenyl or naphthyl radical, optionally substituted with one or more radicals chosen from: a linear or branched C- alkyl radical | C- | 2- preferably in C- | -Cβ, a linear or branched Cι-C- alkoxy radical | 2 _> preferably at C- | -Cβ, a halogen atom, a group -OH, a group -COOH, an ester group - COO-alkyl in which the alkyl part is a linear or branched residue at C- | C- | 2, preferably in C- | -Cg, - the symbols Ar ³ , which may be identical or different between them, each represent a divalent phenylene or naphthylene radical, optionally substituted with one or more radicals chosen from a linear or branched alkyl radical in C- | C- | 2_ preferably in C1-C5, a linear or branched alkoxy radical in C-ι-C-12. preferably at C- \ -CQ, a halogen atom, an -OH group, a -COOH group, an ester group - COO-alkyl in which the alkyl part is a linear or branched residue in C1-C-12, preferably in CiC, - t is an integer equal to 0 or 1, with the additional conditions that ^•

+ when t = 0, the symbol Y is then a monovalent radical Y ¹ representing the group of formula

Y '-S - Ar'

Ar ^" where the symbols Ar ¹ and Ar ² have the meanings given above, + when t = 1

O on the one hand, the symbol Y is then a divalent radical having the following meanings Y ² to Y ⁴

• Y ² a grouping of formula

Ar ^" where the symbol Ar ² has the meanings given above,

• Y ³ . a simple value link,

• Y ⁴ a divalent residue chosen from II oo a linear or branched C-1-C12 alkylene residue. preferably in ^C 1-C6- and a residue of formula - Sι (CH ₃ ) 2θ—, on the other hand, in the case only where the symbol Y represents Y ³ or Y ⁴ , the radicals Ar ¹ and Ar ² ( terminals) have, in addition to the meanings given above, the possibility of being linked together by the remainder Y 'consisting in Y' ¹ a simple valential link or in Y ' ² a divalent remainder chosen from the remainders mentioned in connection with the definition of Y ⁴ , which is installed between the carbon atoms, facing each other, located on each aromatic cycle in position ortho with respect to the carbon atom directly connected to the cation S ⁺ ,

and / or at least one monosulfonium species having a single cationic center S ⁺ per mole of cation and consisting in most cases in species of formula ^•

Ar '- S - Ar' (VIII 2)

Ar ^" in which Ar ¹ and Ar ² have the meanings given above with regard to the formula (III 1), including the possibility of directly connecting together only one of the radicals Ar ¹ to Ar ² in the manner indicated above with regard to the definition of the additional condition in force when t = 1 in formula (II), calling on the remainder Y ';

4) the organometallic salts of formula (IX).

formula in which ^•

M represents a metal from group 4 to 10, in particular iron, manganese, chromium, cobalt,

• L ¹ represents 1 gand é to the metal M by electrons π, hgand chosen from the hgands η ³ -alkyl, η5- cyclopendadiènyl and

and the η6-aromatic compounds chosen from hgands η ^ -benzene optionally substituted and the compounds having from 2 to 4 condensed cycles, each cycle being capable of contributing to the valence layer of the metal M by 3 to 8 π electrons;

• L ² represents a hgand linked to the metal M by π electrons, hgand chosen from the hgands η ⁷ -cycloheptatrιènyl and the compounds

chosen from the hgands η6-benzene optionally substituted and the compounds having from 2 to 4 condensed cycles, each cycle being capable of contributing to the valence layer of the metal M by 6 or 7 π electrons,

• L ³ represents from 0 to 3 identical or different hgands linked to the metal M by electrons σ, hgand (s) choιsi (s) among CO and Nθ2 ⁺ , the total electronic charge q of the complex to which L ¹ , L ^{2 contribute} and L ³ and the ionic charge of the metal M being positive and equal to 1 or 2

4. Use according to the preceding claim characterized in that the cationic entity of the cationic photoinitiator is chosen from onium salts of formula (VI)

5. Use according to any one of the preceding claims, characterized in that the polymerization / crosslinking is carried out cationically in the presence of at least one cationic photoinitiator chosen from onium borates of an element from groups 15 to 17 of the periodic table or an organometallic complex of an element from groups 4 to 10 of the periodic table,

Δ whose borate anionic entity has the formula (X)

[BX " _a R ¹² b] ^" (X) 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 ¹² , 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 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 (fluorine in particular), CF3, OCF3, NO2, CN, and this when the cationic entity is an organometal complex only of one element of the 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 (fluorine in particular), OCF3, CF3 , NO2, CN, whatever the cationic entity

6. Use according to any one of the preceding claims, characterized in that the matrix A is chosen from at least one of the (co) monomers and / or (co) ohgomers and or (co) polymers which consist of at least one of the following species A1) the monomers with oxetane and alkoxy functions, oxetane and hydroxy functions, or oxetane and alkoxysilyl functions of formula

in which

- Ri is (i) a hydrogen atom, (n) a linear or branched alkyl radical comprising from 1 to 30 carbon atoms, (ni) an aryl radical comprising from 6 to 30 carbon atoms optionally substituted by at least one fluorine atom, a carboxy radical, a hydroxy radical, an ester radical or a radical with a ketone function, (iv) a cycloalkyl radical comprising from 5 to 6 carbon atoms optionally substituted by at least one fluorine atom, a hydroxy radical , a carboxy radical, a radical ester or a radical with a ketone function, (v) an OR 'radical where R' is a linear or branched alkyl radical comprising from 1 to 30 carbon atoms, or (vi) an alkenyl radical comprising from 2 to 12 carbon atoms

R ₂ is (i) a hydrogen atom, (n) an alkenyl radical comprising from 2 to 12 carbon atoms (for example a vinyl radical, a propenyl radical), (m) a linear or branched alkyl radical comprising from 1 with 30 carbon atoms optionally substituted for example by an oxirane group, (iv) an aryl radical comprising from 6 to 30 carbon atoms optionally substituted for example by at least one alkyl radical comprising from 1 to 30 carbon atoms, a benzyl radical , a CF ₃ radical, a halogen atom, a hydroxy radical, a carboxy radical, an alkoxy radical, (v) a silyl group (CH2) n-SιR ₃ RR ₅ where n is between 0 and 12, and R ₃ , R ₄ , and R ₅ , identical or different, represent a hydrogen atom, a hydroxy radical, an alkoxy radical OR 'where R' is a linear or branched alkyl radical comprising from 1 to 30 carbon atoms, (vi ) a linear or branched alkyl radical comprising from 1 to 30 carbon atoms, (seen) a radica aryl comprising from 6 to 30 carbon atoms optionally substituted, (vm) an alkenyl radical comprising from 2 to 12 carbon atoms, (ix) an acrylate radical, (x) a methacrylate radical (for example -CO-CH = CH ₂ ), or (xi) a urethane radical -CO-NH-Ri in which Ri has the same definition as that given previously

in which

- R-, has a definition identical to that given in A1),

- R ₂ has the same definition as that given in A1),

A3) the difunctional oxetane monomers of formula

in which

- m, identical or different, is equal to 0 or 1,

- Ri is of identical definition to that given in AV - R ₆ , divalent radical, is (i) a linear or branched alkyl radical comprising from 1 to 30 carbon atoms, (n) an aryl radical comprising from 6 to 30 carbon atoms optionally substituted (by at least one alkyl radical comprising from 1 to 30 carbon atoms; (m) an aryl radical comprising from 6 to 30 carbon atoms (for example a benzyl radical); (iv) a cycloalkyl radical comprising from 5 to 30 carbon atoms (ex cyclohexyl), ( v) a radical -CH ₂ -C ₆ H ₁₀ -CH ₂ -, (vi) a radical -CH ₂ -C ₆ H ₄ -CH ₂ -, (seen) a radical CF ₃ , (viii) an atom of halogen, (ix) a hydroxy radical, (x) a carboxy radical, (xi) an alkoxy radical OR 'where R' has the same definition as that given in A1), (xn) a silyl group = SιR ₃ R ₄ where n is between 0 and 12, and R ₃ , R ₄ , identical or different, represent a hydrogen atom, a hydroxy radical, an alkoxy radical OR 'where R' is of definition identical to that given in A1), a alkyl radical linear or branched comprising from 1 to 30 carbon atoms, an aryl radical comprising from 6 to 30 carbon atoms optionally substituted, a radical -C- ₆ H ₄ -C (CH ₃ ) ₂ -C ₆ H -, or a radical alkenyl comprising from 2 to 12 carbon atoms

= 6 R ⁶

(Si-O) - (II) Z (Si-O) (III

R ⁷ in which the symbols R ⁶ and R ⁷ , similar or different, represent

^• 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-trιfluoropropyle,

^• a cycloalkyl radical containing between 5 and 8 cyclic carbon atoms, possibly substituted,

^• an aryl radical containing between 6 and 12 carbon atoms which may be substituted, preferably phenyl or dichlorophenyl,

^• 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 carbon, optionally substituted on the aryl part by halogens, alkyls and / or alkoxyls containing 1 to 3 carbon atoms, the symbols Z, similar or different, represent

^• an R ⁶ and / or R ^{7 group} ,

^• a hydrogen radical,

^• and / or a crosslinkable oxetane functional group linked to the silicon of the polyorganosiloxane by means of a divalent radical containing from 2 to 20 carbon atoms and which may contain at least one heteroatom, preferably oxygen, the latter possibly being directly hey silicon by forming a bond ≡Si-OC≡

^• with at least one of the symbols Z representing a crosslinkable functional oxetane group

Use according to any one of the preceding claims, characterized in that the matrix B comprises at least one of the following organic species B1 (α-n epoxides and non-cycloaliphatic epoxides, (2) acrylates, (0: 3) alkenyl ethers, linear or cyclical, and

and polyols

Use according to the preceding claim, characterized in that the organic species B1 are chosen from the following α-j ij cycloaliphatic epoxides and in particular epoxides of the 3,4-epoxycyclohexylmethyl-3 ', 4'- epoxycyclohexane carboxylate type

or Bιs (3,4-epoxycyclohexyl) adιpate, ^α 1.2) ^'are epoxides non cycloaliphatic, and in particular

• epoxides of the type of those resulting from the condensation of Bis-phenol A and of epichlorohydrin and of the type di and tπglycidylethers of Bisphenol A alkoxylated of 1, 6 hexane diol, of glycerol, of neopentylglycol and of propane tπmethylol, or diglycidylethers of Bisphenol A,

• alpha-olefin epoxides, NOVOLAC epoxides, epoxidized soybean oil, epoxidized linseed oil, and epoxidized polybutadiene,

012) acrylates, and in particular • epoxidized acrylates, preferably the oligomer of Bisphenol A- epoxydiacrylate (EBECRYL 600),

• acryloglycero-polyester, preferably a mixture of functional acrylate obtained from glycerol and polyester (EBECRYL 810), • multifunctional acrylates, preferably pentaerythrytol triacrylate

(PETA), trimethylol propane triacrylate (TMPTA), 1, 6-hexanedιol diacrylate (HDODA), tnmethylolpropane ethoxylate triacrylate, thiodiethylene glycol diacrylate, tetraethylene glycol diacrylate (TTEGDA), tnaryl tetylene glycol-tacryl diacrylene , tnmethylpropane tnmethacrylate (TMPTMA),

• acrylo-urethanes,

• acrylo-polyethers,

• acrylo-polyesters,

• unsaturated polyesters, • acrylo-acrylics,

013) alkenyl ethers, linear or cyclic, and in particular

• vinyl ethers, in particular dodecylvinyl ether (DDVE), cyclohexylvinyl ether (CVE), butanedioldivinyl ether (BDVE), butanediolmonovinyl ether (HBVE), cyclohexanedimethanol divinyl ether (CHDVE), cycloheinyl ether dimane ether (DVE-3) and the vinyl ethers of formulas

• propenyl ethers,

• and butenyl ethers, α ₄ ) polyols, and preferably the compound of formula

Use according to any one of the preceding claims, characterized in that the matrix B comprises at least one monomer (s) and / or ohgomer (s) and / or polymer (s), of polyorganosiloxane B2 nature, consisting of units of formula (IV) and terminated by units of formula (V) or cyclic units consisting of units of formula (IV) shown below.

- (Si-O) (IV) - (Si-oy- (V)

z in which: the symbols R ⁶ and R ⁷ , similar or different, have definitions identical to those given for A4,

- the symbols Z, similar or different, represent

^• a group R ⁶ and or R ⁷ ,

^• a hydrogen radical,

^• with at least one of the symbols Z representing a crosslinkable functional organic group

10. Use according to the preceding claim characterized in that the (frB) are chosen from the following radicals.

- (CH ₂ ) ₃ O - CH ₂ -C H- -CH, (CH ₂ ) ₃ O - CH -CH,

\ ₀ / \ /

- (0) _n - (CH ₂ ) _n -0-CH = CH ₂ , - (O) _n - (CH ₂ ) n "-R -0-CH = CH ₂ , and

- (0) _n - (CH ₂ ) n _" -0-CH = CH-R ^a in which

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

• R ⁸ represents

a linear, branched or cyclic C- | -Cι ₂ alkylene radical, optionally substituted,

- or a C ₅ -C arylene radical | ₂ , preferably phenylene, optionally substituted, preferably with one to three C- | -C ₆ alkyl groups,

• and R ⁹ represents a linear or branched CC ₆ alkyl radical

11. Glue based on a polymerizable and / or crosslinkable composition, under irradiation and / or under electron beam (s), cationically and / or free-radical, to assemble two plastic surfaces opposite, comprising

- 1 to 99% by weight of at least one matrix A according to the definition given in claim 1, - 99 to 1% by weight of at least one matrix B according to the definition given in claim 1,

- possibly at least one photosensitizer D.

- And an effective amount of at least one cationic photoinitiator C chosen from onium borates of an element from groups 15 to 17 of the periodic table or from an organometallic complex of an element from groups 4 to 10 of the periodic classification,

Δ whose cationic entity is selected from onium salts of formula (VI) defined in claim 3, Δ and whose anionic borate entity has the formula (X) defined in claim 5.