Photosensitive adhesive composition

A photosensitive adhesive composition of polymerizable resin type whose hardening is obtained by polymerization and/or cross-linking characterized in that said composition contains:

• at least one chain polymerization reaction initiator that ensures hardening of said composition, and
• a sufficient quantity of at least one bifunctional monomer including firstly a photocleavable centre comprising at least one photocleavable unit selected from the group consisting of:
• (i) aryl-diazos units defined by formula I:
• in which:
• Ar designates an aromatic system, monocylic or polycylic, carbocyclic or heterocyclic,
• X designates an atom chosen from among:
• C,O,P,S;
• Ri is one or more of the following groups:
• hydrogeno, halogeno, alkyl linear or branched, saturated or unsaturated, optionally substituted, aryl aromatic or heteoaromatic, substituted or unsubstituted, alcoxy comprising at least one selected from the group consisting of methoxy, ethoxy, aryloxy, alkylthio, arylthio, benzyl, halogeno, hydroxy, hydroxyalkyl, thiol, alkyloxycarbonyl, aryloxycarbonyl, cyano, carbonyl, formyl, amino, carboxylic and sulfonic ester, carboxylic sulfonic and phosphoric amide, carboxylic sulfonic and phosphoric acid, sulfonate, phosphonate, —OCONR′R″ group, —OCO2R′, —OSO2R′, —OPOOR′OR″, -R′NHCOOR″, —R′OCO2R″, —NR′R″ (in which R′ and R″ represent an alkyl group, carbocyclic or heterocyclic group, aliphatic, unsaturated, (hetero-)aromatic group, all substituted or unsubstituted, imine whether substituted or not, nitro, —N═N—R′, -Rp-Si—(ORq)3 group (in which Rp is a hydrocarbon chain or a linear alkyl chain comprising at least 3 C atoms, and Rq denotes a hydrogen atom, a hydroxy group, C1-C6 alcoxy chain or —(Si(ORq) group), vinyl group, acrylic group, alcoxycarbonyl group, and an aryltriazene group,
• Rj designates one or more substituents depending upon the valency of the atom designated by X, the same or different and chosen from among:
• an alkyl chain linear or branched, saturated or unsaturated, acyclic or cyclic, optionally substituted;
• an aromatic or heteroaromatic group including, at least one nitrogen or sulfur atom, monocyclic or polycyclic;
• an alcoxy, aryloxy chain or benzyl group;
• (ii) aryl-triazene units defined by formula II:
• in which:
• Ar designates an aromatic system monocyclic or polycyclic, carbocyclic or heterocyclic,
• Ri is chosen from among the following groups:
• alkyl linear or branched, saturated or unsaturated, optionally substituted, aryl aromatic or heteoaromatic, substituted or unsubstituted, alcoxy comprising one selected from the group consisting of methoxy, ethoxy, aryloxy, alkylthio, arylthio, benzyl, halogeno, hydroxy, hydroxyalkyl, thiol, alkyloxycarbonyl, aryloxycarbonyl, cyano, carbonyl, formyl, amino, carboxylic and sulfonic ester, carboxylic sulfonic and phosphoric amide, carboxylic sulfonic and phosphoric acid, sulfonate, phosphonate, —OCONR′R″ group or —OCO2R′, —OSO2R′, —OPOOR′OR″, —R′NHCOOR″, —R′OCO2R″, —NR′R″ (in which R′ and R″ represent an alkyl group, a carbocyclic or heterocyclic group, aliphatic, unsaturated, a (hetero-)aromatic group, all substituted or unsubstituted, imine substituted or unsubstituted, nitro, —N═N—R′, -Rp-Si—(ORq)3 group (Rp and Rq as previously defined above), a vinyl group, acrylic group, alcoxycarbonyl group, and an aryltriazene group,
• R1 and R2 are chosen independently from one another, a —N═N—R′ group, —NR′—N═N—R″ group, OH group, NR′R″ group, (R′ and R″ have the previously given denotations), an alkyl group comprising at least one selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, an alcoxy group substituted or not, a benzyl group, a (hetero)-aromatic group, all substituted or not by substituents of Ri type, a hydroxyethyl, cyanoethyl, aminoethyl, acryloxyethyl, and halogenoethyl group
• (iii) 2-nitrobenzyl units having the formula 1:
• in which:
• Ar designates an aromatic or heteroaromatic radical monocyclic or polycyclic and carrying at least one Rk substituent,
• Rk designates an auxochromic or bathochromic substituent which may be chosen from the following examples:
• hydrogen, halogen, alkyl chain, aliphatic acyclic saturated or unsaturated, linear or branched, a cyclic, aliphatic, unsaturated, aromatic or heteroaromatic radical, these chains and radicals possibly being substituted, interrupted or terminated by a heteroatom comprising at least one selected from the group consisting of B, N, O, Si, P, S and a halogen, a nitro group, cyano group, an alcoxy, aryloxy, alkylthio, arylthio, benzyl, aylalkyl, hydroxy, thiol, alkyloxycarbonyl, aryloxycarbonyl, carbonyl, formyl, amino radical, carboxylic ester, amide, sulfonic ester, sulfonic amide, carboxylic acid, sulfonic acid, sulfonate, phosphonate, a —OCONR′R″ group, —OCO2R′, —OSO2R′, —OPOOR′OR″, —R′NHCOOR″, R′OCO2R″, NR′R″ (R′ and R″ are an alkyl, aryl group, a carbocyclic or heterocyclic group), imine substituted or unsubstituted, diazo —N═N—R′, -Rp-Si(ORq)3 group, alkylglycidyl ether, alkylvinyl ether, cyclohexyl epoxy,
• Rm1/Rm2 are independently chosen from among:a hydrogen, an alkyl, alcenyl, alcynyl, alkylaryl chain, all substituted or unsubstituted, a carbocyclic or heterocyclic chain saturated or unsaturated, aromatic or heteroaromatic, substituted or unsubstituted, an alcoxy, aryloxy, alkylthio, arylthio chain, an alkyloxocarbonyl group, —NR′COR″ group, —OCOR′ group, —OCOOR′ group, —OCONR′R″ group, NR′COOR″ group, —OPOR′R″R′″ group, —OSO2R′ group, —OPOOR′OR″ group, —NR′R″, —COOR′ group, —CONR′R″, SOOR′, —COR′ group (R′, R″ and R′″ have the previously indicated denotations for R′ and R″ an imine group substituted or unsubstituted, a hydroxy, thiol group, a carboxylic acid or derivative of carboxylic acid, a halogen, a nitrile, an alkyl(C1-C6)glycidyl ether group, alkyl(C1-C6)vinyl ether group, cyclohexyl epoxy, -Rp-Si—(ORq)3 group (Rp and Rq as previously defined above)
• (iv) 2-nitrobenzyl units defined by formula 2:
• in which:
• Ar is an aromatic system, monocyclic or polycyclic, carbocyclic or heterocyclic,
• Rm4 is defined as Rm1/Rm2,
• Rm3 is chosen from among a hydrogen, an alkyl, alcenyl, alcynyl, alkylaryl chain, all substituted or unsubstituted, interrupted by a heteroatom, a carbocyclic or heterocyclic chain, saturated or unsaturated, aromatic or heteroaromatic, substituted or unsubstituted, an alkyloxocarbonyl group, NCOOR′ group, —POR′R″R′″ group, —SO2R′ group, —POOR′OR″ group, —COOR′ group, —CONR′R″, COR′ group (R′, R″ and R′″ having the previously indicated denotations for R′ and R″), an alkyl(C1-C6)glycidyl ether group, alkyl(C1-C6)vinyl ether group, cyclohexyl epoxy, -Rp-Si(ORq)3 group (Rp and Rq as previously defined above),
• (v) 2-nitrobenzyl units defined by formula 3:
• in which:
• Ar is defined as previously,
• Rm5 is defined as R11/R12/R13,
• Rm6/Rm7 are defined as a hydrogen, an alkyl, alcenyl, alcynyl, alkylaryl chain, substituted or not, interrupted by a heteroatom, a carbocyclic or heterocyclic chain, (un)saturated, (hetero)-aromatic, substituted or not, an alkyloxycarbonyl group, —R′COR″ group, R′COOR″ group, R′R″, —COOR′ group, —CONR′R″, a COR′ group (R′ and R″ having the denotations previously given), a hydroxy group, alkyl(C1-C6)glycidyl ether or alkyl(C1-C6)vinyl ether, cyclohexyl epoxy, -Rp-Si(ORq)3 group (Rp and Rq as defined previously above), and
• (vi) 2-nitrobenzyl units defined by formula 4:
• in which:
• Ar is defined as previously,
• Rm8/Rm9/Rm10 are defined as R11/R12/R13 as defined above;
• and
• secondly at least two polymerizable units linked by covalent skeletons to said photocleavable centre and positioned either side of the cleavage site or sites of said photocleavable centre so that said hardened composition loses its integrity and adhesiveness under the action of uncrosslinking radiation which causes cleavage of the photocleavable units.