Photosensitive compositions based on polycyclic polymers

A photodefinable dielectric composition comprising:

• a copolymer composition including a vinyl addition copolymer comprising two or more repeat units having structural formula I:
• wherein X is selected from —CH2—, —CH2—CH2— and O;
• m is an integer from 0 to 5;
• and each occurrence of R1, R2, R3 and R4 is independently selected from one of the following groups:
• H, C1 to C25 linear, branched and cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl and alkynyl;
• C1 to C25 linear, branched and cyclic alkyl, aryl, aralkyl, alkaryl, alkenyl and alkynyl containing one or more hetero atoms selected from O, N, and Si;
• an epoxy containing group of structural formula II:
• wherein A is a linking group selected from C1 to C6 linear, branched and cyclic alkylene and R23 and R24 are independently selected from H, methyl and ethyl;
• an epoxy containing group of structural formula III:
• wherein p is an integer of from zero to 6, R23 and R24 are as defined above, and each occurrence of R21 and R22 are independently selected from H, methyl and ethyl;
• —(CH2)nC(O)OR5, —(CH2)nC(O)OR6, —(CH2)nOR6, —(CH2)nOC(O)R6, —(CH2)nC(O)R6, and —(CH2)nOC(O)OR6;
• wherein R5 is an acid labile group and R6 is selected from H, C1 to C6 linear, branched and cyclic alkyl, an epoxy containing group of structural formula II as defined above;
• any combination of two of R1, R2, R3, and R4 linked together by a linking group selected from C1 to C25 linear, branched and cyclic alkylene and alkylene aryl, wherein n is an integer of from 1 to 25;
• and
• up to 25 mole % of one or more repeat units where R5 is selected from the group consisting of —C(CH3)3, —Si(CH3)3, —CH(R7)CH2CH3, —CH(R7)C(CH3)3, dicyclopropylmethyl, dimethylcyclopropylmethyl, and a compound described by one or more of structural units IV–X:
• wherein X is defined as above, y is 0, 1 or 2;
• and R7 is selected from H and C1 to C6 linear, branched and cyclic alkyl;
• wherein from 20 mole % to 60 mole % of the repeat units have the epoxy containing group of structural formula II where such epoxy functional group is a glycidyl methyl ether pendant group;
• the copolymer has a glass transition temperature of from 170° C. to 400° C.;
• and the weight average molecular weight of the copolymer is from 50,000 to 140,000 as determined by gel permeation chromatography using poly(norbornene) standards;
• one or more photoacid generators;
• one or more photosensitizers;
• optionally one or more adhesion promoters comprising one or more compounds described by structural unit XVI:
• wherein z is 0, 1 or 2;
• R8 is a linking group selected from C1 to C20 linear, branched and cyclic alkylene, alkylene oxide containing from 2 to 6 carbon atoms and poly(alkylene oxide), wherein the alkylene portion of the repeat groups contain from 2 to 6 carbon atoms and the poly(alkylene oxide) has a molecular weight of from 50 to 1,000;
• each occurrence of R9 is independently selected from C1 to C4 linear and branched, alkyl and each occurrence of R18 is selected from H and C1 to C4 linear and branched alkyl;
• and
• optionally a solvent comprising reactive and non-reactive compounds selected from hydrocarbon solvents, aromatic solvents, cycloaliphatic cyclic ethers, cyclic ethers, acetates, esters, lactones, ketones, amides, cycloaliphatic vinyl ethers, aromatic vinyl ethers, cyclic carbonates, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,8-octanediol divinyl ether, 1,4-dimethanolcyclohexane divinyl ether, 1,2-ethylene glycol divinyl ether, 1,3-propylene glycol divinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 1,4-butanediol vinyl ether, 1,6-hexanediol vinyl ether, 1,8-octanediol vinyl ether, compounds described by structural units XVII and XVIII:
• CH2═CH—O—R10—O—CH═CH2 (XVII)
• CH2═CH—O—R11 (XVIII)
• wherein R10 is a linking group selected from C1 to C20 linear, branched and cyclic alkylene, arylene and alkylene aryl, alkylene oxide containing from 2 to 6 carbon atoms, and poly(alkylene oxide), wherein the alkylene portion of the repeat groups contain from 2 to 6 carbon atoms and the poly(alkylene oxide) has a molecular weight of from 50 to 1,000;
• R11 is C1 to C20 linear or branched alkyl or alkylol;
• and mixtures thereof.

A photodefinable dielectric composition comprising

• a copolymer resulting from polymerizing a monomer mixture comprising 65 to 75 mole % decyl norbornene and from 25 to 35 mole % glycidyl methyl ether norbornene;
• a solvent comprising decahydronaphthalene;
• a photoacid generator comprising (4-methylphenyl-4-(1-methylethyl)phenyl iodonium tetrakis(pentafluorophenyl) borate;
• a photosensitizer comprising 1-chloro-4-propoxy-9H-thioxanthone;
• an antioxidant comprising 3,5-di-tert-butyl-4-hydroxyhydrocinnamate;
• an adhesion promoter comprising 3-glycidoxypropyl trimethoxysilane;
• and
• a reactive solvent comprising 1,4-dimethanolcyclohexane divinyl ether.