Adhesively bonded photostructurable polyimide film

Claim 2

A process for preparing relief images by means of a photolithographic process, comprising the following steps: (i) coating a substrate surface with a photostructurable negative-working thermostable adhesive (ii) applying a self-supporting photostructurable polyimide film to the adhesive-coated surface, (iii) image-wise exposure of the arrangement with actinic radiation from the side of the polyimide film or of the substrate, and (iv) developing the system with a suitable developer in order to remove in the unexposed areas both the polyimide film and the adhesive film.

Claim 3

A process according to claim 1 where in step (i) the adhesive contains a solvent which is evaporated after the coating step.

Claim 4

A process according to claim 1 where in step (ii) the polyimide film is applied to the adhesive coated surface by employing pressure, heat or both pressure and heat.

Claim 5

A relief image obtained by the process according to claim 1.

Claim 6

A process according to claim 1 wherein the self-supporting photostructurable polyimide film in step (ii) has a thickness of 3-300 μm and comprises a homopolyimide or copolyimide having an average molecular weight of at least 2,000, which contains at least 5 mol %, based on the polymer, of at least one structural element of the formulae IX or X ##STR40## in which R 3 is halogen, nitro, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, which can be substituted by phenyl, or is phenyl, phenoxy or phenylthio, R 4 is a direct bond or a bridge group, R 5 is a hydrogen atom or aroyl or is defined in the same way as R 3 , a is 0, 1, 2 or 3, b is 0, 1, 2, 3 or 4, c and d are 0, 1, 2, 3, 4 or 5, f is 0 or 1, and, when a, b and d are 2, the two R 3 together can also be --CH═CH--CH═CH-- bonded in the o-position and R 2 and R 2 ' are an unsubstituted cycloaliphatic or araliphatic radical, an aromatic radical where two aryl nuclei are linked via an aliphatic group, or an aromatic radical which is substituted by at least one alkyl group, cycloalkyl group, alkoxy group, alkoxylalkyl group, alkylithio group, alkylthioalkyl group, aralkyl group or, on two adjacent C atoms of the aromatic radical, by an alkylene group, R 2 being an aromatic radical which is substituted in the two ortho-positions relative to at least one N atom, when f is 0.

Claim 7

A process according to claim 1 wherein the self-supporting photostructurable polyimide film in step (ii) has a thickness of 3-100 μm and comprises homo-polyimides or copolyimides which contain structural elements of aromatic aminodicarboxylic acids, having an inherent viscosity of at least 0.1 dl/g, measured at 25° C. in a solution of 0.5% by weight of polymimide in N-methylpyrrolidone, which contain recurring sturctural elements of the formula XI ##STR41## in which R 7 and R 8 are halogen, nitro, aryl, aryloxy, alkyl or alkoxy, m is 0 or a number from 1-4, n is 0 or a number from 1 to 3 and p is 0, 1 or 2, the free carbonyl groups are bonded in ortho-position relative to each other and R 6 is a divalent aromatic radical which is substituted by at least one alkyl group or aralkyl group.

Claim 8

A process according to claim 1 wherein the photostructurable negative-working thermostable adhesive in step (i) is a compound or mixture of compounds selected from the group consisting of (b1) photocrosslinkable polyimides which are soluble in organic solvents; (b2) photocrosslinkable polyamidic acids or their esters; (b3) photocrosslinkable organopolysilsesquioxanes; (b4) photocrosslinkable polyamide-imides; (b5) photocrosslinkable epoxy systems; and (b6) photocrosslinkable systems which contain compounds having ethylenically unsaturated groups which can undergo free radical polymerization.

Claim 9

A process according to claim 7 where the adhesive is (b1) a solution of polyimide or (b1) a solution of polymide in combination with an organic chromophoric polyazide.

Claim 10

A process according to claim 7 wherein the adhesive (b1) comprises a homopolymer or copolymer which is derived from at least one aromatic tetracarboxylic acid and at least one diamine and comprises 0.1 to 100 mol % of at least one structural element of the formula II ##STR42## and 99.9 to 0 mol % of at least one structural element of the formulae III and/or IV ##STR43## in which Z 1 is at least one tetravalent radical of the formulae V, VI, VII or VIII ##STR44## in which the free bonds are bonded in the ortho-position relative to each other and Y' is a direct bond, --CH 2 --, --(CH 2 ) 2 --, --O--, --S--, --SO--, --SO 2 --, --CO--, --NR v -- or --CR v R w -- where R v is a hydrogen atom, C 1 -C 10 -alkyl, phenyl, naphthyl or phenyl(C e H 2e )-- where e is 1 to 4 and R w is defined in the same way as R v except that it is not a hydrogen atom, R x is C 1 -C 10 -alkyl, halogen, --CN, --NO 2 , C 1 -C 12 -alkoxy, phenoxy, naphthoxy or phenyl-(C e H 2e )-- where e is 1-4, n' is 0, 1 or 2, X 1 is an unsubstituted or substituted heterocylic, cycloaliphatic or araliphatic radical, an aromatic radical where two aryl nuclei are linked via an aliphatic group, or an aromatic radicl which is substituted by at least one alkyl group, cycloalkyl group, alkoxy group, alkoxyalkyl group, alkylthio group, alkylthioalkyl group, hydroxyakyl group, hydroxyalkoxy group, hydroxylakylthio group, aralkyl group or, on two adjacent C atoms ofthe aromatic radical, by an alkylene group, Q 1 is a trivalent aromatic radical, Z 1 is defined in the same way as Z 1 or is a tetravalenet organic radical different from Z 1 , and X 1 ' is the divalent radical, differnet from X 1 , of an organic diamine, where Z 1 in formulae II can also be tetravalent benzophenone radicals if structural elements of the formula IV are present.

Claim 11

A process according to claim 8 wherein the adhesive (b1) comprises (a) a homopolyimide or copolyimide of aromatic tetracarboxylic acids and aromatic diamines or aromatic and aliphatic diamines which is soluble in organic solvents, at least one aliphatic group being bonded directly or via a bridge group to at least a portion of the tetracarboxylic acid radicals, of the aromatic diamine radials or of the two radicals, and/or at least a portion of these radicals containing, as an aliphatic bridge group, alkylene, alkylidene, cycloalkylidene or Si(alkyl) 2 , and (b) at least 0.1% by weight, based on the polyimide component, of at least one organic chromophoric polyazide in which the azide groups are bonded directly or via an SO 2 group to aromatic hydrocarbon radicals.

Claim 12

A process according to claim 10 wherein the homopolyimide or copolyimide comprises 50 to 100 mol % of recurring structural elements of the formulae XVII and/or XVIII ##STR45## and 50 to 0 mol % of recurring structural elements of the formula XIX ##STR46## where in the formulae XVII, XVIII and XIX the four carbonyl groups are bonded to different carbon atoms and two carbonyl groups each are in ortho- or peri-position relative to each other, Z 2 is a tetravalent radical which contains at least one aromatic ring, Z 2 ' is a divalent organic radical which differs from the groups ##STR47## and is selected from the group consisting of aromatic, alkylaromatic, aliphatic, cycloaliphatic and heterocyclic radicals, combinations thereof and radicals with oxygen-, sulfide-, nitrogen-, silicon- or phosphorus-containing bridge groups, R 17 and R 18 independently of each other are alkyl with 1-4 C atoms, R 19 , R 20 , R 22 , R 23 and R 24 independently of one another are hydrogen or alkyl having 1-4 C atoms and R 25 is a direct bond, --O--, --S--, --SO 2 --, --CO--, --CH 2 --, --C(CF 3 ) 2 --, cycloalkylidene having 5-6 ring carbon atoms, phenylene, ##STR48## or a group ##STR49## in which R 26 and R 27 are alkyl or alkoxy each having 1-6 C atoms, phenyl, benzyl, phenyloxy or benzyloxy.

Claim 13

A process according to claim 7 in which the thickness of the adhesive layer in the full curved state is less than 5 μm and the photostructurable negative-working thermostable adhesive used is na organopolysilsesquioxane of the formula XXXI ##STR50## in which R 50 and R 51 are independently of each other monomvalent hydrocarbon radicals and u is a whole number greater than 30.

Claim 14

A process according to claim 7 in which the adhesive (b4) comprises linear saturated homopolycondensates or copoly-condensates from the group of the polyamide-imides having bezophenonetricarboxylic acid radicals with at least one recurring structural element of the formula XII ##STR51## and in the case of copolycondensaes additionally recurring structural elements of the formulae XIIII and/or XIV ##STR52## in which the imide group in structural element XII is bonded to two adjacent C atoms, m 4 is 0 or a number from 1 to 4 and n 3 is 0 or a number from 1 to 3, X 2 is --S--, --O-- or --NR 15 -- and Y 1 independently is defined in the same way as X 2 , R 9 is alkyl or alkoxy having fewer than 6 C atoms, aryl having 6 to 10 C atoms, aralkyl having 7 to 10 C atoms or halogen, R 12 is an unsubstituted or substituted divalent aliphatic, cycloaliphatic, araliphatic or aromatic radical, and if X 2 and Y 1 are the group --NR 15 --, R 12 and one of the R 15 are together alkylene having 5 to 7 C atoms to which the second --NR 15 -- group is bonded, or R 12 is methylene, ethylene or propylene and the two R 15 of the NR 15 groups are together ethylene or propylene or X 2 or Y 1 are --S-- or --O-- and the other --NR 15 --, R 12 and R 15 together are alkylene having 5-7 C atoms to which the group --O-- or --S-- is bonded, R 10 is an unsubstituted or subsitituted divalent aliphatic or aromatic hydrocarbon radical, R 14 is independently defined in the same way as R 10 , R 11 is a divalent asaturated aliphatic or aromatic radical, R 13 is a trivalent saturated aliphatic or aromatic radical in which the imide group is bonded to two adjacent C atoms and R 15 is a hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl or alkaralkyl, the polycondensates containing the structural elements of the formula XII in an amount of at least 10 mol %, based on the copolymcondensate.

Claim 15

A process according to claim 7 in which the adhesive (b5) comprises a photocrosslinkable epoxy resin or mixture of such resins containing (a) an aromatic, cycloaliphatic or araliphatic compound which contains at least one 1,2-epoxy group, (b) at least one photoinitiator suitable for the photocrosslinking of epoxy resins alone or in combination with (c) a photoaceelerant, and, at least one aromatic, cycloaliphatic or araliphatic compound usable as as latent hot-curing agent.

Claim 16

A process according to claim 14 in which photoinitiator (b) is a halonium salt of the formula XXXIII [R.sup.41 R.sup.42 X.sup.a ].sub.q.sbsb.4.sup.+ [L.sub.2 Q.sub.m.sbsb.4.sup.a ].sup.-q.sbsb.4 XXXIII in which R 41 and R 42 independently of each other are a carbocyclic or heterocyclic aromatic radical having 6 to 20 C atoms or R 41 and R 42 together are a divalent carbocylic or heterocyclic aromatic radial, X a is a halogen atom, m 4 is a number which is equal to the total of the valencies of L 2 and q 4 , L 2 is a divalent to heptavalent metal or non-metal and Q a is a halogen atom, and q 4 is a number from 1 to 3.

Claim 17

A process according to claim 14 in which photoinitiator (b) is an iodosyl salt of the formula XXXIV [R.sup.43 R.sup.44 I=0].sub.q.sbsb.5.sup.+ [L.sub.3 Q.sub.m.sbsb.5.sup.b ].sup.-q.sbsp.5 XXXIV, in which R 43 and R 44 are a carbocyclic or heterocyclic aromatic radical having 6 to 20 C atoms, m 5 is a number which is equal to the total of the valencies of L 3 and q 5 , L 3 is a divalent to heptavalent metal or non-metal and Q b is a halogen atom, and q 5 is a number from 1 to 3.

Claim 18

A process according to claim 14 in which the photoinitiator used is a sulfonium salt of the formula XXXV [R.sup.45 R.sup.46 R.sup.47 S].sub.q.sbsb.6.sup.+ [L.sub.4 Q.sub.m.sbsb.6.sup.c ].sup.-q.sbsp.6 XXXV in which R 45 , R 46 and R 47 independently of one another are a carbocylic or heterocyclic aromatic radical having 6 to 20 C atoms or one of R 45 , R 46 and R 47 is this aromatic radical and the other two together are a divalent carbocylic or heterocyclic aromatic radical, m 6 is a number which is equal to the sum of the valencies of L 4 and q 6 , L 4 is a divalent to heptavalent metal or non-metal and Q c is a halogen atom, and q 6 is a number from 1 to

Claim 19

A process according to claim 14 in which photoinitiator (b) is (I) an active amount of a salt of the formula XXVIII [Y.sub.3 -Q-(CO).sub.a.sbsb.1 ].sup.+ MX.sub.4.sbsb.n 1 .sup.-(XXVIII), in which Y 3 is an arene group or dienylium group, Q is an atom of a transition metal selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, rutheium, rhodium, palladium, silver, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold, a 1 is a positive whole number such that the atom Q has a complete electron shell configuration, M is an atom of a metal or non-metal, n 1 4,5 or 6 and larger by unity than the valency of M and X 4 is a fluorine or chlroine atom, with the proviso that, when M is antimony, n 1 is 6 and five of the symbols X 4 are fluorine, and one can also be a hydroxo group; or (II) an active amount of a salt of the formula XXIX [(R.sup.48)(R.sup.49 Me).sub.a.sbsb.2 ]+a.sub.2 N.sub.2 [(a.sub.2 N.sub.2)/q.sub.2 ][LQ.sub.m.sbsb.2 '].sup.-q.sbsp.2 (XXIX) in which a 2 is 1 or 2 and n 2 and q 2 independently of each other are each a whole number from 1 to 3, Me is the cation of a monovalent to trivalent metal from the group IV to VIIb, VIII or Ib of the Periodic Table of Elements, m 2 is a whole number equal to the valency of L and q 2 and Q' is a halogen atom, L is a divalent to heptavalent metal or non-metal, R 48 is a π-arene and R 49 is a π-arene or the anion of a π-arene.

Claim 20

A process according to claim 18 in which photoinitiator (b) is at least one iron compound of the formula XXX [(R.sup.32)(R.sup.33 Fe.sup.II).sub.a.sbsb.3 ].sup.+a.sbsp. (a.sub.3 q.sub.3) (L.sub.1 Q.sub.m.sbsb.3 ").sup.-q.sbsp.3 (XXX) in which a 3 is 1 or 2 and q 3 is 1, 2 or 3, L 1 is a divalent to heptavalent metal or non-metal, Q" is a halogen atom, m 3 is a whole number which is equal to the total of the valencies of L 1 and q 3 , R 32 is a π-arene and R 33 is the anion of a π-arene; in which the compound of the formula XXX is used together with at least one electron acceptor as oxidizing agent and/or together with a sensitizer for the compound of the formula XXX.

Claim 21

A process according to claim 14 in which adhesive (b5) is a photocrosslinkable and subsequently still heat-curable epoxy resin based on bisphenol diglycidyl ethers, which in addition to free epoxy groups also contains photocrosslinkable radicals ##STR53## which are present in an amount of at least 10 mol %, based on the bisphenol units, as bridges between the aromatic nuclei of the bisphenol.

Claim 22

A process according to claim 14 in which adhesive (b5) comprises a mixture of compounds having ethylenically unsaturated groups which can undergo free radical polymerization, selected from the group consisting of (A) mixtures which comprise (a) at least one ethylenically unsaturated compound which can undergo free radical polymerization and has a boiling point above 100° C. under atmospheric pressure, (b) at least one organic, inorganic or organometallic phootoinitiator which, on irradiation, forms free radicals, and (c) a polymeric binder; or (B) mixtures which comprise (a) compounds or mixtures of copounds having not only at least one medial epoxy group and/or at least one structural element of the formula XXXII, ##STR54## which is bonded terminally directly to an oxygen atom or nitrogen atom, in which R 34 and R 36 are each a hydrogen atom, when R 35 is then a hydrogen atom or a methyl group, or R 34 and R 36 together are --CH 2 --CH 2 , when R 35 is then a hydrogen atom, but also having at least one ethyleically unsaturated double bond in a molecule, and (b) lest one photoinitiator which, on irradiation, forms free radicals along or in combination with (c) polymeric binder, a heat-activatable polymerizing agent for 1,2-epoxy resins and/or photosensitizers or photoinitiators for epoxy polymerization; or (C) mixtures which comprise (a) an epoxy rsin havign at least one medial epoxy group and/or at least one epoxy group of the formula XXXII, as defined above, and (b) a compound which can undergo free radical photopolymerization or in combination with (c) a heat-activatable curing agent for the epoxy resin.

Claim 23

A process according to claim 1 in which the substrate has a scattering surface and in which the adhesive contains a radiation-absorbing additive in such amount that light scattered laterally at the substrate surface does not penetrate into the adhesive or into the polyimide film.

Claim 24

A process according to claim 1 wherein the self-suppporting photostructurable polyimide film in step (ii) has a thickness of 3-300 um and comprises a homopolyimide or copolyimide which has 5 to 100 mol %, based on the total molecule, of at least one structural element of the formula Ia and 95-0 mol % of at least one structural element of the formula Ib, ##STR55## where the carbonyl groups in the formula Ia are in each case pairwise in the ortho-position relative to each other, Z' is a tetravalent benzophenone radical or another unsubstituted or substituted tetravalent aromatic radical to which in each case two carbonyl groups are bonded in the ortho or peri-position, X is a divalent radical of an aromatic diamine wherein the aromatic ring is substituted by alkyl, alkoxy, alkoxyalkyl or aralkyl in both ortho-positions relative to at least one N atom or in at least one ortho-position relative to both N atoms, or two adjacent C atoms of the aromatic ring are substituted by alkylene, and X' is a divalent radical of an aromatic diamine which differs form X or a divalent radical of an aliphatic diamine.

Claim 25

A process according to claim 23 where in the polyimide polymer at least 50 mol % of the polymer, based on the total molecule, comprise structural elements of the formula Ia, and wherein the radical Z' of the structural element of the formula Ib is independently selected from the group consisting of ##STR56## in which R is a direct bond or is ##STR57## in which R a , R b and R c are alkyl having 1 to 6 C atoms, phenyl or benzyl or R b and R c are also alkoxy having 1 to 6 C atoms, phenyloxy or benzyloxy, X' of the structural element Ib is C 2 -C 30 alkylene, C 5 -C 8 cycloalkylene, C 7 -C 30 aralkylene, C 6 -C 22 arylene or polysiloxane, X of structural element Ia is ##STR58## in which, in the formula Ic, the free bonds are in the meta- or para-position relative to each other, in the formula Id the free bonds are in the meta- or para-position relative to the R j group and R d and R e are bonded in the two ortho-positions relative to the free bond, and in the formula Ie the free bonds are bonded in the 2-, 3-, 6- and 7-position and R d and R e are situated in the two ortho-positions relative to the free bonds, R j is a direct bond, --O--, --S--, --SS--, --SO--, --SO 2 , --CO--, --COO--, --NH--, ##STR59## R k is a hydrogen atom, C 1 -C 6 alkyl or phenyl, or the group R j is a linear or branched alkylene group having 1 to 3 C atoms, alkylidene which has 2 to 12 C atoms and can be substituted by Cl or F, cycloalkylidene having 5 to 6 ring carbon atoms, phenylene, phenylenedioxy, or the group R 1 SiR m , ##STR60## in which R 1 and R m are alkyl or alkoxy having 1 to 6 C atoms, phenyl, benzyl, phenyloxy or benzyloxy, r is a number from 1 to 10, t is 0 or 1 and s is 0 or 1, and RY is --O-- or --S-- and Q 2 is C 1 -C 6 alkylene, and q is a number from 1 to 100, R d and R e are alkyl or alkoxy having 1 to 12 C atoms, alkoxyalkyl having 2 to 12 C atoms, cyclopentyl, cyclohexyl or benzyl or in the formulae Ic or Id, R d and R f are in adjacent positions and together are trimethylene or tetramethylene, and R e can also be a hydrogen atom, R f , R g , R h and R i are independently a hydrogen atom or alkyl or alkoxy having 1 to 12 C atoms, alkoxyalkyl having 2 to 12 C atoms, cyclopentyl, cyclohexyl or benzyl or R f and R h in the formula Id together are trimethylene or tetramethylene.

Claim 26

A process according to claim 24 wherein Z' is a radical of the formula ##STR61## in which R n is a direct bond, --O--, --SO 2 --, --CH 2 --, --C(CF 3 ) 2 or --CO--, in which the radical X is selected from the group consisting of ##STR62## in which the free bonds are in the meta- or para-position relative to each other, and ##STR63## in which R o and R p are independently methyl, ethyl, n-propyl or isopropyl and R q and R p are independently methyl, ethyl, n-propyl or isopropyl and R q and R r are a hydrogen atom or are defined in the same way as R o or R o and R q are together trimethylene and R p and R r are a hydrogen atom, and R s is a direct bond, --CH 2 --, --C(CH 3 ) 2 --, 2,2-propylidene or --CO--, and in which the radical X' is selected from the group consisting of ##STR64## in which R u is a direct bond, --O--, --CO--, --C(CF 3 ) 2 -- or --CH 2 --, and R t is methyl, ethyl, isopropyl, methoxy, ethoxy or a hydrogen atom.

Claim 27

A process for preparing relief images by means of photolithographic process, comprising the following steps: (i) coating a substrate surface with the adhesive side of a two-layer system comprising photostructurable negative-working thermostable adhesive and self-supporting photostructurable polyimide film, (ii) image-wise exposure of the arrangement with actinic radiation from the side of the polyimide film or of the substrate and (iii) developing the system with a suitable developer in order to remove in the unexposed areas the polyimide film and the adhesive film.

Claim 28

A process for preparing relief images by means of photolithographic process, comprising the following steps: (i) coating a substrate surface with the adhesive side of a two-layer system comprising photostructurable negative-working thermostable adhesive and self-supporting photostructurable polyimide film, (ii) image-wise exposure of the arrangement with actinic radiation from the side of the polyimide film or of the substrate and (iii) developing the system with a suitable developer in order to remove in the unexposed areas the polyimide film and the adhesive film.

Claim 29

A process according to claim 26 where in step (i) the substrate surface is coated with the adhesive side of the two-layer system by employing pressure, heat or both pressure and heat.

Claim 30

A relief image obtained by the process according to claim 26.

Claim 31

A process according to claim 26 wherein the self-supporting photostructurable polyimide film in step (i) has a thickness of 3-300 μm and comprises a homopolyimide or copolyimide having an average molecular weight of at least 2,000, which contains at least 5 mol %, based on the polymer, of at least one structural element of the formulae IX or X ##STR65## in which R 3 is halogen, nitro, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, which can be substituted by phenyl, or is phenyl, phenoxy or phenylthio, R 4 is a direct bond or a bridge group, R 5 is a hydrogen atom or aroyl or is deifned in the same way as R 3 , a is 0, 1, 2 or 3, b is 0, 1, 2, 3 or 4, c and d are 0, 1 2, 3, 4 or 5, f is 0 or 1, and, when a, b and d are 2, the two R 3 together can also be --CH═CH--CH═CH-- bonded in the o-position, and R 2 and R 2 ' are an unsubstituted or substituted cycloaliphatic or araliphatic radical, an aromatic radical where two aryl nuclei are linked via an aliphatic group, or an aromatic radical which is substituted by at least one alkyl group, cycloalkyl group, alkoxy group, alkoxyalkyl group, alkylthio group, alkylthioalkyl group, aralkyl group or, on two adjacent C atoms of the aromatic radical, by an alkylene group, R 2 being an aromatic radical which is substituted in the two ortho-positions relative to at least one N atom, when f is 0.

Claim 32

A process according to claim 26 wherein the self-supporting photostructurable polyimide film in step (i) has a thickness of 3-100 μm and comprises homopolyimides or copolymides which contain structural elements of aromatic aminodicarboxylic acids, having an inherent viscosity of at least 0.1 dl/g, measured at 25° C. in a solution of 0.5% by weight of polyimide in N-methylpyrrolidone, which contain recurring structural elemetns of the formula XI ##STR66## in which R 7 and R 8 are halogen, nitro, aryl, aryloxy, alkyl or alkoxy, m is 0 or a number from 1-4, n is 0 or a number from 1 to 3 and p is 0, 1 or 2, the free carbonyl groups are bonded in ortho-position relative to each other and R 6 is a divalent aromatic radical which is substituted by at least one alkyl group or aralkyl group.

Claim 33

A process according to claim 26 wherein the photostructurable negative-working thermostable adhesive in step (i) is a compound or mixture of compounds selected from the group consisting of (b1) photocrosslinkable polyimides which are soluble in organic solvents; (b2) photocrosslinkable polyamidic acids or their esters; (b3) photocrosslinkable organopolysilsequioxanes; (b4) photocrosslinkable polyamide-imides; (b5) photocrosslinkable epoxy systems; and (b6) photocrosslinkable systems which contain compounds having ethylenically unsaturated groups which can undergo free radical polymerization.

Claim 34

A process according to claim 31 where the adhesive is (b1) a solution of polyimide or (b1) a solution of polyimide in combination with an organic chromophoric polyazide.

Claim 35

A process according to claim 31 wherein the adhesive (b1) comprises a homopolymer or copolymer which is derived from at least one aromatic tetracarboxylic acid and at least one diamine and comprises 0.1 to 100 mol % of at least one structural element of the formula II ##STR67## and 99.9 to 0 mol % of at least one structural element of the formulae III and/or IV ##STR68## in which Z 1 is at least one tetravalent radical of the formulae V, VI, VII or VIII ##STR69## in which the free bonds are bonded in the ortho-position relative to each other and Y' is a direct bond, --CH 2 --, --(CH 2 ) 2 --, --O--, --S--, --SO--, --SO 2 --, --CO--, --NR v -- or --CR v R w -- where R v is a hydrogen atom, C 1 -C 10 -alkyl, phenyl, naphthyl or phenyl (C e H 2e )-- where e is 1 to 4 and R w is defined in the same way as R v except that it is not a hydrogen atom, R x is C 1 -C 10 -alkyl, halogen --CN, --NO 2 , C 1 -C 12 -alkoxy, phenoxy, naphthoxy or phenyl--(C e H 2e )-- where e is 1-4, n' is 0, 1 or 2, X 1 is an unsubstituted or substituted heterocyclic, cycloaliphatic or araliphatic radical, an aromatic radical where two aryl nuclei are linked via an aliphatic group, or an aromatic radical which is substituted by at least one alkyl group, cycloalkyl group, alkoxy group, alkoxyalkyl group, alkylthio group, alkylthioalkyl group, hydroxyalkyl group, hydroxyalkoxy group, hydroxyalkylthio group, aralkyl group or, on two adjacent C atoms of the aromatic radical, by an alkylene group, Q 1 is a trivalent aromatic radical, Z 1 ' is defined in the same way as Z 1 or is a tetravalent organic radical different from Z 1 , and X 1 ' is the divalent radical, different from X 1 , of an organic diamine, where Z 1 in formula II can also be tetravalent benzophenone radicals if structural elements of the formula IV are present.

Claim 36

A process according to claim 32 wherein the adhesive (b1) comprises (a) a homopolyimide or copolyimide of aromatic tetracarboxylic acids and aromatic diamines or aromatic and aliphatic diamines which is soluble in organic solvents, at least one aliphatic group being bonded directly or via a bridge group to at least a portion of the tetracarboxylic acid radicals, of the aromatic diamine radicals or of the two radicals, and/ or at least a portion of these radicals containing, as an aliphatic bridge group, alkylene, alkylidene, cycloalkylidene or Si(alkyl) 2 , and (b) at least 0.1% by weight, based on the polyimide component, of at least one organic chromophoric polyazide in which the azide groups are bonded directly or via an SO 2 group to aromatic hydrocarbon radicals.

Claim 37

A process according to claim 34 wherein the homopolyimide or copolymide comprises 50 to 100 mol % of recurring structural elements of the formulae XVII and/or XVIII ##STR70## and 50 to 0 mol % of recurring structural elements of the formula XIX ##STR71## where in the formulae XVII, XVIII and XIX the four carbonyl groups are bonded to different carbon atoms and two carbonyl groups each are in ortho- or peri-position relative to each other, Z 2 is a tetravalent radical which contains at least one aromatic ring, Z 2 40 is a divalent organic radical which differs from the groups ##STR72## and is selected from the group consisting of aromatic, alkylaromatic, aliphatic, cycloaliphatic and heterocyclic radicals, combinations thereof and radicals with oxygen-, sulfide-, nitrogen-, silicon- or phosphorous-containing bridge groups, R 17 and R 18 independently of each other are alkyl with 1-4 C atoms, R 19 , R 20 , R 21 , R 22 , R 23 and R 24 independently of one another are hydrogen or alkyl having 1-4 C atoms and R 25 is a direct bond, --O--, --S--, --SO 2 , --CO--, --CH 2 --, --C(CF 3 ) 2 --, cycloalkylidene having 5-6 ring carbon atoms, phenylene, ##STR73## or a group ##STR74## in which R 26 and R 27 are alkyl or alkoxy each having 1-6 C atoms, phenyl, benzyl, phenyloxy or benzyloxy.

Claim 38

A process according to claim 31 in which the thickness of the adhesive layer in the fully cured state is less than 5 μm and the photostructurable negative-working thermostable adhesive used is an organopolysilsesquinoxane of the formula XXXI ##STR75## in which R 50 and R 51 are independently of each other monovalent hydrocarbon radicals and u is a whole number greater than 30.

Claim 39

A process according to claim 31 in which the adhesive (b4) comprises linear saturated homopolycondensates or copolycondensates from the group of the polyamide-imides having benzophenonetricarboxylic acid radicals with at least one recurring structural element of the formula XII ##STR76## and in the case of copolycondensates additionally recurring structural elementrs of the formulae XIII and/or XIV ##STR77## in which the imide group in structural element XII is bonded to two adjacent C atoms, m 4 is 0 or a number from 1 to 4 and n 3 is 0 or a number from 1 to 3, X 2 is --S--, --O-- or --NR 15 -- and Y 1 independently is defined in the same way as X 2 , R 9 is alkyl or alkoxy having fewer than 6 C atoms, aryl having 6 to 10 C atoms, aralkyl having 7 to 10 C atoms or halogen, R 12 is an unsubstituted or substituted divalent aliphatic, cycloaliphatic, araliphatic or aromatic radical, and if X 2 and Y 1 are the group --NR 15 --, R 12 and one of the R 15 are together alkylene having 5 to 7 C atoms to which the second --NR 15 -- group is bonded, or R 12 is methylene, ethylene or propylene and the two R 15 of the NR 15 groups are together ethylene or propylene or X 2 or Y 1 are --S-- or --O-- and the other --NR 15 --, R 12 and R 15 together are alkylene having 5-7 C atoms to which the group --O-- or --S-- is bonded, R 10 is an unsubstituted or substituted divalent aliphatic or aromatic hydrocarbon radical, R 14 is independently defined in the same way as R 10 , R 11 is a divalent saturated aliphatic or aromatic radical, R 13 is a trivalent saturated aliphatic or aromatic radical in which the imide group is bonded to two adjacent C atoms and R 15 is a hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl or alkaralkyl, the polycondensates containing the structural elements of the formula XII in an amount of at least 10 mol %, based on the copolycondensate.

Claim 40

A process according to claim 31 in which the adhesive (b5) comprises a photocrosslinkable epoxy resin or mixture of such resins containing (a) an aromatic, cycloaliphatic or araliphatic compound which contains at least one 1,2-epoxy group, (b) at least one photoinitiator suitable for the photocrosslinking of epoxy resins alone or in combination with (c) a photoaccelerant, and, at least one aromatic, cycloaliphatic or araliphatic compound usable as a latent not-curing agent.

Claim 41

A process according to claim 38 in which photoinitiator (b) is a halonium salt of the formula XXXIII [R.sup.41 R.sup.42 X.sup.a ].sub.q.sbsb.4.sup.+ [L.sub.2 Q.sub.m.sbsb.4.sup.a ].sup.-q.sbsp.4 XXXIII in which R 41 and R 42 independently of each other are a carbocyclic or heterocyclic aromatic radical having 6 to 20 C atoms or R 41 and R 42 together are a divalent carbocyclic or heterocyclic aromatic radical, X a is a halogen atom, m 4 is a number which is equal to the total of the valencies of L 2 and q 4 , L 2 is a divalent to heptavalent metal or non-metal and Q a is a halogen atom, and q 4 is a number from 1 to 3.

Claim 42

A process according to claim 38 in which photoinitiator (b) is an iodosyl salt of the formula XXXIV [R.sup.43 R.sup.44 I=0].sub.q.sbsb.5.sup.+ [L.sub.3 Q.sub.m.sbsb.5.sup.b ].sup.-q.sbsp.5 XXXIV, in which R 43 and R 44 are a carbocyclic or heterocyclic aromatic radical haivng 6 to 20 C atoms, m 5 is a number which is equal to the total of the valencies of L 3 and q 5 , L 3 is a divalent to heptavalent metal or non-metal and Q b is a halogen atom, and q 5 is a number from 1 to 3.

Claim 43

A process according to claim 38 in which the photoinitiator used is a sulfonium salt of the formula XXXV [R.sup.45 R.sup.46 R.sup.47 S].sub.q.sbsb.6.sup.+ [L.sub.4 Q.sub.m.sbsb.6.sup.c ].sup.-q.sbsp.6 XXXV in which R 45 , R 46 , and R 47 independently of one another are a carbocylic or heterocyclic aromatic radical having 6 to 20 C atoms or one of R 45 , R 46 , R 46 and R 47 is this aromatic radical and the other two together are a divalent carbocyclic or heterocyclic aromatic radical, m 6 is a number which is equal to the sum of the valencies of L 4 and q 6 , L 4 is a divalent to heptavalent metal or non-metal and Q c is a halogen atom, and q 6 is a number from 1 to 3.

Claim 44

A process according to claim 38 in which photoinitiator (b) is (I) an active amount of a salt of the formula XXVIII ps [Y.sub.3 -Q-(CO).sub.a.sbsb.1 ].sup.+ MX.sub.4.sbsb.n1 .sup.-(XXVIII), in which Y 3 is an arene group or dienylium group, Q is an atom of a transition metal selected from the group consisting of titanium, vandium, chromium, manganese, iron, cobalt, nickel, copper, niobium, molybdenum, ruthenium, rhodium, palladium, silver, tantalum, tungsten, rhenium, osmium, iridium, platinum and gold, a 1 is a positive whole number such that the atom Q has a complete electron shell configuration, M is an atom of a metal or non-metal, n 1 4, 5 or 6 and larger by unity than the valency of M and X 4 is a fluorine or chlorine atom, with the proviso that, when M is antimony, n 1 is 6 and five of the symbols X 4 are fluorine, and one can also be a hydroxo group; or (II) an active amount of a salt of the formula XXIX [(R.sup.48)(R.sup.49 Me).sub.a.sbsb.2 ].sup.+a.sbsp.2.sup.n.sbsp.2 [(a.sub.2 n.sub.2)/q.sub.2 ][LQ.sub.m.sbsb.2 '].sup.-q.sbsp.2(XXIX) in which a 2 is 1 or 2 and n 2 and q 2 indenpendently of each other are each a whole number from 1 to 3, Me is the cation of a monovalent to trivalent metal from the group IVb to VIIb, VIII or Ib of the Periodic Table of Elements, m 2 is a whole number equal to the valency of L and q 2 and Q' is a halogen atom, L is a divalent to heptavalent metal or non-metal, R 48 is a π-arene and R 49 is a π-arene or the anion of a π-arene.

Claim 45

A process according to claim 42 in which photoinitiator (b) is at least one iron compound of the formula XXX [(R.sup.32)(R.sup.33 Fe.sup.II).sub.a.sbsb.3 ].sup.+.sbsp.a3 (a.sub.3 /q.sub.3)(L.sub.1 Q.sub.m.sbsb.3 ").sup.-q.sbsp.3 (XXX) in which a 3 is 1 or 2 and q 3 is 1, 2 or 3, L 1 is a divalent to heptavalent metal or non-metal, Q" is a halogen atom, m 3 is a whole number which is equal to the total of the valencies of L 1 and q 3 , R 32 is a π-arene and R 33 is the anion of a π-arene; in which the compound of the formula XXX is used together with at least one electron accpetor as oxidizing agent and/or together with a sensitizer for the compound of the formula XXX.

Claim 46

A process according to claim 38 in which adhesive (b5) is a phtocrosslinkable and subsequently still heat-cruable epoxy resin based on bisphenol diglycidyl ethers, which in addition to free epoxy groups also contains photocrosslinkable radicals ##STR78## which are present in an amount of at least 10 mol %, based on the bisphenol units, as bridges between the aromatic nuclei of the bisphenol.

Claim 47

A process according to claim 38 in which adhesive (b5) comprises a mixture of compounds having ethylenically unsaturated groups which can undergo free radical polymerization, selected from the group consisting of (A) mixtures which comprise (a) at least one ethylenically unsaturated compound which can undergo free radical polymerization and has a boiling point above 100° C. under atmospheric pressure, (b) at least one organic, inorganic or organometallic photoinitiator which, on irradiation, forms free radicals, and (c) a polymeric binder; or (B) mixtures which comprise (a) compounds or mixtures of compounds having not only at least one medial epoxy group and/or at least one structural element of the formula XXXII, ##STR79## which is bonded terminally directly to an oxygen atom or nitrogen atom, in which R 34 and R 36 are each a hydrogne atom, when R 35 is then a hydrogen atom or a methyl group, or R 34 and R 36 together are --CH 2 --CH 2 , when R 35 is then a hydrogen atom, but also having at least one ethylenically unsaturated double bond in a molecule, and (b) at least one photoinitiator which, on irradiation, forms free radicals alone or in combination with (c) polymeric binder, a heat-activatable polymerizing agent for 1,2-epoxy resins and/or photosensitizers or photoinitiators for epoxy polymerization; or (C) mixtures which comprise (a) an epoxy resin having at least one medial epoxy group and/or at least one epoxy group of the formula XXXII, as defined above, and (b) a compound which can undergo free radical photopolymeriation or in combination with (c) a heat-activatable curing agent for the epoxy resin.

Claim 48

A process according to claim 26 in which the substrate has a scattering surface and in which the adhesive contains a radiation-absorbing additive in such amount that light scattered laterally at the substrate surface does not penetrate into the adhesive or into the polyimide film.

Claim 49

A process according to claim 26 wherein the self supporting photostructurable polyimide film in step (ii) has a thickness of 3-300 μm and comprises a homopolyimide or copolyimide which has 5 to 100 mol %, based on the total molecule, of at least one structural element of the formula Ia and 95-0 mol % of at least one structural element of the formula Ib, ##STR80## where the carbonyl groups in the formula Ia are in each case pairwise in the ortho-position relative to each other, Z' is a tetravalent benzophenone radical or another unsubstituted or substituted tetravalent aromatic radical to which in each case two carbonyl groups are bonded in the ortho- or peri-position, X is a divalent radical of an aromatic diamine wherein the aromatic ring is substituted by alkyl, alkoxy, alkoxyalkyl or aralkyl in both ortho-positions relative to at least one N atom or in at least one ortho-position relative to both N atoms, or two adjacent C atoms of hte aromatic ring are substituted by alkylene, and X' is a divalent radical of an aromatic diamine which differs from X or a divalent radical of an aliphatic diamine.

Claim 50

A process according to claim 47 where in the polyimide polymer at least 50 mol % of the polymer, based on the total molecule, comprise structural elements of the formula Ia, and wherein the radical Z' of the structural element of the formula Ib is independently selected from the group consisting of ##STR81## in which R is a direct bond or is ##STR82## in which R a , R b and R c are alkyl having 1 to 6 C atoms, phenyl or benzyl or R b and R c are also alkoxy having 1 to 6 C atoms, phenyloxy or benzyloxy, X' of the structural element Ib is C 2 -C 30 alkylene, C 5 -C 8 cycloalkylene, C 7 -C 30 aralkylene, C 6 -C 22 arylene or polysiloxane, X of structural element Ia is ##STR83## in which, in the formula Ic, the free bonds are in the meta- or para-position relative to each other, in the formula Id the free bonds are in the meta- or para-position relative to hte R j group and R d and R e are bonded in the two ortho-positions relative to the free bond, and in the formula Ie the free bonds are bonded in the 2-, 3-, 6- and 7-position and R d and R e are situated in the two ortho-positions relative to the free bonds, R j is a direct bond, --O--, --S--, --SS--, --SO--, --SO 2 , --CO--, --COO--, --NH--, ##STR84## R k is a hydrogen atom, C 1 -C 6 alkyl or phenyl, or the group R j is a linear or branched alkylene grop having 1 to 3 C atoms, alkylidene which has 2 to 12 C atoms and can be subsituted by Cl or F, cycloalkylidene having 5 or 6 ring carbon atoms, phenylene, phenylenedioxy, or the group R 1 SiR m , ##STR85## in which R 1 and R m are alkyl or alkoxy having 1 to 6 C atoms, phenyl, benzyl, phenyloxy or benzyloxy, r is a number from 1 to 10, t is 0 or 1 and s is 0 or 1, and RY is --O-- or --S-- and Q 2 is C 1 -C 6 -alkylene, and q is a number from 1 to 100, R d and R e are alkyl or alkoxy having 1 to 12 C atoms, alkoxyalkyl having 2 to 12 C atoms, cyclopentyl, cyclohexyl or benzyl or in the formulae Ic or Id, R d and R f are in adjacent positions and together are trimethylene or tetramethylene, and R e can also be a hydrogen atom, R f , R g , R h and R i are independently a hydrogen atom or alkyl or alkoxy having a 1 to 12 C atoms, alkoxyalkyl having 2 to 12 C atoms, cyclopentyl, cyclohexyl or benzyl or R f and R h in the formula Id together are trimethylene or tetramethylene.

Claim 51

A process according to claim 48 wherein Z' is a radical of the formula ##STR86## in which R n is a direct bond, --O--, --SO 2 --, --CH 2 --, --C(CF 3 ) 2 or --CO--, in which the radical X is selected from the group consisting of ##STR87## in which the free bonds are in the meta- or para-position relative to each other, and ##STR88## in which R o and R p are independently mthyl, ethyl, n-propyl or isopropyl and R q and R r are a hydrogen atom or are defined on the same way as R o or R o and R q are together trimethylene or tetramethylene and R p and R r are a hydrogen atom, and R s is a direct bond, --CH 2 --, --C(CF 3 ) 2 --, 2,2-propylidene or --CO--, and in which the radical X' is selected from the group consisting of ##STR89## in which R u is a direct bond, --O--, --CO--, --C(CF 3 ) 2 -- or --CH 2 --, and R t is methyl, ethyl, isopropyl, methoxy or a hydrogen atom.