Polynorbornene Negative Photoresist

Claim 2

A negative photoresist formed by exposure of a film about 1 micron thick of a photosensitized ring-opened polycyclic norbornene ("PolyNB") polymer composition to ultraviolet light in the range from about 220-450 nanometers so as to form, in the contact mode, a pattern of lines and spaces by development in a substantially aliphatic hydrocarbon solvent so as to provide a resolution in the range from about I micron to about 2 microns in said pattern, said polymer composition having as an essential component, a major molar amount of a ring-opened unsubstituted or non-polar group substituted tetracyclic norbornene, and a minor amount of another norbornene, and including an effective amount of an aryl bis-azide sensitizer sufficient to yield a photocrosslinked polymer developable into said pattern.

Claim 3

The negative photoresist of claim 1 wherein said PolyNB polymer is represented by the structure wherein, m + q = 1 , and q may be 0; q is less than 0.5, preferably less than 0.2; m is greater than 0.5, preferably greater than 0.8; n is a number in the range from about 10 to about 10,000; M represents a ring-opened monomer having the structure and, Q represents a ring-opened monomer having the structure wherein, R and R 2 are each independently hydrogen, alkyl or alkylene having from 1 to about 10 carbon atoms provided that the total number of carbon atoms for R and R 2 is not greater than 20; or, RI and R 2 are each independently phenyl or naphthyl; or, R 1 and R 2 may be connected to form cycloalkyl or cycloalkylene having from 5 to 10 ring carbon atoms, either of which cycloalkyl or cycloalkylene may have a benzo- or naphtho- substituent.

Claim 4

The negative photoresist of claim 2 wherein the T g of said PolyNB polymer before it is crosslinked is higher than 150°C.

Claim 5

The negative photoresist of claim 3 wherein said development produces lines with essentially vertical walls and substantially unswollen contours.

Claim 6

The negative photoresist of claim 3 wherein the molecular weight distribution or dispersivity of said PolyNB polymer is in the range from about 1.5 to about 4.

Claim 7

The negative photoresist of claim 3 wherein said aryl bis-azide is represented by the structural formula wherein, R represents a moiety selected from the group consisting of wherein, n' is an integer in the range from 1 to 5; X and Y may be hydrogen, alkyl having from I to about 20 carbon atoms, or X and Y may be combined to form cycloalkyl having from 5 to about 8 carbon atoms, optionally with ring substituents.

Claim 8

The negative photoresist of claim 6 wherein said PolyNB polymer is represented by the structural formula wherein, n" + p = q, and either n" or p may be 0; and, R l , R 2 , m, n and q have the same connotation as that given hereinabove.

Claim 9

The negative photoresist of claim 6 wherein said PolyNB is a copolymer of tetracyclic norbornene monomers, the copolymer being represented by the structure wherein, m 1 + m 2 = m, but m is no more than 0.2m 1 ; each of R and R are independently hydrogen, alkyl or alkylene having from 1 to about 10 carbon atoms provided that the total number of carbon atoms for R 3 and R 4 is not greater than 20; or, R 3 and R 4 may be connected to form cycloalkyl or cycloalkylene having from 5 to 10 ring carbon atoms, either of which cycloalkyl or cycloalkylene may have a benzo- or naphto- substituent; and, R 5 and R 6 are each independently phenyl or naphthyl.

Claim 10

The negative photoresist of claim 7 wherein said PolyNB polymer is a copolymer of a tetracyclic norbornene M selected from the group consisting of tetracyclododecene, methyl tetracyclododecene, and another monomer Q selected from the group consisting of norbornene, methyl norbornene and dicyclopentadiene.

Claim 11

The negative photoresist of claim 8 wherein said PolyNB polymer is a copolymer of a tetracyclododecene and phenyl tetracyclododecene; or of methyl tetracyclododecene and phenyl tetracyclododecene.

Claim 12

The negative photoresist of claim 7 wherein said PolyNB polymer is selected from polymers of methyl tetracyclododecene and methyl norbornene; methyl tetracyclododecene, methyl norbornene and dicyclopentadiene; methyl tetracyclododecene and dicyclopentadiene; methyl tetracyclododecene and phenyl norbornene; methyl tetracyclododecene and cyclopentene; tetracyclododecene and methyl norbornene; tetracyclododecene, methyl norbornene and dicyclopentadiene; tetracyclododecene and dicyclopentadiene; tetracyclododecene and phenyl norbornene; homo(methyl tetracyclododecene); methyl tetracyclododecene, methyl norbornene and phenyl norbornene; tetracyclododecene and phenyl tetracyclododecene; and, methyl tetracyclododecene and phenyl tetracyclododecene.

Claim 13

A light-sensitive photographic material comprising a substrate and a coating thereon of a negative photoresist comprising, (a) a ring-opened polycyclic norbornene ("PolyNB") polymer having a structure represented by the formula wherein, m + q =1, and q may be 0; q is less than 0.5, preferably less than 0.2; m is greater than 0.5, preferably greater than 0.8; n is a number in the range from about 10 to about 10,000; M represents a ring-opened monomer having a tetracyclic norbornene structure; and, Q represents another ring-opened monomer having a norbornene structure with less than four fused rings; either M or Q have substituents which are independently hydrogen, alkyl or alkylene having from 1 to about 10 carbon atoms provided that the total number of carbon atoms for both substituents is not greater than 20; or, the substituents are each independently phenyl or naphthyl; or, the substituents may be connected to form cycloalkyl or cycloalkylene having from 5 to 10 ring carbon atoms, either of which cycloalkyl or cycloalkylene may have a benzo- or naphtho- substituent; and, (b) an aryl bis-azide sensitizer which upon exposure to u-v light in the range from 220-450 nanometers yields a crosslinked polymer developable into a pattern with a substantially aliphatic hydrocarbon solvent so as to provide a resolution in the range from I micron to about 2 microns in said pattern.

Claim 14

A light-sensitive photographic material comprising a substrate and a coating thereon of a negative photoresist comprising, (a) a ring-opened polycyclic norbornene ("PolyNB") polymer having a structure represented by the formula wherein, m + q =1, and q may be 0; q is less than 0.5, preferably less than 0.2; m is greater than 0.5, preferably greater than 0.8; n is a number in the range from about 10 to about 10,000; M represents a ring-opened monomer having a tetracyclic norbornene structure; and, Q represents another ring-opened monomer having a norbornene structure with less than four fused rings; either M or Q have substituents which are independently hydrogen, alkyl or alkylene having from 1 to about 10 carbon atoms provided that the total number of carbon atoms for both substituents is not greater than 20; or, the substituents are each independently phenyl or naphthyl; or, the substituents may be connected to form cycloalkyl or cycloalkylene having from 5 to 10 ring carbon atoms, either of which cycloalkyl or cycloalkylene may have a benzo- or naphtho- substituent; and, (b) an aryl bis-azide sensitizer which upon exposure to u-v light in the range from 220-450 nanometers yields a crosslinked polymer developable into a pattern with a substantially aliphatic hydrocarbon solvent so as to provide a resolution in the range from I micron to about 2 microns in said pattern.