Polycyclic polymers containing pendant cyclic anhydride groups

Details Polycyclic polymers containing pendant cyclic anhydride groups Polycyclic polymers containing pendant cyclic anhydride groups

2000-03-09

2003-02-25

Pezzuto, Helen L. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S256000, C526S257000, C526S266000, C526S268000, C526S270000, C526S271000, C526S280000, C526S282000, C526S284000, C526S286000, C526S288000, C526S309000, C430S270100

Reexamination Certificate

active

06525153

ABSTRACT:

BACKGROUND OF THE INVENTION
TECHNICAL FIELD
The present invention relates to polycyclic polymers. More specifically, the invention relates to polymers comprising polycyclic repeating units wherein at least a portion of which contain pendant anhydride functionality. Optionally, the polymer comprises polycyclic co-repeating units having pendant acid labile functionality to afford compositions suitable for use in photolithographic applications.
BACKGROUND
Copolymers polymerized from polycycloolefin monomers and maleic anhydride monomers are disclosed in International Patent Application Publication No. WO 97/33198 to The B. F. Goodrich Company. In one disclosed embodiment, a polycycloolefin containing a pendant acid labile group is copolymerized with maleic anhydride via a free radical process to yield a polymer product wherein the maleic anhydride becomes incorporated directly into the backbone of the polymer generally represented as follows:
In European Patent Application Publication No. EP 0 794 458 to Lucent Technologies Inc. there is disclosed a copolymer polymerized from a polycycloolefin, maleic anhydride, and an acrylate or methacrylate monomer containing an acid labile group. These monomers are also polymerized via a free radical process to yield a polymer product of the general structure:
When polymerized via free radical processes the polycycloolefin and maleic anhydride monomers of the foregoing disclosures incorporate into the polymer backbone in a one-to-one ratio yielding an alternating copolymer. There is no disclosure of polymer products containing anhydride moieties that are pendant to the polycyclic repeating unit.
SUMMARY OF THE INVENTION
It is an object of the invention to provide novel polycyclic polymer compositions comprising repeating units containing a pendant cyclic anhydride group.
It is another object of the invention to provide polycyclic copolymer compositions containing repeating units having pendant cyclic anhydride groups in combination with one or more polycyclic repeating units having a pendant sulfonamide, hydrocarbyl, and/or functional groups.
It is still another object of the invention to provide a polycyclic copolymer composition containing repeating units having a pendant cyclic anhydride group and a pendant acid labile group.
It is a further object of the invention to provide a polycyclic copolymer composition containing repeating units having a pendant cyclic anhydride group and a pendant hydrocarbyl group.
It is another object of the invention to provide a polycyclic copolymer composition containing repeating units having a pendant cyclic anhydride group, a pendant acid labile group, and a pendant sulfonamide group.
It is still a further object of the invention to provide polymer compositions suitable for use in photoresist compositions.
The polymers of this invention are prepared by polymerizing a polycyclic monomer having the respective pendant moieties in the presence of a free radical or nickel addition catalyst. Alternatively, the polycyclic monomers can be polymerized in the presence of a ROMP catalyst.
DETAILED DESCRIPTION OF THE INVENTION
The polycyclic polymers of the present invention comprise repeating units polymerized from at least one polycycloolefin monomer wherein at least a portion of which contain a pendant anhydride group. As stated herein the terms “polycycloolefin,” “polycyclic,” and “norbornene-type” monomer are used interchangeably and mean that the monomer contains at least one norbornene moiety as shown below:
In the formula above, x represents oxygen, nitrogen, sulfur or a methylene group of the formula —(CH
2
)
n
— wherein n′ is an integer of 1 to 5.
The simplest polycyclic monomer of the invention is the bicyclic monomer, bicyclo[2.2.1]hept-2-ene, commonly referred to as norbornene. The term norbornene-type monomer is meant to include norbornene, substituted norbornene(s), and any substituted and unsubstituted higher cyclic derivatives thereof so long as the monomer contains at least one norbornene or substituted norbornene moiety. The substituted norbornenes and higher cyclic derivatives thereof contain a pendant hydrocarbyl substituent(s) or a pendant functional substituent(s) containing a heteroatom such as oxygen or nitrogen.
The anhydride functional norbornene-type monomers are represented by the structure below:
wherein x independently represents oxygen, nitrogen, sulfur or a methylene group of the formula —(CH
2
)
n
—; n′ is an integer of 1 to 5, preferably 1 or 2, and more preferably 1; m is an integer from 0 to 5, preferably 0 or 1; and R
1
and R
4
independently represent hydrogen, linear or branched linear and branched C
1
-C
20
alkyl; R
2
and R
3
independently represent hydrogen, and linear and branched C
1
-C
20
alkyl, with the proviso that at least one of R
2
and R
3
is a pendant cyclic anhydride group of the formula:
or at least one of R
1
and R
2
or R
3
and R
4
can be taken together with the ring carbon atom to which they are attached to form a spirally attached cyclic anhydride group. Monomers containing the spirally attached anhydride group can be represented by the formula:
wherein R
3
, R
4
, x and m are as defined above.
The norbornene-type monomers of Formula I can be copolymerized with norbornene-type monomers containing pendant sulfonamide functional groups, norbornene-type monomers containing pendant hydrocarbyl and/or functional groups , and mixtures of the foregoing monomers.
The norbornene-type monomers containing pendant sulfonamide groups can be represented by Formula II below:
wherein x and m are as defined above and R
5
and R
8
independently represent hydrogen, linear or branched linear and branched C
1
-C
20
alkyl; R
6
and R
7
independently represent hydrogen, linear and branched C
1
-C
20
alkyl or a sulfonamide group, with the proviso that at least one of R
2
and R
3
is a pendant sulfonamide group of the formulae:
—A—NR′SO
2
R″ and —A—SO
2
NR′R′″
or a cyclic sulfonamide group formed by combining R
6
and R
7
together with the two ring carbon atoms to which they are attached to form a heterocyclic ring of the formula:
wherein m′ is an integer from 1 to 3. Monomers containing the foregoing group can be represented by Formula IIa below:
In Formula IIa R
5
, R
8
, x, m, and m′ are as defined previously. In Formula IIa R
5
and, R
8
are preferably hydrogen.
In the formulae above —A— is a divalent radical selected from —(CR
1′
R
2′
)
n′
—, —(CHR
1′
)
n″
O(CHR
1′
)
n″
—, —(CHR
1′
)
n″
C(O)O(CHR
1′
)
n″
—, —(CHR
1′
)
n″
C(O)(CHR
1′
)
n″
—, C
3
-C
8
cycloalkyl, C
6
-C
14
aryl, cyclic ethers and cyclic diethers containing 4 to 8 carbon atoms, wherein n′ independently represents an integer from 0 to 10, n″ represents an integer from 1 to 10, and R
1′
and R
2′
independently represent hydrogen, linear and branched C
1
-C
10
alkyl and halogen, preferably chlorine and fluorine. Divalent radical —A— represents the group —(CHR
1′
)
n″
OC(O)— only when the sulfonamide group is —NR′SO
2
R″.
The divalent cycloalkyl radicals include substituted and unsubstituted C
3
to C
8
cycloalkyl moieties represented by the formula:
wherein “a” is an integer from 2 to 7 and R
q
when present represents linear and branched C
1
-C
10
alkyl groups, linear and branched C
1
-C
10
haloalkyl, and halogen, preferably chlorine and fluorine. As used here and throughout the specification the term haloalkyl means that at least one hydrogen atom on the alkyl radical is replaced by a halogen. The degree of halogenation can range from at least one hydrogen atom being replaced by a halogen atom (e.g., a monofluoromethyl group) to full halogenation (perhalogenation) wherein all hydrogen atoms on the alkyl group have been replaced by a halogen atom (e.g., trifluoromethyl (perfluoromethyl)). Preferred divalent cycloalkylene radicals include cyclopentylene and cyclohexylene moieties represen

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