Acid functional polymers based on benzocyclobutene

Abstract

The invention is a curable cyclobutarene based polymer comprising acid functional pendant groups. The cured polymer displays excellent qualities of toughness, adhesion, dielectric constant, and low stress. The preferred system is soluble in an aqueous base and can be used to generate patterned films with excellent resolution without the need to handle organic developer solvents.

1. A curable polymer comprising the partially polymerized product of at least one cyclobutarene monomer wherein the product comprises a pendant group comprising a —COOH moiety in amounts defined by equivalent weights in the range of about 200 to about 330 g/mole of —COOH moiety. 
     
     
       2. The polymer of  claim 1  wherein the equivalent weight is in the range of about 220 to about 300 g/mole of acid functionality. 
     
     
       3. The polymer of  claim 1  wherein the equivalent weight is in the range of about 230 to about 270 g/mole of acid functionality. 
     
     
       4. The polymer of  claim 1  wherein the polymerization occurs in a solvent selected from di(propylene glycol) methyl ether acetate isomers; toluene; xylene; mesitylene; alcohols having from 3 to 6 carbon atoms; methylcyclohexanone; N-methylpyrrolidinone; butyrolactone; and dipropylene glycol dimethyl ether isomers. 
     
     
       5. The polymer of  claim 1  having a molecular weight in the range of 1000 to about 50,000 grams/mol. 
     
     
       6. The polymer of  claim 1  having a molecular weight in the range of 1500 to about 25,000 grams/mol. 
     
     
       7. The polymer of  claim 1  having a molecular weight in the range of 2000 to about 15,000 grams/mol. 
     
     
       8. A photoreactive polymeric composition comprising the polymer of  claim 1  and a photoactive composition such that the polymeric composition is rendered either soluble or insoluble upon exposure to activating wavelengths of radiation. 
     
     
       9. The polymeric composition of  claim 8  wherein the photoactive composition comprises a dissolution inhibitor such that the polymeric composition is rendered soluble upon exposure to activating radiation. 
     
     
       10. The composition of  claim 9  wherein the photoactive composition comprises a compound selected from sulfonyl esters of trihydroxybenzophenone and cumyl phenol. 
     
     
       11. The composition of  claim 8  wherein the photoactive composition comprises a photo-initiator that initiates further cure of the polymer upon exposure to activating radiation. 
     
     
       12. The composition of  claim 8  wherein the polymer or oligomer is the partially polymerized product of monomers comprising (a) a cyclobutarene monomer having the formula: 
                 
 
       where
 B 1  is an n-valent organic linking group,  
 Ar 1 is a polyvalent aromatic or heteroaromatic group and the carbon atoms of the cyclobutane ring are bonded to adjacent carbon atoms on the same aromatic ring of Ar 1 ;  
 m is an integer of 1 or more;  
 n is an integer of 1 or more; and  
 R 1  is a monovalent group; and 
 (b) is a cyclobutarene monomer comprising a —COOH moiety.  
 
 
     
     
       13. The polymer of  claim 1 , which is the partially polymerized product of monomers comprising:
 (a) a cyclobutarene monomer having the formula: 
                 
 
  wherein 
 B 1  is an n-valent organic linking group;  
 
 Ar 1  is a polyvalent aromatic or heteroaromatic group and the carbon atoms of the cyclobutane ring are bonded to adjacent carbon atoms on the same aromatic ring of Ar 1 ;  
 m is an integer of 1 or more;  
 n is an integer of 1 or more; and  
 R 1  is a monovalent group; and  
 (b) a cyclobutarene monomer comprising a —COOH moiety.  
 
     
     
       14. The polymer of  claim 13  wherein monomer (a) has the following formula: 
                 
 
       wherein each R 3  is independently an alkyl group of 1-6 carbon atoms, trimethylsilyl, methoxy or chloro; each R 4  is independently a divalent, ethylenically unsaturated organic group; each R 5  is independently hydrogen, an alkyl group of 1 to 6 carbon atoms, cycloalkyl, aralkyl or phenyl; each R 6  is independently hydrogen, an alkyl group of 1 to 6 carbon atoms, chloro or cyano; n is an integer of 1 or more; and each q is an integer of 0 to 3. 
     
     
       15. The polymer of  claim 14  wherein the r 4 is —CH 2 ═CH 2 —, R 5  is methyl, R 6  is hydrogen, n is 1 and q is 0. 
     
     
       16. The polymer of  claim 13  wherein the monomer (b) has the following formula: 
                 
 
       wherein
 B 2  is a monovalent organic group comprising a —COOH moiety;  
 Ar 2  is a polyvalent aromatic or heteroaromatic group and the carbon atoms of the cyclobutane ring are bonded to adjacent carbon atoms on the same aromatic ring of Ar 2 ;  
 p is an integer of 1 or more; and  
 R 2  is a monovalent group.  
 
     
     
       17. The polymer of  claim 13  wherein monomer (b) has the formula: 
                 
 
       wherein
 R′ and R″ are independently selected from hydrogen, alkyl groups of 1 to 6 carbon atoms, aryl groups, or R′ and R″ taken together from a cyclic group of 4 to 8 carbon atoms;  
 Z is a carbon-to-carbon bond or an aryl group; and  
 x is an integer from 0 to 3.  
 
     
     
       18. The polymer of  claim 1 , which is the partially polymerized product of monomers comprising:
 (a) a cyclobutarene monomer having the formula: 
                 
 
  wherein 
 B 1  is an n-valent organic linking group;  
 Ar 1  is a polyvalent aromatic or heteroaromatic group and the carbon atoms of the cyclobutane ring are bonded to adjacent carbon atoms on the same aromatic ring of Ar 1 ;  
 m is an integer of 1 or more;  
 n is an integer of 1 or more; and  
 R 1  is a monovalent group; and  
 
 (b′) is a cyclobutarene monomer having a pendant group, which at least partially converts to a carboxylic acid moiety during the polymerization process or by hydrolysis.  
 
     
     
       19. The polymer of  claim 18  wherein (b′) has the formula 
                 
 
       where R′ and R″ are independently selected from hydrogen, alkyl groups of 1 to 6 carbon atoms, aryl groups, or R′ and R″ taken together from a cyclic group of 4 to 8 carbon atoms. 
     
     
       20. A process for making the polymer of  claim 1  comprising the steps of:
 (1) combining, in a solvent selected from di(propylene glycol) methyl ether acetate isomers; toluene; xylene; mesitylene; alcohols having from 3 to 6 carbon atoms; methylcyclohexanone; N-methylpyrrolidonone; butyrolactone; and dipropylene glycol dimethyl ether isomers, a monomer (a) having the formula 
                 
 
  wherein 
 B 1  is an n-valent organic linking group,  
 Ar 1  is a polyvalent aromatic or heteroaromatic group and the carbon atoms of the cyclobutane ring are bonded to adjacent carbon atoms on the same aromatic ring of Ar 1 ;  
 m is an integer of 1 or more;  
 n is an integer of 1 or more;  
 with a monomer selected from monomer (b), which is a cyclobutarene monomer comprising a carboxylic acid moiety and the monomer (b′), which is a cyclobutarene monomer having a pendant group, which at least partially converts to a carboxylic acid moiety during the polymerizatipn process; and  
 
 (2) heating the combination to react with the monomers.  
 
     
     
       21. A partially polymerized product of monomers comprising
 a cyclobutarene monomer (a) having the formula: 
                 
 
  wherein 
 B 1  is an n-valent organic linking group;  
 Ar 1  is a polyvalent aromatic or heteroaromatic group and the carbon atoms of the cyclobutane ring are bonded to adjacent carbon atoms on the same aromatic ring of Ar 1 ;  
 m is an integer of 1 or more;  
 n is an integer of 1 or more; and  
 R 1  is a monovalent group; and  
 
 (b′) is a cyclobutarene monomer having a pendant group, which at least partially converts to a carboxylic acid during the polymerization process.  
 
     
     
       22. A curable polymer comprising the partially polymerized product of (a) a monomer of the formula: 
                 
 
       wherein
 each R 3  is independently an alkyl group of 1-6 carbon atoms, trimethylsilyl, methoxy or chloro;  
 each R 4  is independently a divalent, ethylenically unsaturated organic each R 5  is independently hydrogen, an alkyl group of 1 to 6 carbon atoms, cycloalkyl, aralkyl or phenyl;  
 each R 6  is independently hydrogen, an alkyl group of 1 to 6 carbon atoms, chloro or cyano;  
 n is an integer of 1 or more; and  
 each q is an integer of 0 to 3; and 
 (b) is a monomer of one of the following formulas: 
                 
 
  wherein 
 R′ and R″ are independently selected from hydrogen, alkyl groups of 1 to 6 carbon atoms, aryl groups, or R′ and R″ taken together from a cyclic group of 4 to 8 carbon atoms;  
 Z is a carbon-to-carbon bond or an aryl group;  
 x is an integer from 0 to 3;  
 y is 0 or 1; and  
 Z 2  is an aryl group.  
 
 
 
     
     
       23. A curable polymer comprising the partially polymerized product of at least one cyclobutarene monomer wherein the product comprises acid functionality in amounts defined by equivalent weights in the range of about  200  to about  434  g/mole of acid functionality.  
     
     
       24. A curable polymer comprising the partially polymerized product of at least one cyclobutarene monomer wherein the product comprises acid functionality in amounts defined by equivalent weights in the range of about  200  to about  564  g/mole of acid functionality.