Derivatized polyhydroxystyrenes (DPHS) with a novolak type structure and blocked DPHS (BDPHS) and processes for preparing the same

Abstract

A process for preparing a blocked derivatized poly(4-hydroxystryrene)-DPHS having a novolak type structure which comprises the steps of (i) supplying a solution of methanol containing 4-hydroxyphenylmethylcarbinol, (ii) subjecting said solution to an acid catalyzed displacement reaction for a sufficient period of time and under suitable conditions of temperature and pressure to convert substantially all of said carbinol to 4-hydroxyphenylmethylcarbinol methyl ether in solution, (iii) polymerizing said ether containing solution in the presence of a suitable acid catalyst for a sufficient period of time and under suitable conditions of temperature and pressure to form a novolak type polymer; and (iv) reacting said polymer with a vinyl ether, a dialkyl dicarbonate, or a mixture of vinyl ether and a dialkyl dicarbonate to form the blocked DPHS. New compositions of matter which comprise the blocked derivatized poly(4-hydroxystyrene) prepared in the above manner and which have application in the electronic chemicals market such as in a photoresist composition and MEMS, and in other areas such as in varnishes, printing inks, epoxy resins, copying paper, tackifiers for rubber, crude oil separators, toner resins for photocopying, antireflective coatings, and the like.

1 . A composition of matter having the following structure: 
     
       
         
         
             
             
         
       
     
     wherein n is from about 1 to about 10. 
   
   
       2 . A composition of matter having the following structure: 
     
       
         
         
             
             
         
       
     
     wherein n is from about 1 to about 10. 
   
   
       3 . A photoresist composition containing the composition of matter as set forth in  claim 1 . 
   
   
       4 . A photoresist composition containing the composition of matter as set forth in  claim 2 . 
   
   
       5 . A process for preparing blocked derivatized polyhydroxystyrene (DPHS) having a novolak type structure which comprises the steps of (a) supplying a solution of methanol containing 4-hydroxyphenylmethylcarbinol, (b) contacting said solution with an acid ion exchange resin for a sufficient period of time and under suitable conditions of temperature and pressure to convert substantially all of said carbinol to 4-hydroxyphenylmethylcarbinol methyl ether in solution, (c) polymerizing said ether containing solution in the presence of a suitable acid catalyst for a sufficient period of time and under suitable conditions of temperature and pressure to form a novolak type polymer, and (d) reacting said polymer with a vinyl ether, a dialkyl dicarbonate, or a mixture of a vinyl ether and dialkyl dicarbonate to form said blocked DPHS. 
   
   
       6 . The process as set forth in  claim 5  wherein said acid catalyst is a Lewis acid. 
   
   
       7 . The process as set forth in  claim 5  wherein the temperature in steps (b) and (c) is from about 0° C. to about 100° C. and the pressure is from about 0 psig to about 10 psig. 
   
   
       8 . The process as set forth in  claim 5  wherein the acid catalyst is a mineral acid. 
   
   
       9 . The process as set forth in  claim 8  wherein the acid catalyst is sulfuric acid. 
   
   
       10 . The process as set forth in  claim 5  wherein the acid catalyst is selected from the group consisting of H 2 SO 4 , HCL AlCl 3 , H 3 PO 4 , oxalic acid, SnCl 2 , BF 3 , BBr 3 , BCl 3 , para-toluene sulfonic acid, methane sulfonic acid, trifluoroacetic acid, trichloroacetic acid and mixtures thereof. 
   
   
       11 . The process as set forth in  claim 5  wherein the polymer formed in step d has the structure set forth in  claim 1 . 
   
   
       12 . The process as set forth in  claim 5  wherein the polymer formed in step d has the structure set forth in  claim 2 . 
   
   
       13 . The process as set forth in  claim 5  wherein the polymer formed in step c is a derivatized poly(4-hydroxystyrene) characterized by having from about 6% to about 40% linearity, a polydispersity of less than about 2.0, and a molecular weight of less than about 10,000. 
   
   
       14 . A primary photoresist composition for patterning electronic circuitry based on the composition of matter formed in  claim 5 . 
   
   
       15 . A curing agent for an epoxy resin based on the composition of matter formed in  claim 5 . 
   
   
       16 . A varnish incorporating the composition of matter formed in  claim 5 . 
   
   
       17 . A printing ink incorporating the composition of matter formed in  claim 5 . 
   
   
       18 . A tackifier for rubber incorporating the composition of matter formed in  claim 5 . 
   
   
       19 . A crude oil separator incorporating the composition of matter formed in  claim 5 . 
   
   
       20 . A solder mask or photoimageable coverlay for rigid or flexible printed circuit boards incorporating the composition of matter formed in  claim 5 . 
   
   
       21 . An epoxy material which has been further derivatized by reaction with the hydroxy groups in the composition of matter formed in  claim 5 . 
   
   
       22 . A epoxy or blocked isocyanate containing paint formulation which also has incorporated therein the composition of matter formed in  claim 5 . 
   
   
       23 . A highly viscous polymer having incorporated therein the composition of matter formed in  claim 5  and which acts as a viscosity modifier therefor. 
   
   
       24 . A polymeric material having incorporated therein the composition of matter formed in  claim 5  and which acts as an antioxidant therefor. 
   
   
       25 . The composition of matter as formed in  claim 1  wherein the mole % blocked is from about 10% to about 90% when either the said ether or dicarbonate is used and when both are used, the range is from about 20% to about 70% for each compound. 
   
   
       26 . A micro electromechanical system having incorporated therein the composition of matter as formed in  claim 5 . 
   
   
       27 . A toner resin for use in photocopying containing the composition of matter as formed in  claim 5 . 
   
   
       28 . A toner resin for use in photocopying containing the composition of matter as formed in  claim 5 . 
   
   
       29 . An antireflective coating containing the composition of matter as formed in  claim 5 . 
   
   
       30 . An antireflective coating containing the composition of matter as formed in  claim 5 .