Antistatic Treatment Agent, and Antistatic Film, Coated Article and Pattern Forming Method Using the Agents

Abstract

The invention provides an antistatic treatment agent having an ability of preventing resist film thinning phenomenon in a chemically amplified resist, an antistatic film, a coated article and a pattern forming method using such antistatic treatment agent, in particular, the invention provides an antistatic treatment agent comprising an aqueous solvent-soluble electroconductive polymer, a diamine (divalent) or polyamine (polyvalent) aliphatic basic compound and an anionic surfactant, an antistatic film, a coated article and a pattern forming method using such antistatic treatment agent. As the aqueous solvent-soluble electroconductive polymer, a π-conjugated electroconductive polymer having a Brönsted acid group is a sulfonic acid group is preferred and it is preferable that the amount of the diamine (divalent) or polyamine (polyvalent) aliphatic basic compound be from 0.1 to 75 mol % based on the total number of moles of the basic compounds.

1 . An antistatic treatment agent comprising an aqueous solvent-soluble electroconductive polymer having a Brönsted acid group and a diamine or polyamine aliphatic basic compound.  
   
   
       2 . The antistatic treatment agent as claimed in  claim 1 , further comprising a volatile basic compound.  
   
   
       3 . The antistatic treatment agent as claimed in  claim 1 , wherein the molar ratio of diamine or polyamine aliphatic basic compound in the total mole number of the basic compound is within a range of 0.1 to 75 mol. %.  
   
   
       4 . The antistatic treatment agent as claimed in  claim 1 , wherein at least one kind of the diamine or polyamine aliphatic basic compounds has a boiling point of 80° C. or higher.  
   
   
       5 . The antistatic treatment agent as claimed in  claim 1 , wherein the diamine or polyamine aliphatic basic compound consists of one or more kinds selected from a group of a diaminoalkane, a triaminoalkane, a polyaminoalkane and a polyalkylimine.  
   
   
       6 . The antistatic treatment agent as claimed in  claim 5 , wherein the diamine or polyamine aliphatic basic compound consists of one or more kinds selected from a group of ethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminooctane, diaminodecane and polyethyleneimine.  
   
   
       7 . The antistatic treatment agent as claimed in  claim 1 , wherein the aqueous solvent-soluble electroconductive polymer is a π-conjugated electroconductive polymer.  
   
   
       8 . The antistatic treatment agent as claimed in  claim 1 , wherein the Brönsted acid group is a sulfonic acid group.  
   
   
       9 . The antistatic treatment agent as claimed in  claim 1 , wherein the number of moles of the basic group contained in the diamine or polyamine aliphatic basic compound is within a range of 0.05 to 50 mol % based on the number of moles of the Brönsted acid group contained in the aqueous solvent-soluble electroconductive polymer.  
   
   
       10 . The antistatic treatment agent as claimed in  claim 2 , which is an aqueous solution containing 0,1 to 10 mass % of an aqueous solvent-soluble electroconductive polymer, 0.1 to 20 mass % of a di amine or polyamine aliphatic basic compound and 0.1 to 20 mass % of a volatile basic compound, provided that the entire amount of the antistatic treatment agent is 100 mass %.  
   
   
       11 . The antistatic treatment agent as claimed in  claim 1 , further comprising a surfactant.  
   
   
       12 . The antistatic treatment agent as claimed in  claim 11 , wherein the surfactant is an anionic surfactant, an amphoteric surfactant or a mixture thereof.  
   
   
       13 . The antistatic treatment agent as claimed in  claim 11 , wherein the surfactant is an anionic surfactant.  
   
   
       14 . The antistatic treatment agent as claimed in  claim 13 , which is an aqueous solution containing 0.1 to 10 mass % of an aqueous solvent-soluble electroconductive polymer, 0.1 to 20 mass % of a diamine or polyamine aliphatic basic compound, 0.1 to 20 mass % of a volatile basic compound and 0.001 to 1 mass % of an amphoteric surfactant provided that the entire amount of the antistatic treatment agent is 100 mass %.  
   
   
       15 . The antistatic treatment agent as claimed in  claim 1 , wherein the aqueous solvent-soluble electroconductive polymer includes a chemical structure represented by formula (1):  
     
       
         
         
             
             
         
       
     
     in the formula, m and n each independently represents 0 or 1; X represents S, N—R 1  or O; A represents an alkylene group or an alkenylene group (that may have two or more double bonds) having 1 to 4 carbon atoms and having at least a substituent represented by -B-SO 3   − M + , wherein the alkylene and alkenylene group may be substituted with a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear or branched, saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group or a substituted phenyl group; B represents —(CH 2 ) p —(O) q —(CH 2 ) r — in which p, q and r independently represents 0 or an integer of 1 to 3; and M +  represents a hydrogen ion, an alkali metal ion, or a quaternary ammonium ion.  
   
   
       16 . The antistatic treatment agent described in  claim 1 , wherein the aqueous solvent-soluble electroconductive polymer includes a chemical structure represented by formula (2):  
     
       
         
         
             
             
         
       
     
     in the formula, R 2  to R 4  each independently represents a hydrogen atom, a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear or branched, saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or a -B-SO 3   − M +  group; and B and M +  represent the same meanings as described in  claim 15 .  
   
   
       17 . The antistatic treatment agent as claimed in  claim 1 , wherein the aqueous solvent-soluble electroconductive polymer includes a chemical structure represented by formula (3):  
     
       
         
         
             
             
         
       
     
     in the formula, R 5  represents a hydrogen atom, a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear or branched, saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or a -B-SO 3   − M +  group, and B and M +  represent the same meanings as described in  claim 15 .  
   
   
       18 . The antistatic treatment agent described in  claim 1 , wherein the aqueous solvent-soluble electroconductive polymer includes a chemical structure represented by formula (4):  
     
       
         
         
             
             
         
       
     
     in the formula, R 6  to R 8  each independently represents a hydrogen atom, a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a linear or branched, saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a substituted phenyl group or a SO 3   − M +  group; R 9  represents a hydrogen atom or a monovalent group selected from a group of a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a phenyl group and a substituted phenyl group; and B and M +  represent the same meanings as described in  claim 15 .  
   
   
       19 . The antistatic treatment agent as claimed in  claim 15 , wherein the aqueous solvent-soluble electroconductive polymer is a polymer including 5-sulfonisothianaphthene-1,3-diyl as a chemical structure.  
   
   
       20 . An antistatic film obtained by using the antistatic treatment agent as described in  claim 1 .  
   
   
       21 . A coated article coated with the antistatic film as claimed in  claim 20 .  
   
   
       22 . A coated article described in  claim 21 , wherein the antistatic film is formed on a photosensitive composition or a charged particle-sensitive composition coated on a base substrate.  
   
   
       23 . The pattern forming method using the antistatic film as claimed in  claim 20 .  
   
   
       24 . An aqueous solution for antistatic treatment agent comprising a diamine or polyamine aliphatic basic compound and an anionic surfactant.  
   
   
       25 . An aqueous solution for antistatic treatment agent comprising a diamine or polyamine aliphatic basic compound, a volatile basic compound and an anionic surfactant.  
   
   
       26 . The aqueous solution for antistatic treatment agent as claimed in  claim 24 , wherein the mole fraction of the diamine or polyamine aliphatic basic compound is within a range of 0.1 to 75 mol % based on the total number of moles of the basic compounds.  
   
   
       27 . The aqueous solution for antistatic treatment agent as claimed in  claim 24 , comprising at least one kind of the diamine or polyamine aliphatic basic compounds having a boiling point of 80° C. or higher.  
   
   
       28 . The aqueous solution for antistatic treatment agent as claimed in  claim 24 , wherein the diamine or polyamine aliphatic basic compound consists of one or more kinds selected from a group of a diaminoalkane, a triaminoalkane, a polyaminoalkane and a polyalkylimine.  
   
   
       29 . The aqueous solution for antistatic treatment agent as claimed in  claim 24 , wherein the diamine or polyamine aliphatic basic compound consists of one or more kinds selected from a group of ethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminooctane, diaminodecane and polyethyleneimine.