Polysiloxane, method of manufacturing same, silicon-containing alicyclic compound, and radiation-sensitive resin composition

A radiation-sensitive resin composition comprising:

• (a) a resin which comprises a polysiloxane insoluble or scarcely soluble in alkali and having the following structural unit (I) and/or the following structural unit (II), and the following structural unit (III),
• 101
• wherein A1 and A2 individually represent a monovalent organic group having an acid-dissociable group which dissociates by an action of an acid, R1 represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20carbon atoms, a halogen atom, or a primary, secondary, or tertiary amino group, and R2 represents a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, or a primary, secondary, or tertiary amino group;
• the polysiloxane having a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) in the range of 500-1,000,000 and becoming soluble in alkali when an acid-dissociable group dissociates, and
• (b) a photoacid generator.

A silicon-containing alicyclic compound represented by the following formula (2-A) or (2-B),

• 102
• wherein R individually represents a hydrogen atom or a methyl group;
• R1 individually represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, or a primary, secondary, or tertiary amino group;
• R3 individually represents a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, or the group of the following formula (i),
• 103
• wherein X individually represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, or a linear, branched, or cyclic alkoxyl group having 1-20 carbon atoms, and a indicates an integer of 1-10, or, when m is 0 or 1, two R3 may form a ring together with two oxygen atoms and the silicon atom;
• Y individually represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, a primary, secondary, or tertiary amino group, or a group ═OR3 (wherein R3is the same as defined above);
• m is an integer of 0-3;
• p is an integer of 3-10, and n is an integer of 0-3;
• the silicon atom binding with the 2 or 3 position of the uppermost bicyclo[2.2.1]heptane ring.

A silicon-containing alicyclic compound represented by the following formula (4-A) or formula (4-B),

• 105
• wherein R individually represents a hydrogen atom or a methyl group;
• R1 individually represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20carbon atoms, a halogen atom, or a primary, secondary, or tertiary amino group;
• R3 individually represents a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, or the group of the following formula (i),
• 106
• wherein X individually represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, or a linear, branched, or cyclic alkoxyl group having 1-20 carbon atoms, and a indicates an integer of 1-10, or, when m is 0 or 1, two R3 may form a ring together with two oxygen atoms and the silicon atom;
• Y individually represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, a primary, secondary, or tertiary amino group, or a group ═OR3 (wherein R3 is the same as defined above);
• m is an integer of 0-3;
• p is an integer of 3-10;
• Rf represents a hydrogen atom, methyl group, or trifluoromethyl group;
• Z represents a hydrogen atom or a monovalent organic group dissociating hydrogen atoms with the action of an acid;
• and n is an integer of 0-3;
• the silicon atom binding with the 2 or 3 position of the uppermost bicyclo[2.2.1]heptane ring.

A polysiloxane comprising the following structural unit (I-2) and/or structural unit (II-2),

• 107
• wherein R individually represents a hydrogen atom or a methyl group;
• R1 represents a hydrogen atom, a monovalent hydrocarbon group having 1-20 carbon atoms, a monovalent halogenated hydrocarbon group having 1-20 carbon atoms, a halogen atom, or a primary, secondary, or tertiary amino group, and Rf represents a hydrogen atom, methyl group, or trifluoromethyl group;
• Z represents a hydrogen atom or a monovalent organic group dissociating hydrogen atoms with an action of an acid;
• and n is an integer of 0-3;
• the silicon atom binding with the 2 or 3 position of the uppermost bicyclo[2.2.1]heptane ring;
• The polysiloxane having a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography (GPC) in the range of 500-1,000,000.