Modified hydroxy naphthalene novolak resin, production method for modified hydroxy naphthalene novolak resin, photosensitive composition, resist material and coating
Provided is a modified hydroxy naphthalene novolak resin which is optimal for a photosensitive composition and a resist material having high optical sensitivity, resolution, and alkali developability, and excellent heat resistance and moisture absorption resistance, and the modified hydroxy naphthalene novolak resin includes a structural moiety (I) represented by Structural Formula as a repeating unit: wherein R 1 is any one of a hydrogen atom, a tertiary alkyl group, an alkoxyalkyl group, an acyl group, an alkoxycarbonyl group, a hetero atom-containing cyclic hydrocarbon group, and a trialkylsilyl group; m is 1 or 2; R 2 's each independently is any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and a halogen atom; and at least one of the R 1 's present in the resin is any one of a tertiary alkyl group, an alkoxyalkyl group, an acyl group, an alkoxycarbonyl group, a hetero atom-containing cyclic hydrocarbon group, and a trialkylsilyl group.
1. A modified hydroxy naphthalene novolak resin comprising a structural moiety (I) represented by Structural Formula (1) as a repeating unit:
wherein R 1 is any one of a hydrogen atom, a tertiary alkyl group, an alkoxyalkyl group, an acyl group, an alkoxycarbonyl group, a hetero atom-containing cyclic hydrocarbon group, and a trialkylsilyl group; m is 1or 2, and when m is 2, the two R 1 's may be the same as or different from each other; and R 2 's each independently is any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and a halogen atom,
wherein at least one of R 1 's present in the resin is any one of a tertiary alkyl group, an alkoxyalkyl group, an acyl group, an alkoxycarbonyl group, a hetero atom-containing cyclic hydrocarbon group, and a trialkylsilyl group, and
wherein the modified hydroxy naphthalene novolak resin further comprises a dimer component represented by any one of Structural Formula (3), and the total content of the dimer component in the resin is 5% by mass or less in terms of an area ratio of GPC measurement:
wherein R 1 is any one of a hydrogen atom, a tertiary alkyl group, an alkoxyalkyl group, an acyl group, an alkoxycarbonyl group, a hetero atom-containing cyclic hydrocarbon group, and a trialkylsilyl group; m is 1or 2; and R 2 's each independently is any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and a halogen atom.
2. The modified hydroxy naphthalene novolak resin according to claim 1 , comprising a structural moiety represented by Structural Formula (1-1) or (1-2) as a repeating unit:
wherein R 1 is any one of a hydrogen atom, a tertiary alkyl group, an alkoxyalkyl group, an acyl group, an alkoxycarbonyl group, a hetero atom-containing cyclic hydrocarbon group, and a trialkylsilyl group, and R 2 's each independently is any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and a halogen atom.
3. The modified hydroxy naphthalene novolak resin according to claim 1 ,
wherein the total content of a monomer component represented by Structural Formula (4) in the resin is 2% by mass or less in terms of an area ratio of GPC measurement:
wherein R 1 is any one of a hydrogen atom, a tertiary alkyl group, an alkoxyalkyl group, an acyl group, an alkoxycarbonyl group, a hetero atom-containing cyclic hydrocarbon group, and a trialkylsilyl group; m is 1 or 2, and when m is 2, the two R 1 's may be the same as or different from each other; and R 2 's each independently is any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and a halogen atom.
4. The modified hydroxy naphthalene novolak resin according to claim 1 ,
wherein, with respect to the structural moiety represented by —O—R 1 in Structural Formula (1) (where R l is any one of a hydrogen atom, a tertiary alkyl group, an alkoxyalkyl group, an acyl group, an alkoxycarbonyl group, a hetero atom-containing cyclic hydrocarbon group, and a trialkylsilyl group), an existence ratio [(OX)/(OH)] of the structural moiety (OX) in which R l is any one of a tertiary alkyl group, an alkoxyalkyl group, an acyl group, an alkoxycarbonyl group, a hetero atom-containing cyclic hydrocarbon group, and a trialkylsilyl group to the structural moiety (OH) in which R 1 is a hydrogen atom, is in a range of 5/95 to 50/50.
5. The modified hydroxy naphthalene novolak resin according to claim 1 , comprising:
a chemical structure in which a part of hydrogen atoms of phenolic hydroxy groups of a hydroxy naphthalene novolak intermediate is substituted with any one of a tertiary alkyl group, an alkoxyalkyl group, an acyl group, an alkoxycarbonyl group, a cyclic ether structural moiety, and a trialkylsilyl group,
wherein the hydroxy naphthalene novolak intermediate is one obtained by reacting a hydroxy naphthalene compound and formaldehyde in a mixed solvent of a hydrophobic organic solvent and water under the condition of an acid catalyst.
6. A photosensitive composition comprising:
the modified hydroxy naphthalene novolak resin according to claims 1 ; and a photoacid generator.
7. A resist material comprising the photosensitive composition according to claim 6 .
8. A coating formed of the photosensitive composition according to claim 6 .