Novolac phenol resin, manufacturing method therefor, photosensitive composition, resist material and coating film

Patent metadata

Field	Value
Publication number	US-10047186-B2
Application number	US-201515529475-A
Country	US
Kind code	B2
Filing date	Oct 8, 2015
Priority date	Nov 25, 2014
Publication date	Aug 14, 2018
Grant date	Aug 14, 2018

Abstract

The present invention provides a photosensitive composition having excellent heat resistance, low absorbance at the exposure light at wavelengths of g-line, h-line, and i-line, and satisfactory sensitivity even when the thickness of a resist film is increased, and also provides a resist material, a coating film thereof, a novolac phenol resin suitable for these applications, and a method for producing the phenol resin. Specifically, there is provided a novolac phenol resin produced by reacting a phenolic trinuclear compound (A) with formaldehyde under an acid catalyst, the phenolic trinuclear compound (A) including a phenolic trinuclear compound (A1) produced by condensation reaction of dialkyl-substituted phenol with a hydroxyl group-containing aromatic aldehyde and a phenol trinuclear compound (A2) produced by condensation reaction of dialkyl-substituted phenol having alkyl groups at the 2- and 3-positions, 2- and 5-position, the 3- and 4-positions, or 3- and 5-positions with an aromatic aldehyde not having a hydroxyl group, wherein the molar ratio of the phenolic trinuclear compound (A1) to the phenolic trinuclear compound (A2) is 20:80 to 90:10.

First claim

The invention claimed is:

1. A novolac phenol resin comprising a product of a reaction under an acid catalyst using, as essential reaction raw materials, a phenolic trinuclear compound (A1), one or more phenolic trinuclear compounds (A2), and an aldehyde (B),
the phenolic trinuclear compound (A1) being represented by general formula (1) below,

in the formula (1), R 1 , R 2 , and R 3 each independently represent an alkyl group having 1 to 8 carbon atoms, which may have a substituent, the plurality of R 1 present may be the same or different, the plurality of R 2 present may be the same or different, when a plurality of R 3 are present, they may be the same or different, r represents an integer of 0 to 4, s represents 1 or 2, and the sum of r and s is 5 or less, and
the phenolic trinuclear compounds (A2) being selected from the group consisting of compounds represented by general formulae (2-1), (2-2), (2-3) and (2-4) below,

in the formulae, R represents an alkyl group having 1 to 8 carbon atoms, which may have a substituent, the plurality of R present may be the same or different, R 3 represents an alkyl group having 1 to 8 carbon atoms, which may have a substituent, when a plurality of R 3 are present, they may be the same or different, and t represents an integer of 0 to 5,
wherein the molar ratio of the phenolic trinuclear compound (A1) to the phenolic trinuclear compound (A2) is 20:80 to 90:10.

2. The novolac phenol resin according to claim 1 , wherein the novolac phenol resin has, as a repeating unit, one or more structural parts selected from the group consisting of a structural part (II-1) represented by general formula (I-1) below,

in the formula (I-1), R 1 and R 2 each independently represent an alkyl group having 1 to 8 carbon atoms, which may have a substituent, the plurality of R 1 present may be the same or different, the plurality of R 2 present may be the same or different, and R 4 represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and
a structural part (I-1) represented by general formula (II-1) below,

in the formula (II-1), R 1 , R 2 , and R 4 represent the same meanings as in the formula (I-1).

3. The novolac phenol resin according to claim 1 , wherein the weight-average molecular weight is 5,000 to 35,000.

4. A photosensitive composition comprising the novolac phenol resin according to claim 1 .

5. A resist material comprising the photosensitive composition according to claim 4 .

6. A novolac phenol resin composition comprising:
a novolac phenol resin (A1) which is a product of a reaction of a phenolic trinuclear compound (A1) with an aldehyde (B), the phenolic trinuclear compound (A1) being the phenolic trinuclear compound (A1) being represented by general formula (1) below,

in the formula (1), R 1 , R 2 , and R 3 each independently represent an alkyl group having 1 to 8 carbon atoms, which may have a substituent, the plurality of R 1 present may be the same or different, the plurality of R 2 present may be the same or different, when a plurality of R 3 are present, they may be the same or different, r represents an integer of 0 to 4, s represents 1 or 2, and the sum of r and s is 5 or less; and
a novolac phenol resin (A2) which is a product of a reaction of one or more phenolic trinuclear compounds (A2) with an aldehyde (B), the phenolic trinuclear compounds (A2) being selected from the group consisting of compounds represented by general formulae (2-1), (2-2), (2-3) and (2-4) below,

in the formulae, R represents an alkyl group having 1 to 8 carbon atoms, which may have a substituent, the plurality of R present may be the same or different, R 3 represents an alkyl group having 1 to 8 carbon atoms, which may have a substituent, when a plurality of R 3 are present, they may be the same or different, and t represents an integer of 0 to 5.

7. The novolac phenol resin composition according to claim 6 , wherein the content ratio of the novolac phenol resin (A1) to the novolac phenol resin (A2) is such that the molar ratio of a structural unit derived from the phenolic trinuclear compound (A1) to a structural unit derived from the phenolic trinuclear compound (A2) is within a range of 20:80 to 90:10.

8. A photosensitive composition comprising the novolac phenol resin composition according to claim 6 and a photosensitizer.

9. A resist material comprising the photosensitive composition according to claim 8 .

Assignees

• Dainippon Ink & Chemicals

Inventors

• Imada Tomoyuki
• Sato Yusuke

Classifications

• C09D161/12

  with polyhydric phenols · CPC title

• C08L61/12

  with polyhydric phenols · CPC title

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title

• C08G8/20 Primary

  with polyhydric phenols · CPC title

• G03F7/0236

  Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins · CPC title