Modified novolak phenolic resin, making method, and resist composition

Patent metadata

Field	Value
Publication number	US-9777102-B2
Application number	US-201414560358-A
Country	US
Kind code	B2
Filing date	Dec 4, 2014
Priority date	Oct 25, 2011
Publication date	Oct 3, 2017
Grant date	Oct 3, 2017

Abstract

A modified novolak phenolic resin is obtained by reacting a novolak phenolic resin containing at least 50 wt % of p-cresol with a crosslinker. This method increases the molecular weight of the existing novolak phenolic resin containing at least 50 wt % of p-cresol to such a level that the resulting modified novolak phenolic resin has heat resistance enough for the photoresist application.

First claim

The invention claimed is:

1. A method of preparing a modified novolak phenolic resin having a weight average molecular weight of 2,000 to 30,000, comprising the steps of mixing (A) a novolak phenolic resin obtained from condensation of a phenol containing at least 50% by weight of p-cresol and an aldehyde, or (B) a mixture of (b-1) at least 50% by weight of a p-cresol novolak resin obtained from condensation of p-cresol and an aldehyde and (b-2) the balance of another novolak phenolic resin obtained from condensation of a phenol other than p-cresol and an aldehyde with a crosslinker in an organic solvent, simultaneously or subsequently adding an acidic catalyst selected from the group consisting of benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, p-phenolsulfonic acid, methanesulfonic acid, and ethanesulfonic acid thereto, effecting reaction at a temperature of 10 to 80° C., and deactivating or removing the acidic catalyst to quench the reaction,
wherein the crosslinker is at least one member selected from the group consisting of an amino condensate modified with formalin or formalin-alcohol, a phenol compound having on average at least two methylol or alkoxymethylol groups in a molecule, and an epoxy compound having on average at least two epoxy groups in a molecule, and
wherein the step of deactivating or removing the acidic catalyst is performed by repeating several times the steps of adding deionized water to the reaction solution, stirring, stationary holding for layer separation, and removing the water layer out of the system.

2. The method of claim 1 wherein the phenol from which the novolak phenolic resin (A) is obtained consists of 50 to 80% by weight of p-cresol and the balance of another phenol.

3. The method of claim 1 wherein the mixture (B) consists of 50 to 80% by weight of the p-cresol novolak resin (b-1) and the balance of the other novolak phenolic resin (b-2).

4. The method of claim 1 wherein the novolak phenolic resin (A), the p-cresol novolak resin (b-1), and the other novolak phenolic resin (b-2) each have a weight average molecular weight in the range of 1,500 to 10,000.

5. The method of claim 1 , wherein the crosslinker is a modified melamine condensate or modified urea condensate.

6. The method of claim 1 , wherein the phenol from which the novolak phenolic resin (A) is obtained consists of at least 50% by weight of p-cresol and the balance of another phenol selected from the group consisting of m-cresol, o-cresol, phenol, 2-allylphenol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, and 3,4-xylenol.

7. The method of claim 1 , wherein the reaction is performed at a temperature of 10 to 60° C.

8. The method of claim 1 , wherein the weight average molecular weight is in the range of 3,600 to 10,500.

9. The method of claim 1 , wherein the step of deactivating or removing the acid catalyst is performed by adding a basic substance.

10. The method of claim 9 , wherein the basic substance is pyridine or trimethylamine.

Assignees

• Shinetsu Chemical Co

Inventors

• Hirano Yoshinori
• Yanagisawa Hideyoshi

Classifications

• G03F7/0236

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

• G03F7/023

  Macromolecular quinonediazides; Macromolecular additives, e.g. binders {(G03F7/0226 takes precedence)} · CPC title

• G03F7/0226

  characterised by the non-macromolecular additives · CPC title

• C08G8/28 Primary

  Chemically modified polycondensates · CPC title

• C08G14/10

  Melamines · CPC title