Positive-type photosensitive resin composition and cured film prepared therefrom

Patent metadata

Field	Value
Publication number	US-11487200-B2
Application number	US-201916402284-A
Country	US
Kind code	B2
Filing date	May 3, 2019
Priority date	May 30, 2018
Publication date	Nov 1, 2022
Grant date	Nov 1, 2022

Abstract

The present invention relates to a positive-type photosensitive resin composition and a cured film prepared therefrom. The positive-type photosensitive resin composition comprises an acrylic copolymer having a dissolution rate to a developer in a specific range and a compound containing a phenolic hydroxyl group, so that it is possible to attain a high contrast and a high sensitivity pattern when a cured film is formed. Further, it is possible to further enhance the adhesiveness of a pattern when a half-tone, as well as a full-tone, is formed.

First claim

The invention claimed is:

1. A positive-type photosensitive resin composition, which comprises:
(A) an acrylic copolymer;
(B) a siloxane copolymer;
(C) a compound containing a phenolic hydroxyl group;
(D) 1,2-quinonediazide compound; and
(E) an epoxy compound,
wherein the epoxy compound (E) is a homo oligomer of an unsaturated monomer including at least one epoxy group.

2. The positive-type photosensitive resin composition of claim 1 ,
wherein the acrylic copolymer (A) has a dissolution rate of 400 to 1,300 Å/sec when it dissolves in an aqueous solution of 2.38% by weight of tetramethylammonium hydroxide at 110° C. for 90 seconds.

3. The positive-type photosensitive resin composition of claim 2 ,
wherein the acrylic copolymer (A) has a weight average molecular weight (Mw) of 500 to 50,000 Da.

4. The positive-type photosensitive resin composition of claim 1 ,
wherein the siloxane copolymer (B) comprises a structural unit derived from a silane compound represented by the following Formula 1:
(R 1 ) n Si(OR 2 ) 4-n   [Formula 1]

in the above Formula 1,
n is an integer of 0 to 3;
R 1 is each independently C 1-12 alkyl, C 2-10 alkenyl, C 6-15 aryl, 3- to 12-membered heteroalkyl, 4- to 10-membered heteroalkenyl, or 6- to 15-membered heteroaryl; and
R 2 is each independently hydrogen, C 1-6 alkyl, C 2-6 acyl, or C 6-15 aryl,
wherein the heteroalkyl, the heteroalkenyl, and the heteroaryl groups each independently have at least one heteroatom selected from the group consisting of O, N, and S.

5. The positive-type photosensitive resin composition of claim 4 ,
wherein the siloxane copolymer (B) comprises a structural unit derived from a silane compound represented by the above Formula 1 where n is 0.

6. The positive-type photosensitive resin composition of claim 1 ,
wherein the acrylic copolymer (A) comprises (a-1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a combination thereof; (a-2) a structural unit derived from an unsaturated compound containing an epoxy group; and (a-3) a structural unit derived from an ethylenically unsaturated compound different from the structural units (a-1) and (a-2).

7. The positive-type photosensitive resin composition of claim 1 ,
which comprises the compound containing a phenolic hydroxyl group (C) in an amount of 1 to 50 parts by weight based on 100 parts by weight of the acrylic copolymer (A) on the basis of the solids content.

8. The positive-type photosensitive resin composition of claim 1 ,
wherein the siloxane copolymer (B) is employed in an amount of 5 to 60% by weight based on the total weight of the acrylic copolymer (A) and the siloxane copolymer (B) on the basis of the solids content.

9. The positive-type photosensitive resin composition of claim 1 ,
which further comprises at least one silane compound represented by the following Formula 1:
(R 1 ) n Si(OR 2 ) 4-n   [Formula 1]

in the above Formula 1,
n is an integer of 0 to 3;
R 1 is each independently C 1-12 alkyl, C 2-10 alkenyl, C 6-15 aryl, 3- to 12-membered heteroalkyl, 4- to 10-membered heteroalkenyl, or 6- to 15-membered heteroaryl; and
R 2 is each independently hydrogen, C 1-6 alkyl, C 2-6 acyl, or C 6-15 aryl,
wherein the heteroalkyl, the heteroalkenyl, and the heteroaryl groups each independently have at least one heteroatom selected from the group consisting of O, N, and S.

10. The positive-type photosensitive resin composition of claim 1 ,
wherein when the photosensitive resin composition is coated onto a glass substrate and cured to form a dried film and the dried film is developed, exposed to light at an exposure rate of 200 mJ/cm 2 based on a wavelength of 365 nm, and heated to prepare a cured film having a thickness of 3 μm, the contrast (γ) value of the cured film according to the following Equation 1 is 4.5 to 6.0:
Contrast(γ)=[Log 10 ( D c /D 0 )] −1   [Equation 1]

D c =Log 10 (the energy when the film thickness is 0 upon development)
D 0 =Log 10 [the intersection of the film retention rate (d′/d 0 ) upon development and the straight-line slope of a contrast graph]
d 0 =(initial) film thickness before development
d′=film thickness upon development.

11. A cured film prepared from the positive-type photosensitive resin composition of claim 1 .

Assignees

• Rohm & Haas Elect Materials Korea Ltd

Inventors

• Lee Jung-Hwa
• Huh Geun
• Jung Ju-Young
• Kim Yeonok

Classifications

• G03F7/023

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

• G03F7/0233

  characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides · CPC title

• G03F7/2002

  with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image · CPC title

• C09J4/06 Primary

  {Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond} in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00 · CPC title

• G03F7/039 Primary

  Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023) · CPC title