Photosensitive resin composition, photosensitive dry film, and pattern forming process

Patent metadata

Field	Value
Publication number	US-11187982-B2
Application number	US-201916597128-A
Country	US
Kind code	B2
Filing date	Oct 9, 2019
Priority date	Oct 15, 2018
Publication date	Nov 30, 2021
Grant date	Nov 30, 2021

Abstract

A photosensitive resin composition comprising (A) a silicone resin containing an epoxy and/or phenolic hydroxyl group, (B) a photoacid generator, and (C) a cure promoter selected from diazabicycloundecene, diazabicyclononene, an organic salt of diazabicycloundecene derivative, and an organic salt of diazabicyclononene derivative is shelf stable. A photosensitive resin coating obtained therefrom may be processed to form a fine size pattern. The resin coating has improved film properties including chemical resistance, adhesion to substrates, mechanical properties, electric insulation, and copper migration resistance, and is thus fully reliable as an insulating protective film.

First claim

The invention claimed is:

1. A photosensitive resin composition comprising (A) a silicone resin containing an epoxy and/or phenolic hydroxyl group, (B) a photoacid generator, and (C) at least one cure promoter selected from diazabicycloundecene, diazabicyclononene, an organic salt having a diazabicycloundecene derivative as a cation species, and an organic salt having a diazabicyclononene derivative as a cation species.

2. The photosensitive resin composition of claim 1 wherein the silicone resin (A) comprises recurring units having the formulae (a1) to (a4) and (b1) to (b4):

wherein R 1 to R 4 are each independently a C 1 -C 8 monovalent hydrocarbon group, m is an integer of 1 to 600, a 1 to a 4 and b 1 to b 4 are numbers in the range: 0≤a 1 <1, 0≤a 2 <1, 0≤a 3 <1, 0≤a 4 <1, 0≤b 1 <1, 0≤b 2 <1, 0≤b 3 <1, 0≤b 4 <1, 0<a 1 +a 2 +a 3 <1, 0<b 1 +b 2 +b 3 <1, and a 1 +a 2 +a 3 +a 4 +b 1 +b 2 +b 3 +b 4 =1,
X 1 is a divalent group having the formula (X1):

wherein Y 1 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl, R 11 and R 12 are each independently hydrogen or methyl, R 13 and R 14 are each independently C 1 -C 4 alkyl or C 1 -C 4 alkoxy, p 1 and p 2 are each independently an integer of 0 to 7, q 1 and q 2 are each independently an integer of 0 to 2,
X 2 is a divalent group having the formula (X2):

wherein Y 2 is a single bond, methylene, propane-2,2-diyl, 1,1,1,3,3,3-hexafluoropropane-2,2-diyl or fluorene-9,9-diyl, R 21 and R 22 are each independently hydrogen or methyl, R 23 and R 24 are each independently C 1 -C 4 alkyl or C 1 -C 4 alkoxy, r 1 and r 2 are each independently an integer of 0 to 7, s 1 and s 2 are each independently an integer of 0 to 2,
X 3 is a divalent group having the formula (X3):

wherein R 31 and R 32 are each independently hydrogen or methyl, t 1 and t 2 are each independently an integer of 0 to 7,
X 4 is a divalent group having the formula (X4):

wherein R 41 and R 42 are each independently hydrogen or methyl, R 43 and R 44 are each independently a C 1 -C 8 monovalent hydrocarbon group, u 1 and u 2 are each independently an integer of 0 to 7, v is an integer of 0 to 600.

3. The photosensitive resin composition of claim 1 , further comprising (D) a crosslinker.

4. The photosensitive resin composition of claim 3 wherein the crosslinker is selected from the group consisting of melamine, guanamine, glycoluril and urea compounds having on the average at least two methylol and/or alkoxymethyl groups in the molecule, amino condensates modified with formaldehyde or formaldehyde-alcohol, phenol compounds having on the average at least two methylol or alkoxymethyl groups in the molecule, and epoxy compounds having on the average at least two epoxy groups in the molecule.

5. The photosensitive resin composition of claim 1 , further comprising (E) a solvent.

6. A photosensitive resin coating comprising the photosensitive resin composition of claim 1 .

7. A photosensitive dry film comprising a support and the photosensitive resin coating of claim 6 thereon.

8. A pattern forming process comprising the steps of:
(i) coating the photosensitive resin composition of claim 1 onto a substrate to form a photosensitive resin coating thereon,
(ii) exposing the photosensitive resin coating to radiation to define exposed and unexposed regions, and
(iii) developing the exposed resin coating in a developer to dissolve away the unexposed region of the resin coating and to form a pattern of the resin coating.

9. A pattern forming process comprising the steps of:
(i′) using the photosensitive dry film of claim 7 to form the photosensitive resin coating on a substrate,
(ii) exposing the photosensitive resin coating to radiation to define exposed and unexposed regions, and
(iii) developing the exposed resin coating in a developer to dissolve away the unexposed region of the resin coating and to form a pattern of the resin coating.

10. The pattern forming process of claim 8 , further comprising (iv) post-curing the patterned resin coating resulting from development step (iii) at a temperature of 100 to 250° C.

11. A protective film comprising the photosensitive resin composition of claim 1 , wherein the protective film is on an electrical or electronic part.

12. A layer for bonding two substrates comprising the photosensitive resin composition of claim 1 .

Assignees

• Shinetsu Chemical Co

Inventors

• Maruyama Hitoshi

Classifications

• G03F7/004 Primary

  Photosensitive materials (G03F7/12, G03F7/14 take precedence) · CPC title

• G03F7/30

  Imagewise removal using liquid means · CPC title

• C08G77/16

  to hydroxy groups · CPC title

• G03F7/0752 Primary

  in non photosensitive layers or as additives, e.g. for dry lithography · CPC title

• G03F7/38

  Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)} · CPC title