Epoxy-containing, isocyanurate-modified silicone resin, photosensitive resin composition, photosensitive dry film, laminate, and pattern forming process

Patent metadata

Field	Value
Publication number	US-11294282-B2
Application number	US-201816114474-A
Country	US
Kind code	B2
Filing date	Aug 28, 2018
Priority date	Aug 31, 2017
Publication date	Apr 5, 2022
Grant date	Apr 5, 2022

Abstract

A photosensitive resin composition comprising an isocyanurate-modified silicone resin containing an epoxy group in the molecule is easy to form a resin coating which has high transparency, light resistance and heat resistance, is amenable to micro-processing, and is useful in applications for protecting and encapsulating optical devices. The coating can be processed in thick film form to define a pattern having a fine size and perpendicularity, and becomes a cured coating which has improved adhesion to substrates, electronic parts, semiconductor devices, and supports for circuit boards, mechanical properties, electric insulation, and crack resistance, and is reliable as an insulating protective film.

First claim

The invention claimed is:

1. An epoxy-containing, isocyanurate-modified silicone resin comprising recurring units having the formulae (1) to (6):

wherein R 1 to R 7 are each independently hydrogen or a monovalent organic group, at least one of R 5 to R 7 being an epoxy-containing organic group,
a1, a2, b1, b2, c1 and c2 are numbers in the range: 0≤a1<1, 0≤a2<1, 0≤b1<1, 0≤b2<1, 0≤c1<1, 0.2≤c2<1, 0<a2+b2<1, 0<a2+b2+c2≤1, and a1+a2+b1+b2+c1+c2=1, d is an integer of 0 to 300, e and f are integers in the range: 0≤e≤300, 0≤f≤300, and 0≤e+f≤300,
X 1 is a divalent group having the formula (7):

wherein R 8 is each independently hydrogen or methyl, j and k are each independently an integer of 0 to 7, p is an integer of 0 to 300,
X 2 is a divalent group having the formula (8):

wherein R 9 is each independently hydrogen or methyl, R 10 is a C 1 -C 8 alkyl, allyl, glycidyl or C 6 -C 10 aryl group, q and r are each independently an integer of 0 to 7.

2. The epoxy-containing, isocyanurate-modified silicone resin of claim 1 wherein R 1 to R 7 are each independently hydrogen, a C 1 -C 8 monovalent hydrocarbon group, or an epoxy-containing organic group having the formula (9) or (10), at least one of R 5 to R 7 being an epoxy-containing organic group having the formula (9) or (10),

wherein R 11 and R 13 are each independently hydrogen or methyl, R 12 and R 14 are each independently a single bond or C 1 -C 8 alkylene group in which any methylene moiety may be substituted by an ether bond, sulfide bond or phenylene moiety.

3. A photosensitive resin composition comprising (A) the epoxy-containing, isocyanurate-modified silicone resin of claim 1 and (B) a photoacid generator which is decomposed to generate an acid upon light exposure.

4. The photosensitive resin composition of claim 3 , further comprising (C) a crosslinker containing an epoxy-containing compound.

5. The photosensitive resin composition of claim 4 wherein the epoxy-containing compound is a compound having on the average at least two epoxy groups in the molecule.

6. The photosensitive resin composition of claim 3 , further comprising (D) a solvent.

7. The photosensitive resin composition of claim 3 , further comprising (E) an antioxidant.

8. The photosensitive resin composition of claim 3 , further comprising (F) a quencher.

9. A photosensitive resin coating formed of the photosensitive resin composition of claim 3 .

10. A pattern forming process comprising the steps of:
(i) coating the photosensitive resin composition of claim 3 onto a substrate to form a photosensitive resin coating thereon,
(ii) exposing the photosensitive resin coating to radiation through a photomask, and
(iii) developing the exposed resin coating in a developer.

11. The pattern forming process of claim 10 , further comprising the step of baking the resin coating after exposure and before development.

12. The pattern forming process of claim 10 , further comprising the step of post-curing the resin coating at a temperature of 120 to 300° C. after development.

13. The pattern forming process of claim 10 wherein the substrate has grooves and/or holes having an opening width of 10 to 100 μm and a depth of 10 to 120 μm.

14. A method for producing an opto-semiconductor device, comprising the pattern forming process of claim 10 , the opto-semiconductor device having a pattern of the photosensitive resin coating.

15. A method for producing an optical device, comprising the pattern forming process of claim 10 , the optical device having a pattern of the photosensitive resin coating.

16. A photosensitive resin coating comprising (A) the epoxy-containing, isocyanurate-modified silicone resin of claim 1 and (B) a photoacid generator which is decomposed to generate an acid upon light exposure.

17. A photosensitive dry film comprising a support film and the photosensitive resin coating of claim 16 thereon.

18. A pattern forming process comprising the steps of:
(i′) attaching the photosensitive dry film of claim 17 at its photosensitive resin coating to a substrate to dispose the photosensitive resin coating thereon,
(ii) exposing the photosensitive resin coating to radiation through a photomask, and
(iii) developing the exposed resin coating in a developer.

19. A laminate comprising a substrate having grooves and/or holes having an opening width of 10 to 100 μm and a depth of 10 to 120 μm and the photosensitive resin coating of claim 16 thereon.

20. The epoxy-containing, isocyanurate-modified silicone resin of claim 1 wherein a1, a2, b1, b2, c1 and c2 are numbers in the range: 0≤a1≤0.6, 0≤a2≤0.8, 0≤b1≤0.6, 0≤b2≤0.8, 0≤c1≤0.6, 0.2≤c2≤0.8, 0.2≤a2+b2≤0.8, 0.4≤a2+b2+c2≤1, and a1+a2+b1+b2+c1+c2=1.

21. The epoxy-containing, isocyanurate-modified silicone resin of claim 1 wherein a1, a2, b1, b2, c1 and c2 are numbers in the range: 0≤a1<1, 0≤a2<1, 0≤b1<1, 0≤b2<1, 0≤c1<1, 0.2≤c2<1, 0<a2+b2<1, 0<a2+b2+c2<1, and a1+a2+b1+b2+c1+c2=1.

22. The epoxy-containing, isocyanurate-modified silicone resin of claim 1 wherein 0<c1<1.

Assignees

• Shinetsu Chemical Co

Inventors

• Hayashi Kumiko
• Maruyama Hitoshi
• Kondo Kazunori
• Kato Hideto

Classifications

• H10P14/68

  Organic materials, e.g. photoresists · CPC title

• H10P95/00

  Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass · CPC title

• G03F7/004

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

• C08J5/18

  Manufacture of films or sheets · CPC title

• G03F7/038

  Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021) · CPC title