# US 10,503,067 B2 · Photosensitive resin composition, photosensitive dry film, photosensitive resin coating, and pattern forming process

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- Number: US 10,503,067 B2
- Document ID: US10503067B2
- Status: Granted
- Kind: B2
- Application number: 15/883,265
- Filed: 2018-01-30
- Published: 2018-08-09
- Granted: 2019-12-10
- Earliest claimed: 2017-02-03
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Hitoshi Maruyama; Kazunori Kondo; Hideyoshi Yanagisawa
- Web page: https://patentgrep.com/patent/US10503067B2

## CPC

- G03F 7/0388: {with ethylenic or acetylenic bands in the side chains of the photopolymer}
- C08G 73/22: Polybenzoxazoles
- C08L 83/04: Polysiloxanes
- G03F 7/0387: {Polyamides or polyimides}
- G03F 7/039: Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023)
- G03F 7/0757: {Macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence)}
- G03F 7/40: Treatment after imagewise removal, e.g. baking
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

A photosensitive resin composition comprising (A) a silicone-modified polybenzoxazole resin and (B) a photoacid generator which is decomposed to generate an acid upon exposure to radiation of 190-500 nm is coated onto a substrate to form a thick coating, which is exposed to radiation, baked, and developed to form a pattern. The resin coating is capable of forming a fine pattern and has improved crack resistance and other film properties, and reliability.

## Claims

### Claim 1

A photosensitive resin composition comprising (A) a silicone-modified polybenzoxazole resin comprising repeating units having the formula (1a) and repeating units having the formula (1b), and (B) a photoacid generator which is decomposed to generate an acid upon exposure to radiation of wavelength 190 to 500 nm,
wherein R1 to R4 are each independently a C1-C8 monovalent hydrocarbon group which may contain a glycidyl, acryloyl or methacryloyl moiety, m and n are each independently an integer of 0 to 300, R5 is a straight, branched or cyclic C1-C8 alkylene group or phenylene group, a and b are positive numbers in the range: 0<a<1, 0<b<1, and a+b=1, and X1 is a divalent linker having the following formula (2):
wherein X2 is a single bond or divalent organic group, R11 is each independently hydrogen or a C1-C8 monovalent hydrocarbon group in which some hydrogen may be substituted by halogen, R12 is each independently a straight, branched or cyclic C1-C8 alkylene group in which any methylene moiety may be substituted by an ether bond or phenylene moiety, R13 is each independently a hydroxyl or glycidyloxy group, R14 is each independently a C1-C8 monovalent hydrocarbon group in which some hydrogen may be substituted by halogen, p and q are each independently an integer of 0 to 4, and r and s are each independently an integer of 0 to 3.

### Claim 2 (depends on 1)

The photosensitive resin composition of claim 1 wherein X2 is a group selected from the following groups:
wherein R is each independently halogen, or a straight, branched or cyclic C1-C8 alkyl or haloalkyl group, k is an integer of 1 to 6, x is an integer of 0 to 4, and y and z are each independently an integer of 0 to 4.

### Claim 3 (depends on 1)

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

### Claim 4 (depends on 3)

The photosensitive resin composition of claim 3 wherein the crosslinker (C) is at least one compound selected from the group consisting of an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having on the average at least two methylol or alkoxymethylol groups in the molecule, and an epoxy compound having on the average at least two epoxy groups in the molecule.

### Claim 5 (depends on 1)

The photosensitive resin composition of claim 1, further comprising (E) a basic compound.

### Claim 6 (depends on 1)

The photosensitive resin composition of claim 1, which is a substrate bonding material for bonding two substrates.

### Claim 7

A photosensitive resin coating comprising (A) a silicone-modified polybenzoxazole resin comprising repeating units having the formula (1a) and repeating units having the formula (1b), and (B) a photoacid generator which is decomposed to generate an acid upon exposure to radiation of wavelength 190 to 500 nm,
wherein R1 to R4 are each independently a C1-C8 monovalent hydrocarbon group which may contain a glycidyl, acryloyl or methacryloyl moiety, m and n are each independently an integer of 0 to 300, R5 is a straight, branched or cyclic C1-C8 alkylene group or phenylene group, a and b are positive numbers in the range: 0<a<1, 0<b<1, and a+b=1, and X1 is a divalent linker having the following formula (2):
wherein X2 is a single bond or divalent organic group, R11 is each independently hydrogen or a C1-C8 monovalent hydrocarbon group in which some hydrogen may be substituted by halogen, R12 is each independently a straight, branched or cyclic C1-C8 alkylene group in which any methylene moiety may be substituted by an ether bond or phenylene moiety, R13 is each independently a hydroxyl or glycidyloxy group, R14 is each independently a C1-C8 monovalent hydrocarbon group in which some hydrogen may be substituted by halogen, p and q are each independently an integer of 0 to 4, and r and s are each independently an integer of 0 to 3.

### Claim 8 (depends on 7)

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

### Claim 9 (depends on 7)

A laminate comprising a substrate and the photosensitive resin coating of claim 7 thereon.

### Claim 10 (depends on 1)

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,
(ii) exposing a predetermined region of the photosensitive resin coating to radiation through a photomask and post-exposure baking, 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.

### Claim 11 (depends on 8)

A pattern forming process comprising the steps of:
(i) attaching the photosensitive dry film of claim 8 at its photosensitive resin coating to a substrate,
(ii) exposing a predetermined region of the photosensitive resin coating to radiation through a photomask and post-exposure baking, and
(iii) developing the photosensitive resin coating as post-exposure baked in a developer to dissolve away the unexposed region of the resin coating and to form a pattern of the resin coating.

### Claim 12 (depends on 10)

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