Silicone structure-bearing polymer, resin composition, and photo-curable dry film

Patent metadata

Field	Value
Publication number	US-9366961-B2
Application number	US-201514747573-A
Country	US
Kind code	B2
Filing date	Jun 23, 2015
Priority date	Jan 27, 2012
Publication date	Jun 14, 2016
Grant date	Jun 14, 2016

Abstract

A silicone structure-bearing polymer having a crosslinking group within the molecule, containing an isocyanurate structure bonded within the molecule, and having a Mw of 3,000-500,000 is provided. The polymer overcomes the stripping problem that a coating is stripped from metal wirings of Cu or Al, electrodes, and SiN substrates.

First claim

The invention claimed is:

1. A resin composition comprising
(A) a silicone structure-bearing polymer having a crosslinking group or a reaction site susceptible to crosslinking reaction within the molecule, containing an isocyanurate structure bonded within the molecule or to a terminal group, and having a weight average molecular weight of 3,000 to 500,000,
(B) at least one crosslinker 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 a polyhydric phenol compound having a hydroxyl group substituted by a glycidoxy group,
(C) a photoacid generator which is decomposed to generate an acid upon exposure to radiation of wavelength 190 to 500 nm, and
(D) a solvent
wherein the silicone structure-bearing polymer comprises recurring units having the general formula (1):

 wherein R 1 to R 4 are each independently a monovalent C 1 -C 8 hydrocarbon group, m is an integer of 1 to 100, a, b, c and d are each independently 0 or a positive number, e and f each are a positive number, with the proviso that a, b, c and d are not equal to 0 at the same time and a+b+c+d+e+f=1,
X is a divalent organic group having the general formula (2):

 wherein Z is a divalent organic group selected from the group consisting of

 n is 0 or 1, R 5 and R 6 are each independently a C 1 -C 4 alkyl or alkoxy group, k is 0, 1 and 2,
Y is a divalent organic group having the general formula (3):

 wherein V is a divalent organic group selected from the group consisting of

 p is 0 or 1, R 7 and R 8 are each independently a C 1 -C 4 alkyl or alkoxy group, h is 0, 1 or 2, and
W is a divalent organic group having the general formula (4-1) and/or a monovalent organic group having the general formula (4-2):

 wherein T 1 and T 2 are each independently a monovalent group selected from the group consisting of

 R 9 is a C 1 -C 4 alkyl or alkoxy group, and R 10 is hydrogen, a C 1 -C 4 alkyl or alkoxy group, or —(CH 1 ) s OH wherein s is an integer of 0 to 3.

2. A chemically amplified negative resist composition comprising the resin composition of claim 1 .

3. A photo-curable dry film comprising a photo-curable resin layer having a thickness of 10 to 100 μm sandwiched between a support film and a protective film,
the photo-curable resin layer being formed of a photo curable resin composition which is the resin composition of claim 1 .

4. A pattern forming process comprising the steps of:
(1) coating the chemically amplified negative resist composition of claim 2 onto a substrate, and prebaking to form a resist film,
(2) exposing the resist film to high-energy radiation of wavelength 190 to 500 nm or electron beam through a photomask,
(3) baking and developing in a developer to pattern the resist film.

5. The process of claim 4 , further comprising (4) post curing the patterned resist film resulting from development step (3) at a temperature of 100 to 250° C.

6. A laminate comprising
a substrate provided with grooves and/or holes having an opening width of 10 to 100 μm and a depth of 10 to 120 and
a layer lying on the substrate, the layer being a cured layer of the photo-curable resin composition extracted from the photo-curable dry film of claim 3 .

7. A method of preparing a photo-curable dry film, comprising the steps of:
(i) coating the resin composition of claim 1 onto a support film,
(ii) drying the resin composition to form a photo curable resin layer on the support film, and
(iii) applying a protective film onto the photo curable resin layer.

8. A pattern forming process comprising the steps of:
(i) stripping the protective film from the photo curable dry film of claim 3 and placing the bare photo curable resin layer in close contact with a substrate,
(ii) exposing the photo-curable resin layer to radiation of wavelength 190 to 500 nm through a photomask and through the support film or with the support film stripped off,
(iii) post-exposure bake, and
(iv) developing in a developer to pattern the layer.

9. The process of claim 8 , further comprising (v) post curing the patterned layer resulting from development step (iv) at a temperature of 100 to 250° C.

10. The process of claim 8 wherein the substrate is provided with grooves and/or holes having an opening width of 10 to 100 pm and a depth of 10 to 120 μm.

11. An electric/electronic part protective film comprising the cured film obtained by the process of claim 9 .

12. The resin composition of claim 1 , wherein T 1 or T 2 in formulae (4-1) and (4-2) has the following formula

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

Assignees

• Shinetsu Chemical Co

Inventors

• Urano Hiroyuki
• Takemura Katsuya
• Miyazaki Takashi

Classifications

• C08G77/26

  nitrogen-containing groups · CPC title

• C09D183/14

  in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms (C09D183/10 takes precedence) · CPC title

• G03F7/20

  Exposure; Apparatus therefor (photographic printing apparatus for making copies G03B27/00) · CPC title

• C09D183/06

  containing silicon bound to oxygen-containing groups (C09D183/12 takes precedence) · CPC title

• Y10T428/24537

  Parallel ribs and/or grooves · CPC title